Chlorinated Hydrocarbons 1

Chlorinated Hydrocarbons
Manfred Rossberg, Hoechst Aktiengesellschaft, Frankfurt/Main, Federal Republic of Germany
Wilhelm Lendle, Hoechst Aktiengesellschaft, Frankfurt/Main, Federal Republic of Germany
Gerhard Pfleiderer, Hoechst Aktiengesellschaft, Frankfurt/Main, Federal Republic of Germany
Adolf Tögel, Hoechst Aktiengesellschaft, Frankfurt/Main, Federal Republic of Germany
Eberhard-Ludwig Dreher, Dow Chemical GmbH, Stade, Federal Republic of Germany
Ernst Langer, BASF Aktiengesellschaft, Ludwigshafen, Federal Republic of Germany
Heinz Rassaerts, Chemische Werke Hüls AG, Marl, Federal Republic of Germany
Peter Kleinschmidt, Bayer AG, Dormagen, Federal Republic of Germany
Heinz Strack, formerly Dynamit Nobel AG,
Richard Cook, ICI Chemicals and Polymers, Runcorn, United Kingdom
Uwe Beck, Bayer AG, Leverkusen, Federal Republic of Germany
Karl-August Lipper, Bayer AG, Krefeld, Federal Republic of Germany
Theodore R. Torkelson, Dow Chemical, Midland, Michigan, United States
Eckhard Löser, Bayer AG, Wuppertal, Federal Republic of Germany
Klaus K. Beutel, Dow Chemical Europe, Horgen, Switzerland
Trevor Mann, INEOS Chlor Limited, Runcorn, United Kingdom (Chap. 7)

1. Chloromethanes . . . . . . . . . . . 3 2.1.3. Production . . . . . . . . . . . . . . . . 30

1.1. Physical Properties . . . . . . . . . . 4 2.1.4. Uses and Economic Aspects . . . . . 32
1.2. Chemical Properties . . . . . . . . . 7 2.2. 1,1-Dichloroethane . . . . . . . . . . 32
1.3. Production . . . . . . . . . . . . . . . 9 2.2.1. Physical Properties . . . . . . . . . . 32
1.3.1. Theoretical Bases . . . . . . . . . . . 9 2.2.2. Chemical Properties . . . . . . . . . . 33
1.3.2. Production of Monochloromethane 12 2.2.3. Production . . . . . . . . . . . . . . . . 33
1.3.3. Production of Dichloromethane and 2.2.4. Uses and Economic Aspects . . . . . 34
Trichloromethane . . . . . . . . . . . 13 2.3. 1,2-Dichloroethane . . . . . . . . . . 34
1.3.4. Production of Tetrachloromethane . 18 2.3.1. Physical Properties . . . . . . . . . . 34
1.4. Quality Specifications . . . . . . . . 21 2.3.2. Chemical Properties . . . . . . . . . . 35
1.4.1. Purity of the Commercial Products 2.3.3. Production . . . . . . . . . . . . . . . . 35
and Their Stabilization . . . . . . . . 21 2.3.4. Uses and Economic Aspects . . . . . 42
1.4.2. Analysis . . . . . . . . . . . . . . . . . 22 2.4. 1,1,1-Trichloroethane . . . . . . . . 42
1.5. Storage, Transport, and Handling 22 2.4.1. Physical Properties . . . . . . . . . . 42
1.6. Behavior of Chloromethanes 2.4.2. Chemical Properties . . . . . . . . . . 42
in the Environment . . . . . . . . . 23 2.4.3. Production . . . . . . . . . . . . . . . . 43
1.6.1. Presence in the Atmosphere . . . . . 24 2.4.4. Uses and Economic Aspects . . . . . 46
1.6.2. Presence in Water Sources . . . . . . 24 2.5. 1,1,2-Trichloroethane . . . . . . . . 47
1.7. Applications of the 2.5.1. Physical Properties . . . . . . . . . . 47
Chloromethanes 2.5.2. Chemical Properties . . . . . . . . . . 47
and Economic Data . . . . . . . . . 25 2.5.3. Production . . . . . . . . . . . . . . . . 47
2. Chloroethanes . . . . . . . . . . . . . 26 2.5.4. Uses and Economic Aspects. . . . . 49
2.1. Monochloroethane . . . . . . . . . . 29 2.6. 1,1,1,2-Tetrachloroethane . . . . . 49
2.1.1. Physical Properties . . . . . . . . . . 29 2.6.1. Physical Properties . . . . . . . . . . 49
2.1.2. Chemical Properties . . . . . . . . . . 29 2.6.2. Chemical Properties . . . . . . . . . . 49

c 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a06 233.pub2
2 Chlorinated Hydrocarbons

2.6.3. Production . . . . . . . . . . . . . . . . 49 3.7. Storage and Transportation

2.7. 1,1,2,2-Tetrachloroethane . . . . . 50 of Chloroethanes and
2.7.1. Physical Properties . . . . . . . . . . 50 Chloroethylenes . . . . . . . . . . . . 80
2.7.2. Chemical Properties . . . . . . . . . . 50 3.8. Environmental Aspects in the
2.7.3. Production . . . . . . . . . . . . . . . . 51 Production of Chloroethanes and
2.7.4. Uses and Economic Aspects . . . . . 52 Chloroethylenes . . . . . . . . . . . . 81
2.8. Pentachloroethane . . . . . . . . . . 52 4. Chloropropanes . . . . . . . . . . . . 82
2.8.1. Physical Properties . . . . . . . . . . 52 4.1. 2-Chloropropane . . . . . . . . . . . 82
2.8.2. Chemical Properties . . . . . . . . . . 53 4.2. 1,2-Dichloropropane . . . . . . . . . 83
2.8.3. Production . . . . . . . . . . . . . . . . 53 4.3. 1,2,3-Trichloropropane . . . . . . . 84
2.8.4. Uses and Economic Aspects . . . . . 53 5. Chlorobutanes . . . . . . . . . . . . . 85
2.9. Hexachloroethane . . . . . . . . . . 53 5.1. 1-Chlorobutane . . . . . . . . . . . . 85
2.9.1. Physical Properties . . . . . . . . . . 54 5.2. tert-Butyl Chloride . . . . . . . . . . 86
2.9.2. Chemical Properties . . . . . . . . . . 54 5.3. 1,4-Dichlorobutane . . . . . . . . . . 86
2.9.3. Production . . . . . . . . . . . . . . . . 54 6. Chlorobutenes . . . . . . . . . . . . . 87
2.9.4. Uses and Economic Aspects . . . . . 54 6.1. 1,4-Dichloro-2-butene . . . . . . . . 87
3. Chloroethylenes . . . . . . . . . . . . 54 6.2. 3,4-Dichloro-1-butene . . . . . . . . 87
3.1. Vinyl Chloride (VCM) . . . . . . . 55 6.3. 2,3,4-Trichloro-1-butene . . . . . . 88
6.4. 2-Chloro-1,3-butadiene . . . . . . . 88
3.1.1. Physical Properties . . . . . . . . . . 55
6.4.1. Physical Properties . . . . . . . . . . 88
3.1.2. Chemical Properties . . . . . . . . . . 56
6.4.2. Chemical Properties . . . . . . . . . . 89
3.1.3. Production . . . . . . . . . . . . . . . . 56
6.4.3. Production . . . . . . . . . . . . . . . . 89
3.1.3.1. Vinyl Chloride from Acetylene . . . 57
6.4.3.1. Chloroprene from Butadiene . . . . 89
3.1.3.2. Vinyl Chloride
6.4.3.2. Chloroprene from Acetylene . . . . 90
from 1,2-Dichloroethane . . . . . .. 59
6.4.3.3. Other Processes . . . . . . . . . . . . 91
3.1.3.3. Vinyl Chloride from Ethylene
6.4.4. Economic Importance . . . . . . . . 91
by Direct Routes . . . . . . . . . . . . 63
6.5. Dichlorobutadiene . . . . . . . . . . 91
3.1.3.4. Vinyl Chloride from Ethane . . . . . 64
6.5.1. 2,3-Dichloro-1,3-butadiene . . . . . 91
3.1.3.5. Vinyl Chloride by Other Routes . . 66
6.5.2. Other Dichlorobutadienes . . . . . . 92
3.1.4. Uses and Economic Aspects . . . . . 66
6.6. 3-Chloro-2-methyl-1-propene . . . 92
3.2. 1,1-Dichloroethylene
6.6.1. Physical Properties . . . . . . . . . . 92
(Vinylidene Chloride, VDC) . . . . 67
6.6.2. Chemical Properties . . . . . . . . . . 92
3.2.1. Physical Properties . . . . . . . . . . 67 6.6.3. Production . . . . . . . . . . . . . . . . 93
3.2.2. Chemical Properties . . . . . . . . . . 67 6.6.4. Quality Specifications and Chemical
3.2.3. Production . . . . . . . . . . . . . . . . 67 Analysis . . . . . . . . . . . . . . . . . 94
3.2.4. Uses and Economic Aspects . . . . . 69 6.6.5. Storage and Shipment . . . . . . . . . 95
3.3. 1,2-Dichloroethylene . . . . . . . . . 70 6.6.6. Uses . . . . . . . . . . . . . . . . . . . 95
3.3.1. Physical Properties . . . . . . . . . . 70 6.7. Hexachlorobutadiene . . . . . . . . 95
3.3.2. Chemical Properties . . . . . . . . . . 70 7. Chlorinated Paraffins . . . . . . . . 96
3.3.3. Production . . . . . . . . . . . . . . . . 71 7.1. Physical Properties . . . . . . . . . . 97
3.3.4. Uses and Economic Aspects . . . . . 71 7.2. Chemical Properties
3.4. Trichloroethylene . . . . . . . . . . . 71 and Structure . . . . . . . . . . . . . 97
3.4.1. Physical Properties . . . . . . . . . . 71 7.3. Production . . . . . . . . . . . . . . . 99
3.4.2. Chemical Properties . . . . . . . . . . 72 7.4. Analysis and Quality Control . . . 101
3.4.3. Production . . . . . . . . . . . . . . . . 72 7.5. Storage and Transportation . . . . 101
3.4.4. Uses and Economic Aspects . . . . . 74 7.6. Toxicology, Environmental
3.5. Tetrachloroethylene . . . . . . . . . 75 Impact and Regulation . . . . . . . 102
3.5.1. Physical Properties . . . . . . . . . . 75 7.7. Uses . . . . . . . . . . . . . . . . . . . 103
3.5.2. Chemical Properties . . . . . . . . . . 75 7.8. Summary . . . . . . . . . . . . . . . . 104
3.5.3. Production . . . . . . . . . . . . . . . . 75 8. Nucleus-Chlorinated
3.5.4. Uses and Economic Aspects . . . . . 79 Aromatic Hydrocarbons . . . . . . 104
3.6. Analysis and Quality Control 8.1. Chlorinated Benzenes . . . . . . . . 105
of Chloroethanes 8.1.1. Physical Properties . . . . . . . . . . 105
and Chloroethylenes . . . . . . . .. 80 8.1.2. Chemical Properties . . . . . . . . . . 105
 Chlorinated Hydrocarbons 3

8.1.3. Production . . . . . . . . . . . . . . . . 109 9.1.6. Uses . . . . . . . . . . . . . . . . . . . 137

8.1.3.1. Monochlorobenzene . . . . . . . . . . 112 9.2. Benzal Chloride . . . . . . . . . . . . 137
8.1.3.2. Dichlorobenzenes . . . . . . . . . . . 113 9.2.1. Physical Properties . . . . . . . . . . 137
8.1.3.3. Trichlorobenzenes . . . . . . . . . . . 114 9.2.2. Chemical Properties . . . . . . . . . . 138
8.1.3.4. Tetrachlorobenzenes . . . . . . . . . 114 9.2.3. Production . . . . . . . . . . . . . . . . 138
8.1.3.5. Pentachlorobenzene . . . . . . . . . . 115 9.2.4. Quality Specifications and Analysis 138
8.1.3.6. Hexachlorobenzene . . . . . . . . . . 115 9.2.5. Storage and Transportation . . . . . 138
8.1.4. Quality and Analysis . . . . . . . . . 115 9.2.6. Uses . . . . . . . . . . . . . . . . . . . 139
8.1.5. Storage and Transportation . . . . . 115 9.3. Benzotrichloride . . . . . . . . . . . 139
8.1.6. Uses . . . . . . . . . . . . . . . . . . . 116 9.3.1. Physical Properties . . . . . . . . . . 139
8.2. Chlorinated Toluenes . . . . . . . . 116 9.3.2. Chemical Properties . . . . . . . . . . 139
8.2.1. Physical Properties . . . . . . . . . . 116 9.3.3. Production . . . . . . . . . . . . . . . . 140
8.2.2. Chemical Properties . . . . . . . . . . 117 9.3.4. Quality Specifications and Analysis 140
8.2.3. Production . . . . . . . . . . . . . . . . 117 9.3.5. Storage and Transportation . . . . . 141
8.2.3.1. Monochlorotoluenes . . . . . . . . . 121 9.3.6. Uses . . . . . . . . . . . . . . . . . . . 141
8.2.3.2. Dichlorotoluenes . . . . . . . . . . . . 121 9.4. Side-Chain Chlorinated Xylenes . 141
8.2.3.3. Trichlorotoluenes . . . . . . . . . . . 122 9.4.1. Physical and Chemical Properties . 141
8.2.3.4. Tetrachlorotoluenes . . . . . . . . . . 122 9.4.2. Production . . . . . . . . . . . . . . . . 142
8.2.3.5. Pentachlorotoluene . . . . . . . . . . 123 9.4.3. Storage and Transportation . . . . . 143
8.2.4. Quality and Analysis . . . . . . . . . 123 9.4.4. Uses . . . . . . . . . . . . . . . . . . . 143
8.2.5. Storage and Transportation . . . . . 123
9.5. Ring-Chlorinated Derivatives . . . 143
8.2.6. Uses . . . . . . . . . . . . . . . . . . . 124
9.6. Economic Aspects . . . . . . . . . . 145
8.3. Chlorinated Biphenyls . . . . . . . 124
10. Toxicology and Occupational
8.3.1. Physical and Chemical Properties . 125
Health . . . . . . . . . . . . . . . . . . 145
8.3.2. Disposal . . . . . . . . . . . . . . . . . 125
10.1. Aliphatic Chlorinated
8.3.3. Analysis . . . . . . . . . . . . . . . . . 126
Hydrocarbons . . . . . . . . . . . . . 145
8.3.4. Storage and Transportation . . . . . 126
10.1.1. Chloromethanes . . . . . . . . . . . . 146
8.3.5. Uses . . . . . . . . . . . . . . . . . . . 127
10.1.2. Chlorinated C2 Hydrocarbons . . . 148
8.4. Chlorinated Naphthalenes . . . . . 127
10.1.3. Chloropropanes and
8.4.1. Physical Properties . . . . . . . . . . 127
Chloropropenes . . . . . . . . . . . . 152
8.4.2. Chemical Properties . . . . . . . . . . 128
8.4.3. Production . . . . . . . . . . . . . . . . 129 10.1.4. Chlorobutadienes . . . . . . . . . . . 152
8.4.4. Quality and Analysis . . . . . . . . . 129 10.1.5. Ecotoxicology and Environmental
8.4.5. Storage and Transportation . . . . . 129 Degradation . . . . . . . . . . . . . . . 152
8.4.6. Use . . . . . . . . . . . . . . . . . . . . 130 10.2. Chlorinated Aromatic
8.5. Environmental Protection . . . . . 130 Hydrocarbons . . . . . . . . . . . . . 154
8.6. Economic Facts . . . . . . . . . . . . 131 10.2.1. Chlorinated Benzenes . . . . . . . . . 154
9. Side-Chain Chlorinated Aromatic 10.2.2. Chlorotoluenes . . . . . . . . . . . . . 154
Hydrocarbons . . . . . . . . . . . . . 132 10.2.3. Polychlorinated Biphenyls . . . . . . 155
9.1. Benzyl Chloride . . . . . . . . . . . . 132 10.2.4. Chlorinated Naphthalenes . . . . . . 156
9.1.1. Physical Properties . . . . . . . . . . 132 10.2.5. Benzyl Chloride . . . . . . . . . . . . 156
9.1.2. Chemical Properties . . . . . . . . . . 133 10.2.6. Benzoyl Chloride . . . . . . . . . . . 157
9.1.3. Production . . . . . . . . . . . . . . . . 134 10.2.7. Benzotrichloride . . . . . . . . . . . . 157
9.1.4. Quality Specifications and Analysis 136 10.2.8. Side-Chain Chlorinated Xylenes . . 157
9.1.5. Storage and Transportation . . . . . 137 11. References . . . . . . . . . . . . . . . 157

1. Chloromethanes tetrachloromethane (carbon tetrachloride) [56-

23-5] play an important role from both industrial
Among the halogenated hydrocarbons, the and economic standpoints. These products find
chlorine derivatives of methane monochloro- broad application not only as important chemi-
methane (methyl chloride) [74-87-3], dichloro- cal intermediates, but also as solvents.
methane (methylene chloride) [75-09-2], tri-
chloromethane (chloroform) [67-66-3], and
4 Chlorinated Hydrocarbons

Historical Development. Monochloromethane tained its importance until ca. the 1960s in places
was produced for the first time in 1835 by J. Du- where the preferred starting materials methane
mas and E. Peligot by the reaction of sodium and monochloromethane were in short supply.
chloride with methanol in the presence of sulfu- Today, trichloromethane — along with dichloro-
ric acid. M. Berthelot isolated it in 1858 from methane — is prepared exclusively and on a
the chlorination of marsh gas (methane), as did massive scale by the chlorination of methane
C. Groves in 1874 from the reaction of hydro- and/or monochloromethane. Trichloromethane
gen chloride with methanol in the presence of was introduced into the field of medicine in 1847
zinc chloride. For a time, monochloromethane by J. Y. Simpson, who employed it as an inhaled
was produced commercially from betaine hy- anaesthetic. As a result of its toxicologic proper-
drochloride obtained in the course of beet sugar ties, however, it has since been totally replaced
manufacture. The earliest attempts to produce by other compounds (e.g., Halothane).
methyl chloride by the chlorination of methane Tetrachloromethane was first prepared in
occurred before World War I, with the intent 1839 by V. Regnault by the chlorination of tri-
of hydrolyzing it to methanol. A commercial chloromethane. Shortly thereafter, J. Dumas suc-
methane chlorination facility was first put into ceeded in synthesizing it by the chlorination of
operation by the former Farbwerke Hoechst in marsh gas. H. Kolbe isolated tetrachlorometh-
1923. In the meantime, however, a high-pressure ane in 1843 when he treated carbon disulfide
methanol synthesis based on carbon monoxide with chlorine in the gas phase. The correspond-
and hydrogen had been developed, as a result of ing liquid phase reaction in the presence of a
which the opposite process became practical — catalyst, giving CCl4 and S2 Cl2 , was developed
synthesis of methyl chloride from methanol. a short time later. The key to economical practi-
Dichloromethane was prepared for the first cality of this approach was the discovery in 1893
time in 1840 by V. Regnault, who successfully by Müller and Dubois of the reaction of S2 Cl2
chlorinated methyl chloride. It was for a time with CS2 to give sulfur and tetrachloromethane,
produced by the reduction of trichloromethane thereby avoiding the production of S2 Cl2 .
(chloroform) with zinc and hydrochloric acid in Tetrachloromethane is produced on an indus-
alcohol, but the compound first acquired sig- trial scale by one of two general approaches.
nificance as a solvent after it was successfully The first is the methane chlorination process, us-
prepared commercially by chlorination of meth- ing methane or mono-chloromethane as starting
ane and monochloromethane (Hoechst AG, Dow materials. The other involves either perchlorina-
Chemical Co., and Stauffer Chemical Co.). tion or chlorinolysis. Starting materials in this
Trichloromethane was synthesized indepen- case include C1 to C3 hydrocarbons and their
dently by two groups in 1831: J. von Liebig chlorinated derivatives as well as Cl-containing
successfully carried out the alkaline cleavage residues obtained in other chlorination processes
of chloral, whereas M. E. Soubeirain obtained (vinyl chloride, propylene oxide, etc.).
the compound by the action of chlorine bleach Originally, tetrachloromethane played a role
on both ethanol and acetone. In 1835, J. Dumas only in the dry cleaning industry and as a fire
showed that trichloromethane contained only extinguishing agent. Its production increased
a single hydrogen atom and prepared the sub- dramatically, however, with the introduction of
stance by the alkaline cleavage of trichloroacetic chlorofluoromethane compounds 50 years ago,
acid and other compounds containing a termi- these finding wide application as non-toxic re-
nal CCl3 group, such as β-trichloroacetoacrylic frigerants, as propellants for aerosols, as foam-
acid. In analogy to the synthetic method of M. blowing agents, and as specialty solvents.
E. Soubeirain, the use of hypochlorites was ex-
tended to include other compounds containing
acetyl groups, particularly acetaldehyde. V. Reg- 1.1. Physical Properties
nault prepared trichloromethane by chlorina-
tion of monochloromethane. Already by the The most important physical properties of the
middle of the last century, chloroform was be- four chloro derivatives of methane are presented
ing produced on a commercial basis by using in Table 1; Figure 1 illustrates the vapor pressure
the J. von Liebig procedure, a method which re- curves of the four chlorinated methanes.
 Chlorinated Hydrocarbons 5
Table 1. Physical properties of chloromethanes

Unit Monochlorometh- Dichloromethane Trichloromethane Tetrachloro-

ane methane

Formula CH3 Cl CH2 Cl2 CHCl3 CCl4

Mr 50.49 84.94 119.39 153.84
◦
Melting point C − 97.7 − 96.7 − 63.8 − 22.8
◦
Boiling point at 0.1 MPa C − 23.9 40.2 61.3 76.7
Vapor pressure at 20 ◦ C kPa 489 47.3 21.27 11.94
Density of liquid at 20 ◦ C kg/m3 920 1328.3 1489 1594.7
(0.5 MPa)
Density of vapor at bp kg/m3 2.558 3.406 4.372 5.508
0
Enthalpy of formation ∆H298 kJ/mol − 86.0 − 124.7 − 132.0 − 138.1
Specific heat capacity of liquid at 20 ◦ C kJ kg−1 K−1 1.595 1.156 0.980 0.867
Enthalpy of vaporization at bp kJ/mol 21.65 28.06 29.7 30.0
Critical temperature K 416.3 510.1 535.6 556.4
Critical pressure MPa 6.68 6.17 5.45 4.55
Cubic expansion coeff. of liquid (0 – 40 ◦ C) K−1 0.0022 0.00137 0.001399 0.00116
Thermal conductivity at 20 ◦ C W K−1 m−1 0.1570 0.159 0.1454 0.1070
Surface tension at 20 ◦ C N/m 16.2 × 10−3 28.76 × 10−3 27.14 × 10−3 26.7 ×
10−3
Viscosity of liquid at 20 ◦ C Pa · s 2.7 × 10−4 4.37 × 10−4 5.7 × 10−4 13.5 ×
10−4
(0.5 MPa)
Refractive index n20D 1.4244 1.4467 1.4604
◦
Ignition temperature C 618 605 – –
Limits of ignition in air, lower vol% 8.1 12 – –
Limits of ignition in air, upper vol% 17.2 22 – –
mg/L(air)
Partition coefficient air/water at 20 ◦ C mg/L(water)
0.3 0.12 0.12 0.91

dependence of the solubility at 0.1 MPa (1 bar)

is:
t, ◦ C 15 30 45 60
g of CH3 Cl/kg of H2 O 9.0 6.52 4.36 2.64

Monochloromethane at 20 ◦ C and 0.1 MPa (1

bar) is soluble to the extent of 4.723 cm3 in 100
cm3 of benzene, 3.756 cm3 in 100 cm3 of tetra-
chloromethane, 3.679 cm3 in 100 cm3 of acetic
acid, and 3.740 cm3 in 100 cm3 of ethanol. It
forms azeotropic mixtures with dimethyl ether,
2-methylpropane, and dichlorodifluoromethane
(CFC 12).
Dichloromethane is a colorless, highly
volatile, neutral liquid with a slightly sweet
smell, similar to that of trichloromethane. The
solubility of water in dichloromethane is:
Figure 1. Vapor pressure curves of chloromethanes
t, ◦ C − 30 0 + 25
g of H2 O/kg of 0.16 0.8 1.98
The following sections summarize additional CH2 Cl2
important physical properties of the individual
compounds making up the chloromethane se- The solubility of dichloromethane in water
ries. and in aqueous hydrochloric acid is presented in
Monochloromethane is a colorless, flam- Table 2.
mable gas with a faintly sweet odor. Its solubility Dichloromethane forms azeotropic mixtures
in water follows Henry’s law; the temperature with a number of substances (Table 3).
6 Chlorinated Hydrocarbons
Table 2. Solubility of dichloromethane in water and aqueous hydrochloric acid (in wt %)
Solvent Temperature, ◦ C
15 30 45 60
Water 2.50 1.56 0.88 0.53
10 % HCl 2.94 1.85 1.25 0.60
20 % HCl – 2.45 1.20 0.65

Table 3. Azeotropic mixtures of dichloromethane

iodine and sulfur, and it is completely miscible
wt % Compound Azeotropic boiling with many organic solvents. The solubility of
point, in ◦ C, at trichloromethane in water at 25 ◦ C is 3.81 g/kg
101.3 kPa
30.0 acetone 57.6
of H2 O, whereas 0.8 g of H2 O is soluble in 1 kg
11.5 ethanol 54.6 of CHCl3 .
94.8 1,3-butadiene −5.0
6.0 tert-butanol 57.1
30.0 cyclopentane 38.0
55.0 diethylamine 52.0
30.0 diethyl ether 40.80
8.0 2-propanol 56.6
7.3 methanol 37.8
51.0 pentane 35.5
23.0 propylene oxide 40.6
39.0 carbon disulfide 37.0
1.5 water 38.1

Dichloromethane is virtually nonflammable

in air, as shown in Figure 2, which illustrates
the range of flammable mixtures with oxygen –
nitrogen combinations [1, 2]. Dichloromethane
thereby constitutes the only nonflammable com-
mercial solvent with a low boiling point. The
substance possesses no flash point according to
the definitions established in DIN 51 755 and
ASTM 56–70 as well as DIN 51 758 and ASTM
Figure 2. Range of flammability of mixtures of CH2 Cl2
D 93–73. Thus, it is not subject to the regula- with O2 and N2 [1]
tions governing flammable liquids. As a result
of the existing limits of flammability (CH2 Cl2 Important azeotropic mixtures of chloroform
vapor/air), it is assigned to explosion category G with other compounds are listed in Table 4.
1 (VDE 0165). The addition of small amounts
of dichloromethane to flammable liquids (e.g., Table 4. Azeotropic mixtures of trichloromethane
gasoline, esters, benzene, etc.) raises their flash
points; addition of 10 – 30 % dichloromethane wt % Compound Azeotropic boiling
point, in ◦ C, at
can render such mixtures nonflammable. 101.3 kPa
Trichloromethane is a colorless, highly vol- 15.0 formic acid 59.2
20.5 acetone 64.5
atile, neutral liquid with a characteristic sweet 6.8 ethanol 59.3
odor. Trichloromethane vapors form no explo- 13.0 ethyl formate 62.7
sive mixtures with air [2]. Trichloromethane has 96.0 2-butanone 79.7
excellent solvent properties for many organic 2.8 n-hexane 60.0
4.5 2-propanol 60.8
materials, including alkaloids, fats, oils, resins, 12.5 methanol 53.4
waxes, gums, rubber, paraffins, etc. As a result 23.0 methyl acetate 64.8
of its toxicity, it is increasingly being replaced as 2.8 water 56.1
a solvent by dichloromethane, whose properties
in this general context are otherwise similar. In
addition, trichloromethane is a good solvent for
 Chlorinated Hydrocarbons 7

Ternary azeotropes also exist between tri- into its components at + 7.5 ◦ C and 0.1 MPa
chloromethane and ethanol – water (boiling (1 bar). To the extent that monochloromethane
point 55.5 ◦ C, 4 mol% ethanol + 3.5 mol% still finds application in the refrigeration indus-
H2 O), methanol – acetone, and methanol – hex- try, its water content must be kept below 50 ppm.
ane. This specification is necessary to prevent poten-
Tetrachloromethane is a colorless neutral tial failure of refrigeration equipment pressure
liquid with a high refractive index and a strong, release valves caused by hydrate formation.
bitter odor. It possesses good solubility proper- Monochloromethane is hydrolyzed by wa-
ties for many organic substances, but due to its ter at an elevated temperature. The hydrolysis
high toxicity it is no longer employed (e.g., as a (to methanol and the corresponding chloride)
spot remover or in the dry cleaning of textiles). is greatly accelerated by the presence of alkali.
It should be noted that it does continue to find Mineral acids show no influence on the com-
application as a solvent for chlorine in certain pound’s hydrolytic tendencies.
industrial processes. Monochloromethane is converted in the pres-
Tetrachloromethane is soluble in water at 25 ence of alkali or alkaline-earth metals, as well
◦
C to the extent of 0.8 g of CCl4 /kg of H2 O, the as by zinc and aluminum, into the correspond-
solubility of water in tetrachloromethane being ing organometallic compounds (e.g., CH3 MgCl,
0.13 g of H2 O/kg of CCl4 . Al(CH3 )3 · AlCl3 ). These have come to play a
Tetrachloromethane forms constant-boiling role both in preparative organic chemistry and
azeotropic mixtures with a variety of substances; as catalysts in the production of plastics.
corresponding data are given in Table 5. Reaction of monochloromethane with
a sodium – lead amalgam leads to tetra-
methyllead, an antiknocking additive to gasoline
Table 5. Azeotropic mixtures of tetrachloromethane
intended for use in internal combustion engines.
wt % Compound Azeotropic boiling The use of the compound is declining, however,
point, in ◦ C, at
101.3 kPa
as a result of ecological considerations.
A very significant reaction is that between
88.5 acetone 56.4 monochloromethane and silicon to produce
17.0 acetonitrile 71.0
11.5 allyl alcohol 72.3 the corresponding methylchlorosilanes (the Ro-
81.5 formic acid 66.65 chow synthesis), e.g.:
43.0 ethyl acetate 74.8
15.85 ethanol 61.1 2CH3 Cl+Si→SiCl2 (CH3 )2
71.0 2-butanone 73.8
2.5 butanol 76.6 The latter, through their subsequent conver-
21.0 1,2-dichloroethane 75.6
sion to siloxanes, serve as important starting
12.0 2-propanol 69.0
20.56 methanol 55.7 points for the production of silicones.
11.5 propanol 73.1 Monochloromethane is employed as a com-
4.1 water 66.0 ponent in the Wurtz-Fittig reaction; it is also used
in Friedel-Crafts reactions for the production of
alkylbenzenes.
1.2. Chemical Properties Monochloromethane has acquired particu-
larly great significance as a methylating agent:
Monochloromethane as compared to other
examples include its reaction with hydroxyl
aliphatic chlorine compounds, is thermally quite
groups to give the corresponding ethers (methyl-
stable. Thermal decomposition is observed only
cellulose from cellulose, various methyl ethers
at temperatures in excess of 400 ◦ C, even in
from phenolates), and its use in the preparation
the presence of metals (excluding the alkali and
of methyl-substituted amino compounds (qua-
alkaline-earth metals). The principal products of
ternary methylammonium compounds for ten-
photooxidation of monochloromethane are car-
sides). All of the various methylamines result
bon dioxide and phosgene.
from its reaction with ammonia. Treatment of
Monochloromethane forms with water or wa-
CH3 Cl with sodium hydrogensulfide under pres-
ter vapor a snowlike gas hydrate with the com-
sure and at elevated temperature gives methyl
position CH3 Cl · 6 H2 O, the latter decomposing
mercaptan.
8 Chlorinated Hydrocarbons

Dichloromethane is thermally stable to tem- tion of trichloromethane with phenolates to give

peratures above 140 ◦ C and stable in the pres- salicylaldehydes is well-known as the Reimer-
ence of oxygen to 120 ◦ C. Its photooxidation Thiemann reaction. Treatment with benzene
produces carbon dioxide, hydrogen chloride, under Friedel-Crafts conditions results in tri-
and a small amount of phosgene [3]. Ther- phenylmethane.
mal reaction with nitrogen dioxide gives car- The most important reaction of tri-
bon monoxide, nitrogen monoxide, and hydro- chloromethane is that with hydrogen fluoride
gen chloride [4]. In respect to most industrial in the presence of antimony pentahalides to give
metals (e.g., iron, copper, tin), dichloromethane monochlorodifluoromethane (CFC 22), a pre-
is stable, exceptions being aluminum, magne- cursor in the production of polytetrafluoroeth-
sium, and their alloys; traces of phosgene first ylene (Teflon, Hostaflon, PTFE).
arise above 80 ◦ C. When treated with salicylic anhydride, tri-
Dichloromethane forms a hydrate with water, chloromethane produces a crystalline addition
CH2 Cl2 · 17 H2 O, which decomposes at 1.6 ◦ C compound containing 2 mol of trichlorometh-
and 21.3 kPa (213 mbar). ane. This result finds application in the prepa-
No detectable hydrolysis occurs during the ration of trichloromethane of the highest purity.
evaporation of dichloromethane from extracts or Under certain conditions, explosive and shock-
extraction residues. Only on prolonged action of sensitive products can result from the combina-
steam at 140 – 170 ◦ C under pressure are form- tion of trichloromethane with alkali metals and
aldehyde and hydrogen chloride produced. certain other light metals [9].
Dichloromethane can be further chlorinated Tetrachloromethane is nonflammable and
either thermally or photochemically. Halogen relatively stable even in the presence of light and
exchange leading to chlorobromomethane or air at room temperature. When heated in air in
dibromomethane can be carried out by using the presence of metals (iron), phosgene is pro-
bromine and aluminum or aluminum bromide. duced in large quantities, the reaction starting at
In the presence of aluminum at 220 ◦ C and 90 ca. 300 ◦ C [10]. Photochemical oxidation also
MPa (900 bar), it reacts with carbon monoxide leads to phosgene. Hydrolysis to carbon dioxide
to give chloroacetyl chloride [5]. Warming to and hydrogen chloride is the principal result in a
125 ◦ C with alcoholic ammonia solution pro- moist atmosphere [11]. Liquid tetrachlorometh-
duces hexamethylenetetramine. Reaction with ane has only a very minimal tendency to hydro-
phenolates leads to the same products as are ob- lyze in water at room temperature (half-life ca.
tained in the reaction of formaldehyde and phe- 70 000 years) [12].
nols. Thermal decomposition of dry tetrachlor-
Trichloromethane is nonflammable, al- omethane occurs relatively slowly at 400 ◦ C
though it does decompose in a flame or in contact even in the presence of the common industrial
with hot surfaces to produce phosgene. In the metals (with the exception of aluminum and
presence of oxygen, it is cleaved photochemical- other light metals). Above 500 – 600 ◦ C an equi-
ly by way of peroxides to phosgene and hydro- librium reaction sets in which is shifted signifi-
gen chloride [6, 7]. The oxidation is catalyzed in cantly to the right above 700 ◦ C and 0.1 MPa (1
the dark by iron [8]. The autoxidation and acid bar) pressure. At 900 ◦ C and 0.1 MPa (1 bar), the
generation can be slowed or prevented by sta- equilibrium conversion of CCl4 is > 70 % (see
bilizers such as methanol, ethanol, or amylene. Chaps. 3.5, cf. Fig. 6).
Trichloromethane forms a hydrate, CHCl3 · 17 Tetrachloromethane forms shock-sensitive,
H2 O, whose critical decomposition point is + explosive mixtures with the alkali and alkaline-
1.6 ◦ C and 8.0 kPa (80 mbar). earth metals. With water it forms a hydratelike
Upon heating with aqueous alkali, trichloro- addition compound which decomposes at + 1.45
◦
methane is hydrolyzed to formic acid, orthofor- C.
mate esters being formed with alcoholates. With The telomerization of ethylene and vinyl
primary amines in an alkaline medium the isoni- derivatives with tetrachloromethane under pres-
trile reaction occurs, a result which also finds sure and in the presence of peroxides has
use in analytical determinations. The interac-
 Chlorinated Hydrocarbons 9

acquired a certain preparative significance catalytic methods [16]. The thermal chlorination
[13 – 15]: method is preferred, and it is also the one on
which the most theoretical and scientific inves-
CH2 = CH2 +CCl4 →CCl3 −CH2 −CH2 Cl tigations have been carried out.
The most important industrial reactions of Thermal chlorination of methane and its chlo-
tetrachloromethane are its liquid-phase con- rine derivatives is a radical chain reaction initi-
version with anhydrous hydrogen fluoride ated by chlorine atoms. These result from ther-
in the presence of antimony (III/V) fluo- mal dissociation at 300 – 350 ◦ C, and they lead
rides or its gas-phase reaction over alu- to successive substitution of the four hydrogen
minum or chromium fluoride catalysts, both atoms of methane:
of which give the widely used and important
compounds trichloromonofluoromethane (CFC
11), dichlorodifluoromethane (CFC 12), and
monochlorotrifluoromethane (CFC 13).

1.3. Production
The conversion to the higher stages of chlori-
1.3.1. Theoretical Bases nation follows the same scheme [17 – 21]. The
thermal reaction of methane and its chlorination
The industrial preparation of chloromethane products has been determined to be a second-
derivatives is based almost exclusively on the order process:
treatment of methane and/or monochlorometh-
ane with chlorine, whereby the chlorination dn (Cl2 ) /dt = k·p (Cl2 ) ·p (CH4 )
products are obtained as a mixture of the indi- It has further been shown that traces of oxy-
vidual stages of chlorination: gen strongly inhibit the reaction. Controlling the
Thermodynamic equilibrium lies entirely on high heat of reaction in the gas phase (which av-
the side of the chlorination products, so that the erages ca. 4200 kJ per m3 of converted chlorine)
distribution of the individual products is essen- at STP is a decisive factor in successfully carry-
tially determined by kinetic parameters. ing out the process. In industrial reactors, chlo-
Monochloromethane can be used in place of rine conversion first becomes apparent above
methane as the starting material, where this in 250 to 270 ◦ C, but it increases exponentially with
turn can be prepared from methanol by using increasing temperature [22], and in the region
hydrogen chloride generated in the previous pro- of commercial interest — 350 to 550 ◦ C — the
cesses. The corresponding reaction is: reaction proceeds very rapidly. As a result, it is
In this way, the unavoidable accumulation necessary to initiate the process at a temperature
of hydrogen chloride (hydrochloric acid) can which permits the reaction to proceed by itself,
be substantially reduced and the overall process but also to maintain the reaction under adiabatic
can be flexibly tailored to favor the production conditions at the requisite temperature level of
of individual chlorination products. Moreover, 320 – 550 ◦ C dictated by both chemical and tech-
given the ease with which it can be transported nical considerations. If a certain critical temper-
and stored, methanol is a better starting mate- ature is exceeded in the reaction mixture (ca.
rial for the chloro derivatives than methane, a 550 – 700 ◦ C, dependent both on the residence
substance whose availability is tied to natural time in the hot zone and on the materials making
gas resources or appropriate petrochemical fa- up the reactor), decomposition of the metastable
cilities. There has been a distinct trend in recent methane chlorination products occurs. In that
years toward replacing methane as a carbon base event, the chlorination leads to formation of un-
with methanol. desirable byproducts, including highly chlori-
Methane Chlorination. The chlorination of nated or high molecular mass compounds (tetra-
methane and monochloromethane is carried out chloroethene, hexachloroethane, etc.). Alterna-
industrially by using thermal, photochemical, or tively, the reaction with chlorine can get com-
10 Chlorinated Hydrocarbons

pletely out of control, leading to the separation

of soot and evolution of HCl (thermodynami-
cally the most stable end product). Once such
carbon formation begins it acts autocatalytically,
resulting in a progressively heavier buildup of
soot, which can only be halted by immediate
shutdown of the reaction.
Proper temperature control of this virtually
adiabatic chlorination is achieved by working
with a high methane : chlorine ratio in the range
of 6 – 4 : 1. Thus, a recycling system is em-
ployed in which a certain percentage of inert gas
is maintained (nitrogen, recycled HCl, or even
materials such as monochloromethane or tetra-
chloromethane derived from methane chlorina-
tion). In this way, the explosive limits of methane
and chlorine are moved into a more favorable re-
gion and it becomes possible to prepare the more
highly substituted chloromethanes with lower
CH4 : Cl2 ratios.
Figure 3 shows the explosion range of meth- Figure 4. Product distribution in methane chlorination, plug
ane and chlorine and how it can be limited stream reactor
a) Methane; b) Monochloromethane; c) Dichloromethane;
through the use of diluents, using the exam- d) Trichloromethane; e) Tetrachloromethane
ples of nitrogen, hydrogen chloride, and tetra-
chloromethane.

Figure 3. Explosive range of CH4 – Cl2 mixtures con-

taining N2 , HCl, and CCl4 Test conditions: pressure 100
kPa; temperature 50 ◦ C; ignition by 1-mm spark

The composition and distribution of the prod- Figure 5. Product distribution in methane chlorination, ideal
ucts resulting from chlorination is a definite mixing reactor
function of the starting ratio of chlorine to meth- a) Methane; b) Monochloromethane; c) Dichloromethane;
d) Trichloromethane; e) Tetrachloromethane
ane, as can be seen from Figure 4 and Figure 5.
 Chlorinated Hydrocarbons 11

These relationships have been investigated being consistent with Eq. 1 in page 13 and de-
frequently [23, 24]. The composition of the re- pendent on pressure and temperature (cf. also
action product has been shown to be in excel- Fig. 6).
lent agreement with that predicted by calcula-
tions employing experimental relative reaction
rate constants [25 – 28]. The products arising
from thermal chlorination of monochlorometh-
ane and from the pyrolysis of primary products
can also be predicted quantitatively [29]. The re-
lationships among the rate constants are nearly
independent of temperature in the region of tech-
nical interest. If one designates as k 1 through k 4
the successive rate constants in the chlorination
process, then the following values can be as-
signed to the relative constants for the individual
stages:
k 1 = 1 (methane)
k 2 = 2.91 (monochloromethane)
k 3 = 2.0 (dichloromethane)
Figure 6. Thermodynamic equilibrium 2 CCl4
C2 Cl4 +
k 4 = 0.72 (trichloromethane) 2 Cl2
With this set of values, the selectivity of the a) 0.1 MPa; b) 1 MPa; c) 10 MPa
chlorination can be effectively established with
respect to optimal product distribution for reac- It will be noted that at low pressure (0.1 to 1
tors of various residence time (stream type or MPa, 1 to 10 bar) and temperatures above 700
◦
mixing type, cf. Fig. 4 and Fig. 5). Additional C, conditions under which the reaction takes
recycling into the reaction of partially chlori- place at an acceptable rate, a significant amount
nated products (e.g., monochloromethane) per- of tetrachloroethene arises. For additional de-
mits further control over the ratios of the indi- tails see Chap. 3.5. Under conditions of high
vidual components [30, 31]. pressure — greater than 10 MPa (100 bar) —
It has been recognized that the yield of par- the reaction occurs at a temperature as low as
tially chlorinated products (e.g., dichlorometh- 600 ◦ C. As a result of the influence of pressure
ane and trichloromethane) is diminished by re- and by the use of a larger excess of chlorine,
cycling. This factor has to be taken into account the equilibrium can be shifted essentially 100 %
in the design of reactors for those methane chlo- to the side of tetrachloromethane. These circum-
rinations which are intended to lead exclusively stances are utilized in the Hoechst high-pressure
to these products. If the emphasis is to lie more chlorinolysis procedure (see below) [32, 33].
on the side of trichloro- and tetrachloromethane, Methanol Hydrochlorination. Studies
then mixing within the reactor plays virtually no have been conducted for purposes of reactor
role, particularly since less-chlorinated materi- design [34] on the kinetics of the gas-phase re-
als can always be partially or wholly recycled. action of hydrogen chloride with methanol in
Details of reactor construction will be discussed the presence of aluminum oxide as catalyst to
below in the context of each of the various pro- give monochloromethane. Aging of the catalyst
cesses. has also been investigated. The reaction is first
Chlorinolysis. The technique for the produc- order in respect to hydrogen chloride, but nearly
tion of tetrachloromethane is based on what is independent of the partial pressure of methanol.
known as perchlorination, a method in which The rate constant is proportional to the specific
an excess of chlorine is used and C1 - to C3 - surface of the catalyst, whereby at higher tem-
hydrocarbons and their chlorinated derivatives peratures (350 – 400 ◦ C) an inhibition due to
are employed as carbon sources. In this process, pore diffusion becomes apparent.
tetrachloroethene is generated along with tetra-
chloromethane, the relationship between the two
12 Chlorinated Hydrocarbons

1.3.2. Production of Monochloromethane drogen chloride and methanol, are warmed over
heat exchangers and led, after mixing and ad-
Monochloromethane is produced commercially ditional preheating, into the reactor, where con-
by two methods: by the hydrochlorination (es- version takes place at 280 – 350 ◦ C and ca. 0.5
terification) of methanol using hydrogen chlo- MPa (5 bar).
ride, and by chlorination of methane. Methanol The reactor itself consists of a large number
hydrochlorination has become increasingly im- of relatively thin nickel tubes bundled together
portant in recent years, whereas methane chlo- and filled with aluminum oxide. Removal of heat
rination as the route to monochloromethane as generated by the reaction (33 kJ/mol) is accom-
final product has declined. The former approach plished by using a heat conduction system. A
has the advantage that it utilizes, rather than hot spot forms in the catalyst layer as a result of
generating, hydrogen chloride, a product whose the exothermic nature of the reaction, and this
disposal — generally as hydrochloric acid — migrates through the catalyst packing, reaching
has become increasingly difficult for chlorinated the end as the latter’s useful life expires.
hydrocarbon producers. Moreover, this method The reaction products exiting the reactor are
leads to a single target product, monochloro- cooled with recycled hydrochloric acid (> 30 %)
methane, in contrast to methane chlorination (cf. in a subsequent quench system, resulting in sep-
Figs. 4 and 5). As a result of the ready and low- aration of byproduct water, removed as ca. 20 %
cost availability of methanol (via the low pres- hydrochloric acid containing small amounts of
sure methanol synthesis technique) and its facile methanol. Passage through a heat exchanger ef-
transport and storage, the method also offers the fects further cooling and condensation of more
advantage of avoiding the need for placing pro- water, as well as removal of most of the ex-
duction facilities in the vicinity of a methane cess HCl. The quenching fluid is recovered and
supply. subsequently returned to the quench circula-
Since in the chlorination of methane each tion system. The gaseous crude product is led
substitution of a chlorine atom leads to gener- from the separator into a 96 % sulfuric acid col-
ation of an equimolar amount of hydrogen chlo- umn, where dimethyl ether and residual water
ride — cf. Eqs. 2 – 5 in page 7 — a combination (present in a quantity reflective of its partial va-
of the two methods permits a mixture of chlori- por pressure) are removed, the concentration of
nated methanes to be produced without creating the acid diminishing to ca. 80 % during its pas-
large amounts of hydrogen chloride at the same sage through the column. In this step, dimethyl
time; cf. Eq. 6. ether reacts with sulfuric acid to form “onium
Monochloromethane production from meth- salts” and methyl sulfate. It can be driven out
anol and hydrogen chloride is carried out cat- later by further dilution with water. It is advan-
alytically in the gas phase at 0.3 – 0.6 MPa (3 tageous to use the recovered sulfuric acid in the
– 6 bar) and temperatures of 280 – 350 ◦ C. The production of fertilizers (superphosphates) or to
usual catalyst is activated aluminum oxide. Ex- direct it to a sulfuric acid cleavage facility.
cess hydrogen chloride is introduced in order to Dry, crude monochloromethane is subse-
provide a more favorable equilibrium point (lo- quently condensed and worked up in a high-pres-
cated 96 – 99 % on the side of products at 280 – sure (2 MPa, 20 bar) distillation column to give
350 ◦ C) and to reduce the formation of dimethyl pure liquid monochloromethane. The gaseous
ether as a side product (0.2 to 1 %). product emerging from the head of this column
The raw materials must be of high purity in (CH3 Cl + HCl), along with the liquid distillation
order to prolong catalyst life as much as possi- residue — together making up ca. 5 – 15 % of
ble. Technically pure (99.9 %) methanol is em- the monochloromethane product mixture — can
ployed, along with very clean hydrogen chlo- be recovered for introduction into an associated
ride. In the event that the latter is obtained from methane chlorination facility. The overall yield
hydrochloric acid, it must be subjected to spe- of the process, calculated on the basis of meth-
cial purification (stripping) in order to remove anol, is ca. 99 %.
interfering chlorinated hydrocarbons. The commonly used catalyst for vapor-phase
Process Description. In a typical production hydrochlorination of methanol is γ-aluminum
plant (Fig. 7), the two raw material streams, hy- oxide with an active surface area of ca. 200 m2 /g.
 Chlorinated Hydrocarbons 13

Figure 7. Production of monochloromethane by methanol hydrochlorination

a) Heat exchangers; b) Heater; c) Multiple-tube reactor; d) Quench system; e) Quench gas cooler; f) Quenching fluid tank;
g) Sulfuric acid column; h) CH3 Cl condensation; i) Intermediate tank; j) CH3 Cl distillation column

Catalysts based on silicates have not achieved [39]. Treatment of dimethyl sulfate with alu-
any technical significance. Catalyst aging can be minum chloride [40] or sodium chloride [41]
ascribed largely to carbon deposition. Byprod- results in the formation of monochloromethane.
uct formation can be minimized and catalyst life Methane reacts with phosgene at 400 ◦ C to give
considerably prolonged by doping the catalyst CH3 Cl [42]. The methyl acetate – methanol mix-
with various components and by introduction of ture that arises during polyvinyl alcohol synthe-
specific gases (O2 ) into the reaction components sis can be converted to monochloromethane with
[35]. The life of the catalyst in a production fa- HCl at 100 ◦ C in the presence of catalysts [43]. It
cility ranges from about 1 to 2 years. has also been suggested that monochlorometh-
Liquid-Phase Hydrochlorination. The ane could be made by the reaction of methanol
once common liquid-phase hydrochlorination with the ammonium chloride that arises during
of methanol using 70 % zinc chloride solution sodium carbonate production [44].
at 130 – 150 ◦ C and modest pressure is currently The dimethyl ether which results from
of lesser significance. Instead, new production methylcellulose manufacture can be reacted
techniques involving treatment of methanol with with hydrochloric acid to give monochlorometh-
hydrogen chloride in the liquid phase without the ane [45]. The process is carried out at 80 –
addition of catalysts are becoming preeminent. 240 ◦ C under sufficient pressure so that wa-
The advantage of these methods, apart from cir- ter remains as a liquid. Similarly, cleavage of
cumventing the need to handle the troublesome dimethyl ether with antimony trichloride also
zinc chloride solutions, is that they utilize aque- leads to monochloromethane [46].
ous hydrochloric acid, thus obviating the need In methanolysis reactions for the manufac-
for an energy-intensive hydrochloric acid distil- ture of silicones, monochloromethane is reco-
lation. The disadvantage of the process, which vered and then reintroduced into the process of
is conducted at 120 – 160 ◦ C, is its relatively silane formation [47]:
low yield on a space – time basis, resulting in Si+2CH3 Cl→SiCl2 (CH3 )2 (11)
the need for large reaction volumes [36 – 38].
Other Processes. Other techniques for pro-
ducing monochloromethane are of theoretical 1.3.3. Production of Dichloromethane and
significance, but are not applied commercially. Trichloromethane
Monochloromethane is formed when a mix-
ture of methane and oxygen is passed into the The industrial synthesis of dichloromethane also
electrolytes of an alkali chloride electrolysis leads to trichloromethane and small amounts of
14 Chlorinated Hydrocarbons

tetrachloromethane, as shown in Figure 4 and being the principal products), and small amounts
Figure 5. Consequently, di- and trichlorometh- of tetrachloromethane. The product composition
ane are prepared commercially in the same fa- is approximately 70 wt % dichloromethane, is
cilities. In order to achieve an optimal yield of approximately 27 wt % trichloromethane, and 3
these products and to ensure reliable tempera- wt % tetrachloromethane.
ture control, it is necessary to work with a large Methane chlorination is carried out in a sim-
methane and/or monochloromethane excess rel- ilar way by Chemische Werke Hüls AG, whose
ative to chlorine. Conducting the process in this work-up process employs prior separation of hy-
way also enables the residual concentration of drogen chloride by means of an adiabatic ab-
chlorine to be kept in the fully reacted prod- sorption system. After the product gas has been
uct at an exceptionally low level (< 0.01 vol%), washed to neutrality with sodium hydroxide, it
which in turn simplifies workup. Because of the is dried with sulfuric acid and compressed to ca.
large excess of carbon-containing components, 0.8 MPa (8 bar), whereby the majority of the re-
the operation is customarily accomplished in a sulting chloromethanes can be condensed with
recycle mode. relatively little cooling (at approximately − 12
Process Description. One of the oldest pro- to − 15 ◦ C). Monochloromethane is recycled to
duction methods is that of Hoechst, a recycle the chlorination reactor. The subsequent workup
chlorination which was introduced as early as to pure products is essentially analogous to that
1923 and which, apart from modifications re- employed in the Hoechst process.
flecting state-of-the-art technology, continues Other techniques, e.g., those of Montecatini
essentially unchanged, retaining its original im- and Asahi Glass, function similarly with respect
portance. The process is shown in Figure 8. to drying and distillation of the products.
The gas which is circulated consists of a mix- The loop reactor used by these and other
ture of methane and monochloromethane. To manufacturers (e.g., Stauffer Chem. Co.) [49]
this is added fresh methane and, as appropriate, has been found to give safe and trouble-free
monochloromethane obtained from methanol service, primarily because the internal circula-
hydrochlorination. Chlorine is then introduced tion in the reactor causes the inlet gases to be
and the mixture is passed into the reactor. The brought quickly to the initiation temperature,
latter is a loop reactor coated with nickel or high- thereby excluding the possibility of formation
alloy steel in which internal gas circulation is of explosive mixtures. This benefit is achieved
constantly maintained by means of a coaxial in- at the expense of reduced selectivity in the con-
let tube and a valve system. The reaction is con- duct of the reaction, however (cf. Figs. 4 and
ducted adiabatically, the necessary temperature 5). In contrast, the use of an empty tube reactor
of 350 – 450 ◦ C being achieved and maintained with minimal axial mixing has unquestionable
by proper choice of the chlorine to starting mate- advantages for the selective preparation of di-
rial (CH4 + CH3 Cl) ratio and/or by prewarming chloromethane [50, 51]. The operation of such a
the mixture [48]. The fully reacted gas mixture reactor is considerably more complex, however,
is cooled in a heat exchanger and passed through especially from the standpoint of measurement
an absorber cascade in which dilute hydrochlo- and control technology, since the starting gases
ric acid and water wash out the resulting hy- need to be brought up separately to the ignition
drogen chloride in the form of 31 % hydrochlo- temperature and then, after onset of the reaction
ric acid. The last traces of acid and chlorine with its high enthalpy, heat must be removed by
are removed by washing with sodium hydrox- means of a cooling system. By contrast, mainte-
ide, after which the gases are compressed, dried, nance of constant temperature in a loop reactor
and cooled and the reaction products largely is relatively simple because of the high rate of
condensed. Any uncondensed gas — methane gas circulation. A system operated by Frontier
and to some extent monochloromethane — is re- Chem. Co. employs a tube reactor incorporating
turned to the reactor. The liquified condensate recycled tetrachloromethane for the purpose of
is separated by distillation under pressure into temperature control [52].
its pure components, monochloromethane, di- Reactor Design. Various types of reactors
chloromethane, trichloromethane (the latter two are in use, with characteristics ranging between
 Chlorinated Hydrocarbons 15

Figure 8. Methane chlorination by the Hoechst method (production of dichloromethane and trichloromethane)
a) Loop reactor; b) Process gas cooler; c) HCl absorption; d) Neutralization system; e) Compressor; f) First condensation step
(water); g) Gas drying system; h) Second condensation system and crude product storage vessel (brine); i) Distillation columns
for CH3 Cl, CH2 Cl2 , and CHCl3

those of fully mixing reactors (e.g., the loop re- action system consists of two reactors connected
actor) and tubular reactors. Chem. Werke Hüls in series. After separation of higher boiling com-
operates a reactor that permits partial mixing, ponents, the low-boiling materials from the first
thereby allowing continuous operation with lit- reactor, including hydrogen chloride, are further
tle or no preheating. treated with chlorine in a second reactor. Re-
Instead of having the gas circulation take actors of this kind must be constructed of spe-
place within the reactor, an external loop can also cial materials with high resistance to both ero-
be used for temperature control, as, e.g., in the sion and corrosion. Special steps are required
process described by Montecatini [53] and used (e.g., washing with liquid chloromethanes) to
in a facility operated by Allied Chemical Corp. remove from the reaction gas dust derived from
In this case, chlorine is added to the reacted the fluidized-bed solids.
gases outside of the chlorination reactor, nec- Raw Materials. Very high purity standards
essary preheating is undertaken, and only then must be applied to methane which is to be chlo-
is the gas mixture led into the reactor. rinated. Some of this methane is derived from
The space – time yield and the selectivity of petrochemical facilities in the course of naph-
the chlorination reaction can be increased by op- tha cleavage to ethylene and propene, whereas
erating two reactors in series, these being sep- some comes from low-temperature distillation
arated by a condensation unit to remove high- of natural gas (the Linde process). Components
boiling chloromethanes [54]. such as ethane, ethylene, and higher hydrocar-
Solvay [55] has described an alternative bons must be reduced to a minimum. Otherwise,
means of optimizing the process in respect to these would also react under the conditions of
selectivity, whereby methane and monochloro- methane chlorination to give the corresponding
methane are separately chlorinated in reactors chlorinated hydrocarbons, which would in turn
driven in parallel. The monochloromethane pro- cause major problems in the purification of the
duced in the methane chlorination reactor is iso- chloromethanes. For this reason, every effort is
lated and introduced into the reactor for chlo- made to maintain the level of higher hydrocar-
rination of monochloromethane, which is also bons below 100 mL/m3 . Inert gases such as ni-
supplied with raw material from a methanol hy- trogen and carbon dioxide (but excluding oxy-
drochlorination system. The reaction is carried gen) have no significant detrimental effect on the
out at a pressure of 1.5 MPa (15 bar) in order to thermal chlorination reaction, apart from the fact
simplify the workup and separation of products. that their presence in excessive amounts results
Because of its effective heat exchange charac- in the need to eliminate considerable quantities
teristics, a fluidized-bed reactor is used by Asahi of off-gas from the recycling system, thus caus-
Glass Co. for methane chlorination [56]. The re-
16 Chlorinated Hydrocarbons

ing a reduction in product yield calculated on by distillation to the point of azeotrope forma-
the basis of methane introduced. tion (20 % HCl).
Chlorine with a purity of ca. 97 % (residue: Newer technologies have as their goal
hydrogen, carbon dioxide, and oxygen) is com- workup of the chlorination off-gas by dry meth-
pressed and utilized just as it emerges from ods. These permit use of less complicated con-
electrolysis. Newer chlorination procedures are struction materials. Apart from the reactors, in
designed to utilize gaseous chlorine of higher which nickel and nickel alloys are normally
purity, obtained by evaporization of previously used, all other apparatus and components can be
liquified material. constructed of either ordinary steel or stainless
Similarly, monochloromethane destined for steel.
further chlorination is a highly purified prod- Hydrogen chloride can be removed from the
uct of methanol hydrochlorination, special pro- off-gas by an absorption – desorption system de-
cedures being used to reduce the dimethyl ether veloped by Hoechst AG and utilizing a wash
content, for example, to less than 50 mL/m3 . with monochloromethane, in which hydrogen
Depending on the level of impurities present chloride is very soluble [57]. A similar proce-
in the starting materials, commercial processes dure involving HCl removal by a wash with tri-
incorporating recycling can lead to product chloromethane and tetrachloromethane has been
yields of 95 – 99 % based on chlorine or 70 described by Solvay [55].
– 85 % based on methane. The relatively low Other Processes. The relatively compli-
methane-based yield is a consequence of the cated removal of hydrogen chloride from meth-
need for removal of inert gases, although the ane can be avoided by adopting processes that
majority of this exhaust gas can be subjected to begin with methanol as raw material. An in-
further recovery measures in the context of some tegrated chlorination/hydrochlorination facility
associated facility. (Fig. 9) has been developed for this purpose and
Off-Gas Workup. The workup of off-gas brought on stream on a commercial scale by
from thermal methane chlorination is relatively Stauffer Chem. Co. [58].
complicated as a consequence of the methane Monochloromethane is caused to react with
excess employed. Older technologies accom- chlorine under a pressure of 0.8 – 1.5 MPa (8 –
plished the separation of the hydrogen chloride 15 bar) at elevated temperature (350 – 400 ◦ C)
produced in the reaction through its absorption with subsequent cooling occurring outside of the
in water or azeotropic hydrochloric acid, leading reactor. The crude reaction products are sep-
to ordinary commercial 30 – 31 % hydrochloric arated in a multistage condensation unit and
acid. This kind of workup requires a major out- then worked up by distillation to give the in-
lay for materials of various sorts: on the one dividual pure components. Monochlorometh-
hand, coatings must be acid-resistant but at the ane is returned to the reactor. After conden-
same time, materials which are stable against at- sation, gaseous hydrogen chloride containing
tack by chlorinated hydrocarbons are required. small amounts of monochloromethane is reacted
A further disadvantage frequently plagues with methanol in a hydrochlorination system
these “wet” processes is the need to find a use for corresponding to that illustrated in Figure 7 for
the inevitable concentrated hydrochloric acid, the production of monochloromethane. Follow-
particularly given that the market for hydrochlo- ing its compression, monochloromethane is re-
ric acid is in many cases limited. Hydrogen turned to the chlorination reactor. This process
chloride can be recovered from the aqueous hy- is distinguished by the fact that only a mini-
drochloric acid by distillation under pressure, mal amount of the hydrogen chloride evolved
permitting its use in methanol hydrochlorina- during the synthesis of dichloromethane and tri-
tion; alternatively, it can be utilized for oxychlo- chloromethane is recovered in the form of aque-
rination of ethylene to 1,2-dichloroethane. Dis- ous hydrochloric acid.
advantages of this approach, however, are the As a substitute for thermal chlorination at
relatively high energy requirement and the fact high temperature, processes have also been
that the hydrogen chloride can only be isolated developed which occur by a photochemical-
ly-initiated radical pathway. According to one
 Chlorinated Hydrocarbons 17

Figure 9. Chlorination of monochloromethane by the Stauffer process [59]

a) Chlorination reactor; b) Quench system; c) Multistage condensation; d) Crude product storage vessel; e) Drying;
f) Distillation and purification of CH2 Cl2 and CHCl3 ; g) Hydrochlorination reactor; h) Quench system; i) H2 SO4 drying
column; j) Compressor

patent [59], monochloromethane can be chlo- in turn leads to undesirable side products and
rinated selectively to dichloromethane at − 20 an unacceptably high loss of methane through
◦
C by irradiation with a UV lamp, the tri- combustion.
chloromethane content being only 2 – 3 %. A In this context, the “Transcat” process of the
corresponding reaction with methane is not pos- Lummus Co. is of commercial interest [61].
sible. In this process, methane is chlorinated and
Liquid-phase chlorination of monochloro- oxychlorinated in two steps in a molten salt mix-
methane in the presence of radical-producing ture comprised of copper(II) chloride and potas-
agents such as azodiisobutyronitrile has been sium chloride. The starting materials are chlo-
achieved by the Tokuyama Soda Co. The reac- rine, air, and methane. The process leaves virtu-
tion occurs at 60 – 100 ◦ C and high pressure [60]. ally no residue since all of its byproducts can be
The advantage of this low-temperature reaction recycled.
is that it avoids the buildup of side products com- Experiments involving treatment of meth-
mon in thermal chlorination (e.g., chlorinated ane with other chlorinating agents (e.g., phos-
C2 -compounds such as 1,1-dichloroethane, 1,2- gene, nitrosyl chloride, or sulfuryl chloride)
dichloroethene, and trichloroethene). Heat gen- have failed to yield useful results. The fluidized-
erated in the reaction is removed by evaporation bed reaction of methane with tetrachlorometh-
of the liquid phase, which is subsequently con- ane at 350 to 450 ◦ C has also been suggested
densed. Hydrogen chloride produced during the [62].
chlorination is used for gas-phase hydrochlori- The classical synthetic route to trichloro-
nation of methanol to give monochloromethane, methane proceeded from the reaction of chlo-
which is in turn recycled for chlorination. rine with ethanol or acetaldehyde to give chloral,
It is tempting to try to avoid the inevitable which can be cleaved with calcium hydroxide to
production of hydrogen chloride by carrying out trichloromethane and calcium formate [63]. Tri-
the reaction in the presence of oxygen, as in the chloromethane and calcium acetate can also be
oxychlorination of ethylene or ethane. Despite produced from acetone using an aqueous solu-
intensive investigations into the prospects, how- tion of chlorine bleach at 60 – 65 ◦ C. A descrip-
ever, no commercially feasible applications have tion of these archaic processes can be found in
resulted. The low reactivity of methane requires [64].
the use of a high reaction temperature, but this
18 Chlorinated Hydrocarbons

1.3.4. Production of Tetrachloromethane result from gaseous emissions from the chlori-
nation reaction, from the purification systems
Chlorination of Carbon Disulfide. The (hydrolysis), and from the molten sulfur pro-
chlorination of carbon disulfide was, until the cessing.
late 1950s, the principal means of producing The carbon disulfide method is still employed
tetrachloromethane, according to the following in isolated plants in the United States, Italy,
overall reaction: and Spain. Its advantage is that, in contrast to
chlorine substitution on methane or chlorinat-
CS2 +2Cl2 →CCl4 +2S (12) ing cleavage reactions, no accumulation of hy-
drogen chloride or hydrochloric acid byproduct
The resulting sulfur is recycled to a reactor for occurs.
conversion with coal or methane (natural gas) to
carbon disulfide. A detailed look at the reaction Perchlorination (Chlorinolysis). Early in
shows that it proceeds in stages corresponding the 1950s commercial production of tetra-
to the following equations: chloromethane based on high-temperature chlo-
rination of methane and chlorinating cleavage
2CS2 +6Cl2 →2CCl4 +2S2 Cl2 (13) reactions of hydrocarbons (≤ C3 ) and their chlo-
rinated derivatives was introduced. In processes
CS2 +2S2 Cl2
CCl4 +6S (14) of this sort, known as perchlorinations or chlo-
rinolyses, substitution reactions are accompa-
The process developed at the Bitterfeld plant of nied by rupture of C – C bonds. Starting mate-
I.G. Farben before World War II was improved rials, in addition to ethylene, include propane,
by a number of firms in the United States, includ- propene, dichloroethane, and dichloropropane.
ing FMC and the Stauffer Chem. Co. [65 – 67], Increasing use has been made of chlorine-con-
particularly with respect to purification of the taining byproducts and the residues from other
tetrachloromethane and the resulting sulfur. chlorination processes, such as those derived
In a first step, carbon disulfide dissolved in from methane chlorination, vinyl chloride pro-
tetrachloromethane is induced to react with chlo- duction (via either direct chlorination or oxy-
rine at temperatures of 30 – 100 ◦ C. Either iron chlorination of ethylene), allyl chloride prepa-
or iron(III) chloride is added as catalyst. The ration, etc. The course of the reaction is gov-
conversion of carbon disulfide exceeds 99 % in erned by the position of equilibrium between
this step. In a subsequent distillation, crude tetra- tetrachloromethane and tetrachloroethene, as il-
chloromethane is separated at the still head. The lustrated earlier in Figure 6, whereby the latter
disulfur dichloride recovered from the still pot always arises as a byproduct. In general, these
is transferred to a second stage of the process processes are employed for the production of
where it is consumed by reaction with excess tetrachloroethylene (see Section 3.5.3 and [68]),
carbon disulfide at ca. 60 ◦ C. The resulting sul- in which case tetrachloromethane is the byprod-
fur is separated (with cooling) as a solid, which uct. Most production facilities are sufficiently
has the effect of shifting the equilibrium in the re- flexible such that up to 70 wt % tetrachlorometh-
actions largely to the side of tetrachloromethane. ane can be achieved in the final product [69].
Tetrachloromethane and excess carbon disulfide The product yield can be largely forced to the
are withdrawn at the head of a distillation ap- side of tetrachloromethane by recycling tetra-
paratus and returned to the chlorination unit. A chloroethylene into the chlorination reaction, al-
considerable effort is required to purify the tetra- though the required energy expenditure is sig-
chloromethane and sulfur, entailing hydrolysis nificant. Higher pressure [70] and the use of hy-
of sulfur compounds with dilute alkali and sub- drocarbons containing an odd number of carbon
sequent azeotropic drying and removal from the atoms increases the yield of tetrachlorometh-
molten sulfur by air stripping of residual disulfur ane. When the reaction is carried out on an in-
dichloride. Yields lie near 90 % of the theoret- dustrial scale, a temperature of 500 to 700 ◦ C
ical value based on carbon disulfide and about and an excess of chlorine are used. The cor-
80 % based on chlorine. The losses, which must responding reactors either can be of the tube
be recovered in appropriate cleanup facilities, type, operated adiabatically by using a recycled
 Chlorinated Hydrocarbons 19

coolant (N2 , HCl, CCl4 , or C2 Cl4 ) [71 – 73], components must be added to increase the en-
or else they can be fluidized-bed systems op- thalpy of the reaction. In this way, even chlorine-
erated isothermally [74, 75]. Byproducts un- containing residues containing modest amounts
der these reaction conditions include ca. 1 – 7 % of aromatics can be utilized. Hexachloroben-
perchlorinated compounds (hexachloroethane, zene, for example, can be converted (albeit rel-
hexachlorobutadiene, hexachlorobenzene), the atively slowly) at the usual temperature of this
removal of which requires an additional expen- process and in the presence of excess chlorine to
diture of effort. tetrachloromethane according to the equilibrium
Pyrolytic introduction of chlorine into chlo- reaction:
rinated hydrocarbons has become increasingly C6 Cl6 +9Cl2
6CCl4
important due to its potential for consuming
chlorinated hydrocarbon wastes and residues The mixture exiting the reactor is comprised
from other processes. Even the relatively high of tetrachloromethane, the excess chlorine, hy-
production of hydrogen chloride can be toler- drogen chloride, and small amounts of hexachlo-
ated, provided that reactors are used which op- robenzene, the latter being recycled. This mix-
erate at high pressure and which can be cou- ture is quenched with cold tetrachlorometh-
pled with other processes that consume hydro- ane, its pressure is reduced, and it is subse-
gen chloride. Another advantage of the method quently separated into crude tetrachloromethane
is that it can be used for making both tetra- and chlorine and hydrogen chloride. The crude
chloromethane and tetrachloroethylene. The de- product is purified by distillation to give tetra-
crease in demand for tetrachloromethane in the chloromethane meeting the required specifica-
late 1970s and early 1980s, a consequence of tions. This process is advantageous in those situ-
restrictions (related to the ozone hypothesis) on ations in which chlorine-containing residues ac-
the use of chlorofluorocarbons prepared from it, cumulate which would otherwise be difficult to
has led to stagnation in the development of new deal with (e.g., hexachloroethane from methane
production capacity. chlorination facilities and high-boiling residues
from vinyl chloride production).
Hoechst High-Pressure Chlorinolysis. The A number of serious technical problems had
high-pressure chlorinolysis method developed to be overcome in the development of this pro-
and put in operation by Hoechst AG has the same cess, including perfection of the nickel-lined
goals as the process just described. It can be seen highpressure reactor, which required the design
in Figure 6 that under the reaction conditions of of special flange connections and armatures.
this process — 620 ◦ C and 10 to 15 MPa (100 to
150 bar) — the equilibrium Multistep Chlorination Process. Despite
the fact that its stoichiometry results in high
2CCl4
C2 Cl4 +2Cl2 yields of hydrogen chloride or hydrochloric
lies almost exclusively on the side of tetra- acid, thermal chlorination of methane to tetra-
chloromethane, especially in the presence of an chloromethane has retained its decisive impor-
excess of chlorine [32, 33, 76]. This method tance. Recent developments have assured that
utilizes chlorine-containing residues from other the resulting hydrogen chloride can be fed into
processes (e.g., methane chlorination and vinyl other processes which utilize it. In principle,
chloride) as raw material, although these must be tetrachloromethane can be obtained as the major
free of sulfur and cannot contain solid or poly- product simply by repeatedly returning all of the
merized components. lower boiling chloromethanes to the reactor. It is
The conversion of these materials is carried not possible to employ a 1 : 4 mixture of the re-
out in a specially constructed high-pressure tube actants methane and chlorine at the outset. This
reactor which is equipped with a pure nickel liner is true not only because of the risk of explosion,
to prevent corrosion. Chlorine is introduced in but also because of the impossibility of dealing
excess in order to prevent the formation of by- with the extremely high heat of reaction. Unfor-
products and in order maintain the final reac- tunately, the simple recycling approach is also
tion temperature (620 ◦ C) of this adiabatically uneconomical because it necessitates the avail-
conducted reaction. If hydrogen-deficient start- ability of a very large workup facility. There-
ing materials are to be employed, hydrogen-rich fore, it is most advantageous to employ several
20 Chlorinated Hydrocarbons

reactors coupled in series, the exit gases of each and phase separation. Wastewater exiting from
being cooled, enriched with more chlorine, and the quench system is directed to a stripping col-
then passed into the next reactor [77]. Processes umn where it is purified prior to being discarded.
employing supplementary circulation of an in- Residual off-gas is largely freed from remain-
ert gas (e.g., nitrogen) have also been suggested ing traces of halogen compounds by low-tem-
[78]. perature cooling and are subsequently passed
The stepwise chlorination of methane and/or through an off-gas purification system (activated
monochloromethane to tetrachloromethane is charcoal) before being released into the atmo-
based on a process developed in the late 1950s sphere, by which point the gas consists mainly
and still used by Hoechst AG (Fig. 10) [79]. of nitrogen along with traces of methane.
The first reactor in a six-stage reactor cas- The liquids which have been collected in the
cade is charged with the full amount of methane crude product containment vessel are freed of
and/or monochloromethane required for the en- gaseous components — Cl2 , HCl, CH3 Cl — by
tire production batch. Nearly quantitative chlo- passage through a degassing/dehydrating col-
rine conversion is achieved in the first reactor umn, traces of water being removed by distil-
at 400 ◦ C, using only a portion of the neces- lation. Volatile components are returned to the
sary overall amount of chlorine. The gas mix- reaction system prior to HCl absorption. The
ture leaving the first reactor is cooled and intro- crude product is then worked up to pure car-
duced into the second reactor along with addi- bon tetrachloride in a multistage distillation fa-
tional chlorine, the mixture again being cooled cility. Foreruns (light ends) removed in the first
after all of the added chlorine has been con- column are returned to the appropriate stage of
sumed. This stepwise addition of chlorine with the reactor cascade. The residue in the final col-
intermittent cooling is continued until in the last umn (heavy ends), which constitutes 2 – 3 wt %
reactor the component ratio CH4 : Cl2 = 1 : 4 is of the tetrachloromethane production, is made
reached. The reactors themselves are loop reac- up of hexachloroethane, tetrachloroethylene, tri-
tors with internal circulation, a design which, be- chloroethylene, etc. This material can be con-
cause of its efficient mixing, effectively shifts the verted advantageously to tetrachloromethane in
product distribution toward more highly chlo- a high-pressure chlorinolysis unit.
rinated materials. The gas mixture leaving the Overall yields in the process are ca. 95 %
reactors is cooled in two stages to − 20 ◦ C, in based on methane and > 98 % based on chlo-
the course of which the majority of the tetra- rine.
chloromethane is liquified, along with the less Other Processes. Oxychlorination as a way
chlorinated methane derivatives (amounting to of producing tetrachloromethane (as well as par-
ca. 3 % of the tetrachloromethane content). This tially chlorinated compounds) has repeatedly
liquid mixture is then accumulated in a crude been the subject of patent documents [80 – 82],
product storage vessel. particularly since it leads to complete utiliza-
The residual gas stream is comprised largely tion of chlorine without any HCl byproduct.
of hydrogen chloride but contains small amounts Pilot-plant studies using fluidized-bed technol-
of less highly chlorinated materials. This is sub- ogy have not succeeded in solving the problem
jected to adiabatic absorption of HCl using either of the high rate of combustion of methane. On
water or azeotropic (20 %) hydrochloric acid, the other hand the Transcat process, a two-stage
whereby technical grade 31 % hydrochloric acid approach mentioned in page 13 and embodying
is produced. Alternatively, dry hydrogen chlo- fused copper salts, can be viewed more posi-
ride can be withdrawn prior to the absorption tively.
step, which makes it available for use in other Direct chlorination of carbon to tetrachloro-
processes which consume hydrogen chloride methane is thermodynamically possible at atmo-
(e.g., methanol hydrochlorination). The steam spheric pressure below 1100 K, but the rate of
which arises during the adiabatic absorption is the reaction is very low because of the high acti-
withdrawn from the head of the absorption col- vation energy (lattice energy of graphite). Sulfur
umn and condensed in a quench system. The compounds have been introduced as catalysts in
majority of the chloromethanes contained in this these experiments. Charcoal can be chlorinated
outflow can be separated by subsequent cooling
 Chlorinated Hydrocarbons 21

Figure 10. Production of tetrachloromethane by stepwise chlorination of methane (Hoechst process)

a) Reactor; b) Cooling; c) First condensation (air); d) Second condensation (brine); e) Crude product storage vessel;
f) Degassing/dewatering column; g) Intermediate tank; h) Light-end column; i) Column for pure CCl4 ; j) Heavy-end column;
k) HCl stream for hydrochlorination; l) Adiabatic HCl absorption; m) Vapor condensation; n) Cooling and phase separation;
o) Off-gas cooler

to tetrachloromethane in the absence of catalyst purity (> 99.9 wt %). Dichloromethane, the sol-
with a yield of 17 % in one pass at 900 to 1100 K vent with the broadest spectrum of applications,
and 0.3 – 2.0 MPa (3 – 20 bar) pressure. None of is also distributed in an especially pure form (>
these suggested processes has been successfully 99.99 wt %) for such special applications as the
introduced on an industrial scale. A review of extraction of natural products.
direct chlorination of carbon is found in [83]. Monochloromethane and tetrachlorometh-
In this context it is worth mentioning the dis- ane do not require the presence of any stabilizer.
mutation of phosgene Dichloromethane and trichloromethane, on the
other hand, are normally protected from adverse
2COCl2 →CCl4 +CO2 influences of air and moisture by the addition
another approach which avoids the formation of of small amounts of efficient stabilizers. The
hydrogen chloride. This reaction has been stud- following substances in the listed concentration
ied by Hoechst [84] and occurs in the presence ranges are the preferred additives:
of 10 mol% tungsten hexachloride and activated
charcoal at 370 to 430 ◦ C and a pressure of 0.8 Ethanol 0.1 – 0.2 wt %
Methanol 0.1 – 0.2 wt %
MPa. The process has not acquired commercial Cyclohexane 0.01 – 0.03 wt %
significance because the recovery of the WCl6 Amylene 0.001 – 0.01 wt %
is very expensive.
Other substances have also been described
as being effective stabilizers, including phenols,
1.4. Quality Specifications amines, nitroalkanes, aliphatic and cyclic ethers,
epoxides, esters, and nitriles.
1.4.1. Purity of the Commercial Products Trichloromethane of a quality corresponding
and Their Stabilization to that specified in the Deutsche Arzneibuch,
8th edition (D.A.B. 8), is stabilized with 0.6 –
The standard commercial grades of all of the 1 wt % ethanol, the same specifications as ap-
chloromethanes are distinguished by their high pear in the British Pharmacopoeia (B.P. 80). Tri-
22 Chlorinated Hydrocarbons

chloromethane is no longer included as a sub- Since it is normally handled as a com-

stance in the U.S. Pharmacopoeia, it being listed pressed gas, monochloromethane must, in the
only in the reagent index and there without any Federal Republic of Germany, be stored in ac-
specifications. cord with Accident Prevention Regulation (Un-
fallverhütungsvorschrift, UVV) numbers 61 and
62 bearing the title “Gases Which Are Com-
1.4.2. Analysis pressed, Liquified, or Dissolved Under Pres-
sure” (“Verdichtete, verflüssigte, oder unter
Table 6 lists those classical methods for test- Druck gelöste Gase”) and issued by the Trade
ing the purity and identity of the chlorometh- Federation of the Chemical Industry (Verband
anes that are most important to both producers der Berufsgenossenschaften der chemischen In-
and consumers. Since the majority of these are dustrie). Additional guidelines are provided
methods with universal applicability, the corre- by general regulations governing high-pressure
sponding Deutsche Industrie Norm (DIN) and storage containers. Stored quantities in excess
American Society for the Testing of Materials of 500 t also fall within the jurisdiction of the
(ASTM) recommendations are also cited in the Emergency Regulations (Störfallverordnung) of
Table. the German Federal law governing emission pro-
tection.
Table 6. Analytical testing methods for chloromethanes Gas cylinders with a capacity of 40, 60,
Parameter Method
300, or 700 kg are suitable for the transport
of smaller quantities of monochloromethane.
DIN ASTM
Shut-off valves on such cylinders must be left-
Boiling range 51 751 D 1078 threaded. Larger quantities are shipped in con-
Density 51 757 D 2111
Refraction index 53 491 D 1218
tainers, railroad tank cars, and tank trucks, these
Evaporation residue 53 172 D 2109 generally being licensed for a working pressure
Color index (Hazen) 53 409 D 1209 of 1.3 MPa (13 bar).
Water content (K. Fischer) 51 777 D 1744 The three liquid chloromethanes are also nor-
pH value in aqueous extract – D 2110
mally stored and transported in vessels con-
structed of iron or steel. The most suitable ma-
Apart from these test methods, gas chro- terial for use with products of very high purity is
matography is also employed for quality con- stainless steel (material no. 1.4 571). The use in
trol both in the production and shipment of storage and transport vessels of aluminum and
chloromethanes. Gas chromatography is espe- other light metals or their alloys is prevented
cially applicable to chloromethanes due to their by virtue of their reactivity with respect to the
low boiling point. Even a relatively simple chro- chloromethanes.
matograph equipped only with a thermal con- Storage vessels must be protected against the
ductivity (TC) detector can be highly effective incursion of moisture. This can be accomplished
at detecting impurities, usually with a sensitivity by incorporating in their pressure release sys-
limit of a few parts per million (mg/kg). tems containers filled with drying agents such as
silica gel, aluminum oxide, or calcium chloride.
Alternatively, the liquids can be stored under a
dry, inert gas. Because of its very low boiling
1.5. Storage, Transport, and Handling point, dichloromethane is sometimes stored in
containers provided either with external water
Dry monochloromethane is inert with respect
cooling or with internal cooling units installed
to most metals, thus permitting their presence
in their pressure release systems.
during its handling. Exceptions to this general-
Strict specifications with respect to safety
ization, however, are aluminum, zinc, and mag-
considerations are applied to the storage and
nesium, as well as their alloys, rendering these
transfer of chlorinated hydrocarbons in order to
unsuitable for use. Thus most vessels for the
prevent spillage and overfilling. Illustrative is the
storage and transport of monochloromethane are
document entitled “Rules Governing Facilities
preferentially constructed of iron and steel.
for the Storage, Transfer, and Preparation for
 Chlorinated Hydrocarbons 23

Shipment of Materials Hazardous to Water Sup- containing chloromethane solvents. The central
plies” (“Verordnung für Anlagen zum Lagern, authorities of the various industrial trade organi-
Abfüllen und Umschlagen wassergefährdender zations issue informational and safety brochures
Stoffe”, VAwS). Facilities for this purpose must for chlorinated hydrocarbons, and these should
be equipped with the means for safely recover- be studied with care.
ing and disposing of any material which escapes The standard guidelines for handling mono-
[94]. chloromethane as a compressed gas are the
Shipment of solvents normally entails the use “Pressure Vessel Regulation” (“Druckbehälter-
of one-way containers (drums, barrels) made Verordnung”) of February 27, 1980, with the re-
of steel and if necessary coated with protec- lated “Technical Rules for Gases” (“Technische
tive paint. Where product quality standards are Regeln Gase”, TRG) and the “Technical Rules
unusually high, especially as regards minimal for Containers” (“Technische Regeln Behälter”,
residue on evaporation, stainless steel is the ma- TRB), as well as “Accident Prevention Guide-
terial of choice. line 29 — Gases” (“Unfallverhütungsvorschrift
Larger quantities are shipped in containers, [UVV] 29, Gase”).
railroad tank cars, tank trucks, and tankers of For MAK values, TLV values, and consid-
both the transoceanic and inland-waterway va- erations concerning the toxicology see Chap.
riety. So that product specifications may be met 10. The ecology and the ecotoxicology of the
for material long in transit, it is important during chloromethanes are described in Chapter 10.1.5.
initial transfer to ensure high standards of purity
and the absence of moisture.
Rules for transport by all of the various stan- 1.6. Behavior of Chloromethanes in the
dard modes have been established on an in- Environment
ternational basis in the form of the following
agreements: RID, ADR, GGVSee, GGVBinSch, Chloromethanes are introduced into the envi-
IATA-DGR. The appropriate identification num- ronment from both natural and anthropogenic
bers and warning symbols for labeling as haz- sources. They are found in the lower atmosphere,
ardous substances are collected in Table 7. and tetrachloromethane can even reach into
the stratosphere. Trichloromethane and tetra-
Table 7. Identification number and hazard symbols of chloromethane can be detected in many water
chloromethanes
supplies.
Product Identification Hazard symbol The chloromethanes, like other halogenated
number
hydrocarbons, are viewed as water contami-
Monochloromethane UN 1063 H (harmful) nants. Thus, they are found in both national and
IG (inflammable
gas)
international guidelines related to water quality
Dichloromethane UN 1593 H (harmful) protection [85, 86].
Trichloromethane UN 1888 H (harmful) There are fundamental reasons for needing
Tetrachloromethane UN 1846 P (poison) to restrict chlorocarbon emissions to an abso-
lute minimum. Proven methods for removal of
chloromethanes from wastewater, off-gas, and
The use and handling of chloromethanes — residues are
both by producers and by consumers of the
substances and mixtures containing them — are Vapor stripping with recycling
governed in the Federal Republic of Germany Adsorption on activated charcoal and recy-
by regulations collected in the February 11, 1982 cling
version of the “Rules Respecting Working Mate- Recovery by distillation
rials” (“Arbeitsstoff-Verordnung”). To some ex- Reintroduction into chlorination processes
tent, at least, these have their analogy in other [87]
European countries as well. Included are stipu- Combustion in facilities equipped with offgas
lations regarding the labeling of the pure sub- cleanup
stances themselves as well as of preparations
24 Chlorinated Hydrocarbons
Table 8. Atmospheric concentration of chloromethanes (in 10−10 vol.%) [90]

Compound Continents Oceans Urban areas

CH3 Cl 530 . . . 1040 1140 . . . 1260 834

CH2 Cl2 36 35 <20 . . . 144
CHCl3 9 . . . 25 8 . . . 40 6 . . . 15 000
CCl4 20 . . . 133 111 . . . 128 120 . . . 18 000

Table 9. Velocity of decomposition of chloromethanes in the

atmosphere [88]
which is presumed to occur in the stratosphere
(Table 9) [93].
Compound Reaction velocity Half-life,
with OH radicals weeks
k OH ×1012 cm3
molecule−1 s−1 1.6.2. Presence in Water Sources
CH3 Cl 0.14 12
CH2 Cl2 0.1 15 Seawater has been found to contain relatively
CHCl3 0.1 15 high concentrations of monochloromethane (5.9
CCl4 <0.001 >1000 – 21×10−9 mL of gas/mL of water) [89], in
addition to both trichloromethane (8.3 – 14×
10−9 g/L) [90] and tetrachloromethane (0.17 –
1.6.1. Presence in the Atmosphere 0.72×10−9 g/L) [90]. Dichloromethane, on the
other hand, could not be detected [88].
All four chloromethanes are emitted to the atmo- Chloromethanes can penetrate both surface
sphere from anthropogenic sources. In addition, and groundwater through the occurrence of ac-
large quantities of monochloromethane are re- cidents or as a result of improper handling dur-
leased into the atmosphere by the combustion of ing production, transportation, storage, or use
plant residues and through the action of sunlight (Table 10). Groundwater contamination by rain
on algae in the oceans. Estimates of the extent which has washed chlorinated hydrocarbons out
of nonindustrial generation of monochlorometh- of the air is not thought to be significant on the
ane range from 5 × 106 t/a [88] to 28 × 106 t/a basis of current knowledge. One frequent addi-
[89]. tional cause of diffuse groundwater contamina-
Natural sources have also been considered for tion that can be cited is defective equipment (es-
trichloromethane [90] and tetrachloromethane pecially leaky tanks and wastewater lines) [94].
[91] on the basis of concentration measurements The chloromethanes are relatively resistant
in the air and in seawater (Table 8). to hydrolysis. Only in the case of monochloro-
The emission of chloromethanes from indus- methane in seawater is abiotic degradation of
try is the subject of legal restrictions in many significance, this compound being subject in
countries. The applicable regulations in the Fed- weakly alkaline medium to cleavage with the
eral Republic of Germany are those of the TA elimination of HCl.
Luft [92]. The microbiological degradability of di-
The most important sink for many volatile chloromethane has been established [97 – 103].
organic compounds is their reaction in the This is understood to be the reason for the ab-
lower atmosphere with photochemically gener- sence or only very low concentrations of di-
ated OH radicals. The reactivity of monochloro- chloromethane in the aquatic environment [94].
methane, dichloromethane, and trichlorometh- Since trichloromethane and tetrachlorometh-
ane with OH radicals is so high that in the tro- ane are stable compounds with respect to both
posphere these substances are relatively rapidly biotic and abiotic processes, their disappearance
destroyed. is thought to be largely a consequence of trans-
By contrast, the residence time in the tropo- fer into the atmosphere by natural stripping phe-
sphere of tetrachloromethane is very long, with nomena.
the result that it can pass into the stratosphere, Treatment with chlorine is a widespread
where it is subjected to photolysis from hard technique for disinfecting drinking water. In
ultraviolet radiation. The Cl atoms released in the process, trihalomethanes result, largely tri-
this process play a role in the ozone degradation chloromethane as a result of the reaction of chlo-
 Chlorinated Hydrocarbons 25
Table 10. Chloromethane concentration in the Rhine river (µg/L) [95, 96]

Compound Date Mean value Max. value

CH2 Cl2 1980 not detected
CHCl3 1980 4.5
CHCl3 1982 0.4 . . . 12.5 50.0
CCl4 1982 <0.1 . . . 3.3 44.4

rine with traces of organic material. A level of 25 11 (trichloromonofluoromethane) and CFC 12

µg/L of trihalomethanes is regarded in the Fed- (dichlorodifluoromethane). These fluorochloro-
eral Republic of Germany as the maximum ac- carbons possess outstanding properties, such as
ceptable annual median concentration in drink- nonflammability and toxicological safety, and
ing water [104]. are employed as refrigerants, foaming agents,
aerosol propellants, and special solvents.
The production level of tetrachloromethane
1.7. Applications of the Chloromethanes is directly determined by the market for its flu-
and Economic Data orinated reaction products CFC 11 and CFC 12.
The appearance of the so-called ozone theory,
As a result of very incomplete statistical records which asserts that the ozone layer in the strato-
detailing production and foreign trade by indi- sphere is affected by these compounds, has re-
vidual countries, it is very difficult to describe sulted since 1976 in a trend toward reduced pro-
precisely the world market for chloromethanes. duction of tetrachloromethane. This has been
The information which follows is based largely especially true since certain countries (United
on systematic evaluation of the estimates of ex- States, Canada, Sweden) have imposed a ban on
perts, coupled with data found in the secondary aerosol use of fully halogenated fluorochlorocar-
literature, as well as personal investigations and bons. However, since 1982/1983 there has been
calculations. a weak recovery in demand for tetrachlorometh-
The Western World includes about 40 pro- ane in the production of fluorine-containing
ducers who produce at least one of the chlori- compounds.
nated C1 hydrocarbons. No authoritative infor- Outside Europe, a smaller amount of tetra-
mation is available concerning either the pro- chloromethane finds use as a disinfectant and as
duction capacity or the extent of its utilization a fungicide for grain.
in the Comecon nations or in the People’s Re- Monochloromethane and dichloromethane
public of China. It can be assumed, however, each account for about 25 % of the world market
that a large part of the domestic requirements in for chloromethanes (Table 11). The demand for
these countries is met by imports. In reference monochloromethane can be attributed largely
to production capacity, see [105]. (60 – 80 %) to the production of silicones. Its
In comparing the reported individual capac- use as a starting material for the production of
ities it is important to realize that a great many the gasoline anti-knock additive tetramethyllead
facilities are also capable of producing other is in steep decline.
chlorinated hydrocarbons. This situation is a The most important use of dichloromethane,
result of the opportunities for flexibility both representing ca. 40 – 45 % of the total market, is
in the product spectrum (cf. Sect. 1.3.1) and as a cleaning agent and paint remover. An ad-
in the various manufacturing techniques (e.g., ditional 20 – 25 % finds application as a pres-
tetrachloromethane/tetrachloroethene, cf. Sect. sure mediator in aerosols. One further use of di-
1.3.4). If one ignores captive use for further chlo- chloromethane is in extraction technology (de-
rination (especially of monochloromethane), it caffeination of coffee, extraction of hops, paraf-
can be concluded that the largest portion of the fin extraction, and the recovery of specialty phar-
world use of chloromethanes (ca. 34 %) can maceuticals).
be attributed to tetrachloromethane. The most In all of these applications, especially those
important market, accounting for over 90 % of related to the food and drug industries, the pu-
the material produced, is that associated with rity level requirements for dichloromethane are
the production of the fluorochlorocarbons CFC exceedingly high (> 99.99 wt %).
26 Chlorinated Hydrocarbons
Table 11. Production capacities of chloromethanes 1000 t/year [115]

Western Europe (FRG) United States Japan

1981 1993 1981 1993 1981 1993

Monochloromethane 265 295 300 274 70 106

(100)
Dichloromethane 410 237 370 161 65 86
(170)
Trichloromethane 140 247 210 226 65 53
(60)
Tetrachloromethane 250 182 380 140 70 40
(150)

Trichloromethane holds the smallest market ity with water vapor, and their tendency to form
share of the chloromethane family: 16 %. Its azeotropic mixtures.
principal application, amounting to more than Boiling point, density, viscosity, and surface
90 % of the total production, is in the produc- tension increase with increasing chlorine sub-
tion of monochlorodifluoromethane (CFC 22), a stitution, whereas heat of formation, solubil-
compound important on the one hand as a refrig- ity, and inflammability decrease. Substitution
erant, but also a key intermediate in the prepara- of vicinal positions generally has a greater im-
tion of tetrafluoroethene. The latter can be poly- pact than geminal substitution, as shown in Ta-
merized to give materials with exceptional ther- ble 13. With the exception of gaseous mono-
mal and chemical properties, including PTFE, chloroethane (ethyl chloride) and solid hex-
Hostaflon, Teflon, etc. achloroethane, the chloroethanes are colorless
Chloroform is still used to a limited extent liquids at ambient conditions. Figure 11 shows
as an extractant for pharmaceutical products. the vapor pressure as a function of tempera-
Due to its toxicological properties, its use as an ture. If light and oxygen are absent, most chlori-
inhalatory anaesthetic is no longer significant. nated ethanes are fairly stable. At higher tem-
Small amounts are employed in the synthesis of peratures (> 300 ◦ C), they are susceptible to
orthoformic esters. the elimination of hydrogen chloride. In the
Table 12 provides an overview of the struc- presence of light and oxygen, oxidation occurs
ture of the markets for the various chlorinated yielding phosgene, carbon oxides, and acetyl or
C1 compounds, subdivided according to region. chloroacetyl chlorides. The latter easily hydro-
lyze with traces of moisture forming the cor-
responding chloroacetic acids, which are well-
2. Chloroethanes known as strongly corrosive agents. To pre-
vent this unwanted decomposition, most indus-
The class of chloroethanes comprises: trially used chlorinated hydrocarbons are stabi-
lized with acid acceptors such as amines, unsat-
Monochloroethane (ethyl chloride) urated hydrocarbons, ethers, epoxides or phe-
1,1-Dichloroethane nols, antioxidants, and other compounds able to
1,2-Dichloroethane (ethylene dichloride, inhibit free radical chain reactions. Longer stor-
EDC) age periods and use without appreciable effect
1,1,1-Trichloroethane on tanks and equipment is then possible.
1,1,2-Trichloroethane Of all chlorinated ethanes, approxi-
1,1,1,2-Tetrachloroethane (asymmetric Tetra) mately half are of industrial importance.
1,1,2,2-Tetrachloroethane (symmetric Tetra) Monochloroethane (ethyl chloride) is an inter-
Pentachloroethane mediate in the production of tetraethyllead and
Hexachloroethane is widely used as an ethylating agent. 1,2-Di-
As with other chlorinated hydrocarbons, a chloroethane has by far the highest production
common characteristic of these compounds is rates. It is an intermediate for the production
their low solubility in water and excellent sol- of 1,1,1-trichloroethane and vinyl chloride (see
ubility in most organic solvents, their volatil- page 43 and 3.1.3.2), but it is also used in syn-
 Chlorinated Hydrocarbons 27
Table 12. Demand and use pattern of chloromethanes (1983)

Western United Japan

Europe States

Monochloromethane 230 000 t 250 000 t 50 000 t

Silicone 52 % 60 % 83 %
Tetramethyllead 12 % 15 % –
Methylcellulose 15 % 5% 1%
Other methylation reactions, e.g., tensides,
pharmaceuticals ca. 21 % ca. 20 % ca. 16 %
Dichloromethane 210 000 t 270 000 t 35 000 t
Degreasing and paint remover 46 % 47 % 54 %
Aerosols 18 % 24 % 19 %
Foam-blowing agent 9% 4% 11 %
Extraction and other uses 27 % 25 % 16 %
Trichloromethane 90 000 t 190 000 t 45 000 t
CFC 22 production 78 % 90 % 90 %
Other uses, e.g., pharmaceuticals, intermediate 22 % 10 % 10 %
Tetrachloromethane 250 000 t 250 000 t 75 000 t
CFC 11/12 production 94 % 92 % 90 %
Special solvent for chemical reactions 6% 8% 10 %

thetic applications (e.g., polyfunctional amines)

and as a fuel additive (lead scavenger).

Table 13. Physical properties of chlorinated ethanes

Compound Boiling point Relative

(at 101 kPa), ◦ C density, d20
4

Monochloroethane 12.3 0.9240

1,1-Dichloroethane 57.3 1.1760
1,2-Dichloroethane 83.7 1.2349
1,1,1-Trichloroethane 74.1 1.3290
1,1,2-Trichloroethane 113.5 1.4432
1,1,1,2-Tetrachloroethane 130.5 1.5468
1,1,2,2-Tetrachloroethane 146.5 1.5958
Pentachloroethane 162.0 1.6780
Hexachloroethane mp 186 – 187 2.0940

1,1,1-Trichloroethane, trichloroethylene,
(see Section 3.4) and tetrachloroethylene (see
Section 3.5) are important solvents widely used Figure 11. Vapor pressure as a function of temperature for
in dry cleaning, degreasing, and extraction pro- chlorinated hydrocarbons
cesses.
The other chlorinated ethanes have no im- ethane or ethylene and chlorine (Fig. 12). The
portant end uses. They are produced as interme- availability of ethylene from naphtha feedstocks
diates (e.g., 1,1-dichloroethane) or are formed has shifted the production of chlorinated C2 hy-
as unwanted byproducts. Their economical con- drocarbons during the past three decades in the
version into useful end products is achieved ei- Western World from the old carbide –acetylene
ther by cracking — tetrachloroethanes yield tri- – vinyl chloride route toward the ethylene route.
chloroethylene — or more commonly by chlori- With the dramatic increase of naphtha prices
nolysis, which converts them into carbon tetra- during the past decade, the old carbide route has
chloride and tetrachloroethylene (see page 76 ). regained some of its attractiveness [106]. Even
Basic feedstocks for the production of chlo- though a change cannot be justified presently in
rinated ethanes and ethylenes (see Chap. 3) are
28 Chlorinated Hydrocarbons

Figure 12. Chlorinated hydrocarbons from ethane and ethylene (simplified)

most countries, it could offer an alternative for ysis unit. The hydrocarbon feedstock is either
countries where cheap coal is readily available. supplied from a nearby cracker, — typical for
The use of ethanol derived from biomass as a U.S. gulf coast, — or via pipelines and bulk ship
starting material could likewise also be consid- transports. The chlorine value of the hydrogen
ered [107, 108]. chloride produced as a byproduct in most chlo-
In a few cases, ethane is used directly as rination processes can be recovered by oxychlo-
a hydrocarbon feedstock. This ‘direct’ ethane rination techniques, hydrochlorination reactions
route could offer an attractive alternative in some (for synthesis of methyl and ethyl chloride) or,
cases, because of the substantial cost differences — less economically — by aqueous HCl elec-
between ethane and ethylene. It becomes evi- trolysis. A minor but highly valuable outlet is
dent why numerous patents on ethane-based pro- ultrapure-grade anhydrous HCl used for etching
cesses have been filed. However, the major cost in the electronic industry.
advantage of such processes is the reduced cap- Although most unwanted byproducts can be
ital investment for cracker capacity. The direct used as feed for the chlorinolysis process [109]
ethane route must certainly be considered for fu- (see page 76 ), the byproducts of this process,
ture grass-root-plants, but at present, the conver- mostly hexachloroethane, hexachlorobutadiene,
sions and selectivities obtained seem not to jus- and hexachlorobenzene together with residual
tify the conversion of existing plants if cracker tars from spent catalysts and vinyl chloride pro-
capacity is available. duction, represent a major disposal problem. The
Less is known about the situation in Eastern optimal ecological solution is the incineration of
block countries. The available information indi- these residues at a temperature above 1200 ◦ C,
cates, however, that in some Eastern European which guarantees almost complete degradation.
countries the acetylene route is still used. Presently, incineration is performed at sea on
Because chlorine is needed as a second feed- special ships [110] without HCl scrubbing or on
stock, most plants producing chlorinated hydro- site with subsequent HCl or chlorine recovery.
carbons are connected to a chlor-alkali electrol- The aqueous HCl recovered can then be used for
 Chlorinated Hydrocarbons 29
Vapor pressure at
pH adjustment in biological effluent treatment or − 50 ◦ C 4.480 kPa
brine electrolysis. − 20 ◦ C 25.090 kPa
Due to their unique properties, the market for − 10 ◦ C 40.350 kPa
chlorinated C2 hydrocarbons has shown excel- 0 ◦C 62.330 kPa
+ 10 ◦ C 92.940 kPa
lent growth over the past 30 years and reached its + 20 ◦ C 134.200 kPa
maximum in the late 1970s. With increasing en- + 30 ◦ C 188.700 kPa
vironmental consciousness, the production rate + 60 ◦ C 456.660 kPa
of some chlorinated hydrocarbons such as ethyl + 80 ◦ C 761.100 kPa
0
Heat of formation (liquid) ∆H298 − 133.94
chloride, trichloroethylene (see page 73), and kJ/mol
◦
tetrachloroethylene (see 3.5.4) will in the long Specific heat at 0 C 1.57 kJ kg−1
run decrease due to the use of unleaded gasoline, K−1
Heat of evaporation at 298 K 24.7 kJ/mol
solvent recovery systems, and partial replace- Critical temperature 456 K
ment by other solvent and extraction chemicals. Critical pressure 5270 kPa
However, new formulations for growing mar- Viscosity (liquid, 10 ◦ C) 2.79 × 10−4 Pa
s
kets such as the electronic industry, the availabil- Viscosity (vapor, bp) 9.3 × 10−5 Pa
ity of ecologically safe handling systems, know- s
how in residue incineration, and the difficulty in Thermal conductivity (vapor) 1.09 × 10−3 W
m−1 K−1
finding superior replacements — causing fewer Surface tension (air, 5 ◦ C) 21.18 × 10−3
problems — guarantee chlorinated ethanes and N/m
ethylenes a long-term and at least constant mar- Dielectric constant (vapor, 23.5 ◦ C) 1.0129
Flash point (open cup) − 43 ◦ C
ket share.
Ignition temperature 519 ◦ C
Explosive limits in air 3.16 – 15 vol%
monochloroethane
Solubility in water at 0 ◦ C 0.455 wt %
2.1. Monochloroethane Solubility of water in monochloroethane at 0 ◦ C 0.07 wt %

Monochloroethane (ethyl chloride) [75-00-3] is At ambient temperature, monochloroethane

thought to be the first synthesized chlorinated is a gas with an etheral odor.
hydrocarbon. It was produced in 1440 by Valen- Monochloroethane burns with a green-edged
tine by reacting ethanol with hydrochloric acid. flame.
Glauber obtained it in 1648 by reacting etha- Combustion products are hydrogen chloride,
nol (spirit of wine) with zinc chloride. Because carbon dioxide, and water.
of the growing automotive industry in the early Binary azeotropic mixtures of monochloro-
1920s, monochloroethane became an important ethane have been reported [111]. The data, how-
bulk chemical. Its use as a starting material for ever, have not been validated.
the production of tetraethyl-lead (→ Lead Com-
pounds) initiated a significant increase in ethyl
chloride production and is still its major con- 2.1.2. Chemical Properties
sumer. The trend toward unleaded gasoline in
most countries, however, will in the long run Monochloroethane has considerable thermal
lead to a significant decrease in production. stability. Only at temperatures above 400 ◦ C,
considerable amounts of ethylene and hydrogen
chloride are formed due to dehydrochlorination
2.1.1. Physical Properties [111]a. This decomposition can be catalyzed by
a variety of transition metals (e.g. Pt), transition-
Mr 64.52 metal salts, and high-surface area oxides such as
mp − 138.3 ◦ C
bp at 101.3 kPa 12.3 ◦ C alumina and silica. Catalyzed decomposition is
 of the liquid at 0 ◦ C 0.924 g/cm3 complete at temperatures slightly above 300 ◦ C
 of the vapor at 20 ◦ C 2.76 kg/m3 according to the thermodynamic equilibrium.
n20 1.3798
D At ambient atmospheric conditions, both,
hydrolysis (to ethanol) and oxidation (to acet-
aldehyde) are moderate.
30 Chlorinated Hydrocarbons

At temperatures up to 100 ◦ C, monochloro- an optimized process has been patented [113].

ethane shows no detrimental effect on most In other process variations, the formed mono-
structural materials if kept dry. Contact with alu- chloroethane (sump phase) is washed with di-
minum, however, should be avoided under all luted NaOH to remove catalyst and acid and then
circumstances for safety reasons. dried and distilled. Excess ethylene is recycled.
Monochloroethane has the highest reactivity
of all chlorinated ethanes. It is mainly used as
an ethylating agent in Grignard- and Friedel-
Crafts-type reactions, for ether, thioether, and
amine synthesis. Halogene exchange [111]b and
fluorination is also possible [111]c.

2.1.3. Production

Monochloroethane can be produced by a variety

of reactions. Only two are of industrial impor-
tance: the hydrochlorination of ethylene and the
thermal chlorination of ethane.
Figure 13. Schematic diagram (simplified) of an ethylene
Hydrochlorination of Ethylene. Exother- hydrochlorination process
mic hydrochlorination of ethylene can be carried a) Reactor; b) Cooler; c) Knock-out drum; d) Light-end
out in either the liquid or gas phase. columns; e) Reboiler; f) Stripper column (heavy ends)

C2 H4 +HCl→C2 H5 −Cl∆H = −98kJ/mol Ethylene and HCl yields for hydrochlori-

The liquid-phase reaction is carried out mostly nation are almost quantitative; selectivities of
at near ambient temperatures (10 – 50 ◦ C) and 98 – 99 % have been reported. In addition to
moderate pressure (0.1 – 0.5 MPa) in a boiling- AlCl3 , other Lewis-acid catalysts, such as FeCl3
bed type reactor. The heat of reaction is used to [114], BiCl3 [116], and GaCl3 [117], have been
vaporize part of the monochloroethane formed, patented. Suggestions to perform the reaction in
which in turn is then cooled down, purified, or benzene or higher boiling hydrocarbons [118],
partially recycled. The reactor temperature is in 1,1,2-trichloroethane [119] or to complex
controlled by the recycle ratio and the feed rate of AlCl3 by nitrobenzene [120] have not found in-
the reactants. Unconverted ethylene and hydro- dustrial acceptance.
gen chloride from reflux condensers and over- The troublesome handling of the catalyst is
head light end columns are recycled back to the minimized when ethylene and hydrogen chlo-
reactor. Sufficient mixing and catalyst contact ride are reacted in the gas phase. Although the
time is achieved through recirculation of the re- reaction equilibrium becomes unfavorable at a
actor sump phase. Aluminum chloride in a 0.5 temperature above 200 ◦ C, the process is carried
– 5 wt % concentration is mostly used as a cat- out at temperatures of 250 – 450 ◦ C in order to
alyst. A part of it is continuously or intermit- achieve sufficient conversion. Ethylene and HCl
tently removed via a recirculation slip stream, are preheated, mixed, and sent across the cat-
together with unwanted high boiling impurities alyst, which can be used as fixed or fluidized
consisting mostly of low molecular mass ethyl- bed. The chloroethane formed is separated and
ene oligomers formed in a Ziegler-type reaction purified. Unreacted ethylene and HCl are recy-
of the catalyst with the ethylene feed. New cat- cled. Selectivities are comparable to those of the
alyst is added to the system either by a hopper liquid-phase process, conversion per pass, how-
as a solid or preferably as a solution after pre- ever, may not exeed 50 %, so that relatively high
mixing with monochloroethane or monochloro- recycle rates are necessary. Because high pres-
ethane/ethylene. A gaseous feed of vaporized sure favors the formation of monochloroethane,
AlCl3 has also been suggested [112]. A sim- the reaction is preferably carried out at 0.5 – 1.5
plified process diagram is shown in Figure 13; MPa.
 Chlorinated Hydrocarbons 31

Thorium oxychloride on silica [121], pla- section can be used. Conversion at this stage
tinium on alumina [122], and rare-earth oxides is 50 – 80 %. The products are then separated
on alumina and silica [123] have been patented in a second tower. Unconverted ethane, ethyl-
as catalysts. ene, and hydrogen chloride are recycled to the
Chlorination of Ethane. Thermal chlorina- first reactor. The monochloroethane formed by
tion of ethane for the production of monochloro- hydrochlorination is drawn off and purified to-
ethane can be used industrially in a tandem gether with the stream from the first tower.
process developed by the Shell Oil Company Even though the recycled ethylene from the
(Fig. 14) [124]. This process was especially de- hydrochlorination step is present during ther-
signed for a plant in which sufficient ethylene mal chlorination, the formation of 1,2-dichloro-
feedstock could only be supplied by increas- ethane is insignificant. Because the first reaction
ing the cracker capacity. Ethane and chlorine is carried out at high temperatures, chlorine ad-
were available, but not hydrogen chloride. For dition to the ethylene double bond is suppressed.
this feedstock constellation, the tandem process The process is balanced by the overall reac-
seems advantageous. tion equation:
C2 H6 +Cl2 →C2 H5 Cl+HCl

HCl+C 2 H4 →C2 H5 Cl

A 90 % overall yield for ethane and ethylene

and a 95 % chlorine yield to monochloroethane
are reported.
Monochlorination of ethane is favored be-
cause ethane chlorination is four times faster
than the consecutive chlorination of mono-
chloroethane to dichloroethanes.
Major byproducts from the chlorination step
are 1,1-, 1,2-dichloroethane and vinyl chloride.
To achieve a high selectivity for monochloro-
Figure 14. Production of monochloroethane by the Shell
process [124]
ethane, a high ethane surplus — preferably a 3
a) Preheater; b) Ethane chlorinator; c) Cooler; d) Lightend – 5-fold excess over chlorine [125, 126] — and
tower; e) Crude chloroethane storage; f) Hydrochlorinator; good mixing is required. Insufficient heat dis-
g) Compressor sipation may enhance cracking and coking. A
thermal chlorination reactor providing thorough
In the first stage, ethane and chlorine are re- premixing and optimal heat transfer by means
acted noncatalytically after sufficient preheating of a fluidized bed has been described in [126].
at 400 – 450 ◦ C in an adiabatic reactor. The re- Other patents claim contact of the reaction gases
action gases are separated after cooling in a first with metal chlorides [127] or graphite [128].
monochloroethane distillation tower. The heavy The photochemical chlorination of ethane de-
bottoms of this tower containing chloroethane scribed in several patents [129] is less important,
and more higly chlorinated products (mostly because it is difficult to implement in large vol-
1,1-dichloroethane and 1,2-dichloroethane) are ume plants and offers no major advantages over
sent to the purification stage. The overheads con- the thermal process.
sisting mainly of unconverted ethane, hydro-
Monochloroethane as a Byproduct of the
gen chloride, and ethylene are sent to a second
Oxy-EDC Process. Monochloroethane is a ma-
isothermal fixed-bed reactor. Before entering
jor byproduct in the Oxy-EDC process (see page
this reactor, fresh ethylene is added to achieve a
35), in which it is formed by direct hydrochlo-
1 : 1 ethylene to HCl feed ratio. Even though the
rination of ethylene. It can be condensed or
type of catalyst used in the isothermal section
scrubbed from the light vent gases and recovered
is not described, any of the catalysts mentioned
after further purification.
for gas-phase hydrochlorination in the previous
32 Chlorinated Hydrocarbons

Monochloroethane from Ethanol. The es- blowing agent and solvent for extraction pro-
terification of ethanol with HCl is possible in the cesses for the isolation of sensitive natural fra-
liquid phase by using ZnCl2 or similar Lewis- grances.
acid catalysts at 110 – 140 ◦ C [130]. Similar Production in 1984 in the Western World was
to the production of monochloromethane (see about 300 000 t. Almost all processes in use at
1.3.2), the reaction can also be carried out in present are ethylene based.
the gas phase by using γ-alumina [131], ZnCl2
and rare earth chlorides on carbon [132] or zeo-
lites [133] as catalysts. At the present ethanol 2.2. 1,1-Dichloroethane
prices, these procedures are prohibitive. With
some modification, however, they can offer out- 1,1-Dichloroethane [75-34-3] is the less impor-
lets for surplus byproducts such as ethyl acetate tant of the two dichloroethane isomers.
from PVA production which can be converted to It occurs — often as an unwanted byprod-
monochloroethane by HCl using a ZnCl2 /silica uct — in many chlorination and oxychlorination
catalyst [134]. processes of C2 hydrocarbons.
Other Synthetic Routes to Monochloro- The most important role of 1,1-dichloro-
ethane. Non-commercial routes to mono- ethane is as an intermediate in the production
chloroethane consist of electrolytic chlorination of 1,1,1-trichloroethane.
of ethane in melts [135], reactions with diethyl Other uses are negligible.
sulfates [136], metathesis of 1,2-dichloroethane
[137], hydrogenation of vinyl chloride [138],
and conversion of diethyl ether [139]. The oxy- 2.2.1. Physical Properties
chlorination of ethane is discussed later in this
Mr 98.97
Chapter. mp − 96.6 ◦ C
Small amounts of monochloroethane are bp at 101.3 kPa 57.3 ◦ C
formed during the reaction of synthesis gas –  at 20 ◦ C 1.176 g/cm3
n20 1.4164
chlorine mixtures over Pt/alumina [140] and D
Vapor pressure at
methane – chlorine mixtures in the presence of ◦
0 C 9.340 kPa
cation-exchange resins complexed with TaF5 10 ◦ C 15.370 kPa
[141]. 20 ◦ C 24.270 kPa
30 ◦ C 36.950 kPa
Heat of formation (liquid) − 160.0 kJ/mol
0
∆H298
2.1.4. Uses and Economic Aspects Specific heat at 20 ◦ C 1.38 kJ kg−1 K−1
Heat of evaporation at 298 30.8 kJ/mol
K
Monochloroethane became industrially signif- Critical temperature 523 K
icant as a result of the developing automo- Critical pressure 5070 kPa
◦
tive industry. It is the starting material for Viscosity at 20 C 0.38 × 10−3 Pa s
Surface tension at 20 ◦ C 23.5 × 10−3 N/m
tetraethyllead, the most commonly used octane Dielectric constant at 20 10.9
booster. In the United States, about 80 – 90 % ◦
C
and in Europe ca. 60 % of the monochloroethane Flash point (closed cup) − 12 ◦ C
Ignition temperature 458 ◦ C
production is used for the production of tetra- Explosive limits in air at 255.4 – 11.4 vol%
ethyl lead. ◦
C
Production has already been cut significantly 1,1-dichloroethane
Solubility in water at 20 ◦ C0.55 wt %
due to the increased use of unleaded fuel for en-
Solubility of water in
vironmental reasons. U.S. projections indicate 1,1-dichloroethane at 20 0.97 wt %
◦
an average annual decline of ca. 10 % per year. C
With some delay, the same trend can also be pre-
dicted for Western Europe. 1,1-Dichloroethane is a colorless liquid. It is
Minor areas of use for monochloroethane are readily soluble in all liquid chlorinated hydro-
the production of ethyl cellulose, ethylating pro- carbons and in a large variety of other organic
cesses for fine chemical production, use as a solvents (ethers, alcohols).
 Chlorinated Hydrocarbons 33

Binary azeotropes are formed with water and 1,1-Dichloroethane via the 1,2-Di-
ethanol: with 1.9 % water, bp 53.3 ◦ C (97 kPa) chloroethane – Vinyl Chloride Route. Hydro-
and with 11.5 % ethanol, bp 54.6 ◦ C (101 kPa). gen chloride and vinyl chloride obtained from
1,2-dichloroethane cracking see page 58) are re-
acted in a boiling-bed-type reactor [144] in the
2.2.2. Chemical Properties presence of a Friedel-Crafts catalyst, preferably
ferric chloride (FeCl3 ). 1,1-Dichloroethane is
At room temperature, 1,1-dichloroethane is ad- used as solvent and the temperature ranges from
equately stable. Cracking to vinyl chloride and 30 to 70 ◦ C.
hydrogen chloride takes place at elevated tem- Depending on the process design, hydrogen
peratures. However, compared to other chlori- chloride can be used in excess to achieve com-
nated C2 hydrocarbons, the observed cracking plete conversion of the vinyl chloride. The heat
rates are moderate. This reaction can be pro- of reaction, which differs only slightly from the
moted by traces of chlorine and iron [142]. 2,3- heat required for 1,2-dichloroethane cracking,
Dichlorobutane is often found as a dimeric by- can be used to distill the 1,1-dichloroethane and
product of decomposition. recover part of the energy input. Downstream
1,1-Dichloroethane was also found to en- hydrogen chloride and unconverted vinyl chlo-
hance 1,2-dichloroethane cracking when added ride are separated and recycled. If necessary, the
in lower concentrations (≤ 10 wt %) [143]. 1,1-dichloroethane can then be further purified
Corrosion rates for dry 1,1-dichloroethane by distillation. Due to the formation of heavy
are marginal, increase however, with water con- byproducts (vinyl chloride polymers) and deac-
tent and temperature. Aluminum is easily at- tivation of the catalyst, a slipstream from the
tacked. reactor bottom must be withdrawn and new cat-
In the presence of water or in alkaline solu- alyst added.
tion, acetaldehyde is formed by hydrolysis. Improved processes use column-type reac-
tors with optimized height [145] (hydrostatic
pressure to avoid flashing of vinyl chloride!)
2.2.3. Production and recycled 1,1-dichloroethane with intermit-
tent cooling stages. In this case, the stoichiomet-
Theoretically 1,1-dichloroethane can be pro- ric ratio of hydrogen chloride to vinyl chloride,
duced by three routes: as obtained from 1,2-dichloroethane cracking,
can often be used. In such a process, the down-
1) Addition of HCl to acetylene:
stream distillation equipment can be less com-
plex and expensive, because almost complete
conversion is achieved and because no excess
hydrogen chloride or the entrained vinyl chlo-
2) Thermal or photochemical chlorination of ride must be separated. However, the energy re-
monochloroethane: quirements may be higher because most of the
heat of formation must be dissipated by cooling.
Both process variations yield between ca. 95
and 98 %. Yield losses result through polymer-
3) Addition of HCl to vinyl chloride: ization of vinyl chloride. The concentration as
well as the nature of the catalyst determine this
side reaction. Zinc chloride (ZnCl2 ) and alu-
minum chloride (AlCl3 ), which also can be used
as catalysts, promote the formation of high mo-
For the synthesis of 1,1-dichloroethane as lecular mass byproducts more than ferric chlo-
an intermediate in the production of 1,1,1-tri- ride (FeCl3 ) [120, 146]. The removed spent cat-
chloroethane only the latter route is important alyst can be burned together with the heavy
and industrially used. byproducts in an incinerator, if the vent gases
are subsequently scrubbed and the wash liquor
appropriately treated. Environmental problems
34 Chlorinated Hydrocarbons

caused by the residues are thereby almost elim- 2.3.1. Physical Properties
inated.
Mr 98.97
1,1-Dichloroethane via the Acetylene mp − 35.3 ◦ C
Route. As with the synthesis of vinyl chlo- bp at 101.3 kPa 83.7 ◦ C
ride (see 3.1.3.1), 1,1-dichloroethane can be  at 20 ◦ C 1.253 g/cm3
produced from acetylene by adding 2 mol of hy- n20
D 1.4449
Vapor pressure at
drogen chloride. For the first reaction sequence 0 ◦C 3.330 kPa
— the formation of vinyl chloride — mercury 20 ◦ C 8.530 kPa
catalyst is required [147]. 30 ◦ C 13.300 kPa
50 ◦ C 32.000 kPa
Because ethylene has become the major feed- 70 ◦ C 66.650 kPa
stock for chlorinated C2 hydrocarbons, this pro- 80 ◦ C 93.310 kPa
cess has lost its importance. Heat of formation (liquid) − 157.3 kJ/mol
∆H◦ 298
1,1-Dichloroethane from Ethane. 1,1-Di- Specific heat (liquid, at 20 ◦ C) 1.288 kJ kg−1 K−1
chloroethane may also be obtained by ethane or Heat of evaporation at 298 K 34.7 kJ/mol
chloroethane chlorination. This chlorination can Critical temperature 563 K
Critical pressure 5360 kPa
be carried out as thermal chlorination [148], pho- Viscosity at 20 ◦ C 0.84 × 10−3 Pa s
tochlorination, or oxychlorination [149]. These Surface tension at 20 ◦ C 31.4 × 10−3 N/m
processes, however, are impaired by a lack of Coefficient of cubical expansion
selectivity and are not used industrially. (0 – 30 ◦ C) 0.00116 K−1
Dielectric constant 10.5
Flash point (closed cup) 17 ◦ C
Flash point (open cup) 21 ◦ C
2.2.4. Uses and Economic Aspects Ignition temperature (air) 413 ◦ C
Explosive limits in air at 25 ◦ C 6.2 – 15.6 vol%
As mentioned earlier, 1,1-dichloroethane is pri- 1,2-dichloroethane
Solubility in water at 20 ◦ C 0.86 wt %
marily used as a feedstock for the production of Solubility of water in
1,1,1-trichloroethane. 1,2-dichloroethane at 20 ◦ C 0.16 wt %
Although several other applications have
been patented [150], currently 1,1-dichloro- 1,2-Dichloroethane is a clear liquid at ambi-
ethane is rarely used for extraction purposes or ent temperature, which is readily soluble in all
as a solvent. chlorinated hydrocarbons and in most common
Based on estimated production figures of organic solvents.
1,1,1-trichloroethane and disregarding other Binary azeotropes with 1,2-dichloroethane
uses, the total Western World production of are listed in Table 14.
1,1-dichloroethane is estimated at 200 000 – 250
000 t for 1985. Table 14. Binary azeotropes formed by 1,2-dichloroethane

wt % Component Azeotrope
boiling point
2.3. 1,2-Dichloroethane (101.3 kPa),
◦
C
The first synthesis of 1,2-dichloroethane (ethyl- 18.0 2-propen-1-ol 79.9
ene dichloride, EDC) [107-06-2] was achieved 38.0 formic acid 77.4
in 1795. 37.0 ethanol 70.3
19.5 1,1-dichloroethane 72.0
Presently, 1,2-dichloroethane belongs to 43.5 2-propanol 74.7
those chemicals with the highest production 32.0 methanol 61.0
rates. Average annual growth rates of > 10 % 19.0 1-propanol 80.7
were achieved during the past 20 years. 79.0 tetrachloromethane 75.6
18.0 trichloroethylene 82.9
Although these growth rates declined during 8.2 water 70.5
the past several years, in the long run 1,2-di-
chloroethane will maintain its leading position
among the chlorinated organic chemicals due to
its use as starting material for the production of
poly(vinyl chloride) (→ Poly(Vinyl Chloride)).
 Chlorinated Hydrocarbons 35

2.3.2. Chemical Properties (perchloroethylene and tetrachloromethane pro-

duction, see page 18 and Section 3.5.3) or 1,1,1-
Pure 1,2-dichloroethane is sufficiently stable trichloroethane (see page 43) can be fed to the
even at elevated temperatures and in the pres- oxychlorination stage for proper balancing and
ence of iron. Above 340 ◦ C, decomposition be- chlorine recovery.
gins, yielding vinyl chloride, hydrogen chloride, The use of ethane as a starting material, al-
and trace amounts of acetylene [111]a, [151]. though the subject of numerous patent claims,
This decomposition is catalyzed by halogens and is still in the experimental stage. It could offer
more highly substituted chlorinated hydrocar- economic advantages if the problems related to
bons [152]. catalyst selectivity, turnover, and long-term per-
Long-term decomposition at ambient tem- formance are solved.
perature caused by humidity and UV light can Direct Chlorination in the Ethylene Liquid
be suppressed by addition of stabilizers, mostly Phase.. In the direct chlorination process, ethyl-
amine derivatives. Oxygen deficient burning and ene and chlorine are most commonly reacted in
pyrolytic and photooxidative processes convert the liquid phase (1,2-dichloroethane for temper-
1,2-dichloroethane to hydrogen chloride, carbon ature control) and in the presence of a Lewisacid
monoxide, and phosgene. catalyst, primarily iron(III) chloride:
Both chlorine atoms of 1,2-dichloroethane
can undergo nucleophilic substitution reactions,
which opens routes to a variety of bifunctional
compounds such as glycol (by hydrolysis or re-
action with alkali), succinic acid dinitrile (by
reaction with cyanide), or ethylene glycol di- To avoid problems in product purification,
acetate (by reaction with sodium acetate). The the use of high-purity ethylene is recommended.
reaction with ammonia to ethylenediamine and Especially its propane/propene content must be
use of 1,2-dichloroethane for the production of controlled in order to minimize the formation
polysulfides is of industrial importance. of chloropropanes and chloropropenes, which
Iron and zinc do not corrode when dry 1,2-di- are difficult to separate from 1,2-dichloroethane
chloroethane is used, whereas aluminum shows by distillation. Purified liquid chlorine is used
strong dissolution. Increased water content leads to avoid brominated byproducts. Oxygen or air
to increased corrosion of iron and zinc; alu- is often added to the reactants, because oxy-
minum, however, corrodes less [153]. gen was found to inhibit substitution chlorina-
tion, yielding particularly 1,1,2-trichloroethane
and its more highly chlorinated derivatives [154,
2.3.3. Production 155]. Through this and an optimized reactor de-
sign, the use of excess ethylene is no longer re-
1,2-Dichloroethane is industrially produced by quired to control byproduct formation. In most
chlorination of ethylene. cases, the reactants are added in the stoichio-
This chlorination can either be carried out metric chlorine/ethylene ratio or with a slight
by using chlorine (direct chlorination) or hydro- excess of chlorine. This simplifies the process-
gen chloride (oxychlorination) as a chlorinating ing equipment because an excess of ethylene,
agent. which was often used in the past [156], requires
In practice, both processes are carried out to- complicated condensor and post reactor equip-
gether and in parallel because most EDC plants ment to avoid the loss of expensive ethylene in
are connected to vinyl chloride (VCM) units the off-gas [155, 157].
and the oxychlorination process is used to bal- Although several other Lewis-acid catalysts
ance the hydrogen chloride from VCM pro- with higher selectivities such as antimony, cop-
duction (see page 62 and Fig. 24). Depending per, bismuth, tin, and tellurium chlorides [158]
on the EDC/VCM production ratio of the inte- have been patented, iron chloride is widely used.
grated plants, additional surplus hydrogen chlo- Because the reaction selectivities are not depen-
ride from other processes such as chlorinolysis dent on the catalyst concentration, it is used in
a diluted concentration between ca. 100 mg/kg
36 Chlorinated Hydrocarbons

and 0.5 wt %. Some processes use iron filler

bodies in the reactor to improve mass and heat
transfer or use iron as a construction material.
This equipment generates sufficient FeCl3 in situ
[159].
In the liquid-phase reaction, ethylene absorp-
tion was found to be the rate-controlling step
[160].
In addition to the distinct process modifica-
tions with which each producer of 1,2-dichloro-
ethane has improved his process during the past
years, two fundamental process variations can
be characterized:
1) low-temperature chlorination (LTC) and
2) high-temperature chlorination (HTC)
In the LTC process, ethylene and chlorine re-
act in 1,2-dichloroethane as a solvent at temper- Figure 15. Simplified DC – HTC process
atures (ca. 20 – 70 ◦ C) below the boiling point a) Reactor; b) Cooler; c) Knock-out drum; d) Heavy-end
tower; e) Reboiler
of 1,2-dichloroethane.
The heat of reaction is transferred by exter-
The light ends are drawn off from the head
nal cooling either by means of heat exchangers
section, and ethylene is condensed and recycled.
inside the reactor or by circulation through ex-
In the following condensation section, vinyl
terior heat exchangers [161].
chloride is separated and can then be processed
This process has the advantage that due to
with vinyl chloride from EDC cracking (see
the low temperature, byproduct formation is low.
page 58). The remaining vent gas is incinerated.
The energy requirements, however, are consider-
Pure EDC is taken from an appropriate section
ably higher in comparison to the HTC process,
and condensed. In order to maintain a constant
because steam is required for the rectification
composition in the reactor sump phase, a slip-
of 1,2-dichloroethane in the purification section.
stream is continuously withdrawn, from which
Conversions up to 100 % with chlorine and eth-
the heavy byproducts are separated by rectifica-
ylene selectivities of 99 % are possible.
tion and sent to a recovery stage or incinerated.
In the HTC process, the chlorination reaction
In some designs, the reactor is separated from
is carried out at a temperature between 85 and
the distillation tower [164]. In others, two tow-
200 ◦ C, mostly, however, at about 100 ◦ C. The
ers are used for light ends/EDC separation. Solid
heat of reaction is used to distill the EDC. In ad-
adsorption has been patented for iron chloride
dition, EDC from the Oxy-EDC process or un-
removal [165].
converted EDC from the vinyl chloride section
For optimal heat recovery, cross exchange
can be added, since the heat of formation equals
can be used for chlorine feed evaporation [166].
the heat required for vaporization by a factor of
Due to the relatively low temperatures and an-
ca. 6.
hydrous conditions, carbon steel equipment can
By sophisticated reactor design and thorough
be used [167].
mixing conversion, and yields comparable to the
Process developments using cracking gases
LTC process may be obtained with considerably
instead of highly purified ethylene [168] and the
lower energy consumption for an integrated DC-
use of nitrosyl chloride [169] as a chlorinating
Oxy-VCM process [162].
agent have not found any industrial importance.
Description of the HTC Process (Fig. 15).
Gaseous chlorine and ethylene are fed thor- Direct Chlorination in the Gas Phase. A
oughly mixed into a reaction tower which is also catalytic gasphase process was patented by the
supplied with dry EDC from oxychlorination or Société Belge de l’Azote [170]. Because of the
recycled EDC from the VCM section. highly exothermic reaction, adequate dilution is
 Chlorinated Hydrocarbons 37

necessary. Several catalysts have been patented Byproducts of ethylene oxychlorination are
[171]. monochloroethane, formed by direct HCl ad-
The noncatalytic chlorine addition reaction dition to ethylene, VCM from the cracking of
has been thoroughly studied [172], but is not in- EDC, 1,1,2-trichloroethane formed by substitu-
dustrially used, as is the case for the catalytic tion chlorination of EDC or chlorine addition to
gas-phase chlorination of chloroethane [173]. VCM, 1,1-dichloroethane formed by the addi-
Oxychlorination of Ethylene in the Gas tion of HCl to VCM, and other crack or sub-
Phase. In the oxychlorination process, ethylene stitution products such as 1,1-dichloroethylene,
and hy-drogen chloride are reacted with oxygen cis- and trans-1,2-dichloroethylene, trichloro-
in the presence of an ambivalent metal catalyst. ethylene, and tetrachloroethanes. Because oxy-
In most cases, copper salts are used at a temper- gen is present, additional oxidation products
ature above 200 ◦ C. The overall reaction can be such as acetaldehyde and its chlorinated deriva-
formulated as tives, primarily trichloroacetaldehyde (chloral),
are found in the reactor effluent. Oxirane (eth-
ylene oxide) and glycols may also be formed.
The ethylene feed is partially consumed, espe-
cially at higher temperatures, by deep oxidation
to yield carbon oxides (CO, CO2 ) and formic
The reaction sequence is similar to that of the
acid.
Deacon process (see → Chlorine Chap. 10.2.1),
In some plants, major byproducts such as
although mechanistic studies indicate that eth-
chloroethane and 1,1,2-trichloroethane are reco-
ylene is involved in the early reaction stages and
vered and sold or used as feedstock for other
the process may differ greatly from the clas-
chlorinated hydrocarbon (CHC) processes such
sic Deacon process (e.g., oxidation of HCl to
as 1,1-dichloroethylene production (see Section
chlorine with subsequent addition of chlorine to
3.2.3) and chlorinolysis (see page 76).
ethylene by which chlorine is withdrawn from
Reactor Feed. Polymerization grade ethyl-
the Deacon equilibrium a high HCl conversion
ene is used to minimize byproduct formation and
is achieved). The reaction sequence probably
purification problems.
proceeds via chlorination of ethylene by cupric
In most cases, HCl from the EDC cracking
chloride. The copper salt is then regenerated by
section (see page 58) is used as a source of chlo-
HCl and oxygen:
rine. The acetylene content (derived from VCM
cracking) of this hydrogen chloride may be crit-
ical and should be controlled, because acetylene
tends to form more highly chlorinated byprod-
ucts and tars, which can lead to catalyst deacti-
Several investigations on the reaction mech- vation by coking (pore plugging) and may also
anisms have been performed [174]. influence down-stream operations. Selective hy-
Ethylene oxychlorination has attained com- drogenation to ethylene is often used to remove
mercial importance since about 1960, when acetylene from this HCl [181]. An other method
VCM producers began to pursue the ethylene proposes catalytic hydrochlorination with sub-
route and HCl from EDC cracking had to be sequent adsorption of the vinyl chloride formed
recovered. Due to this historic development, sev- [182]. In addition to HCl from EDC cracking,
eral process variations are presently used by the HCl from other CHC processes like 1,1,1-tri-
major EDC/VCM producers and will be dis- chloroethane-, tri-, and tetrachloroethylene pro-
cussed in detail later [175 – 179]. A common duction can be used without problems, if kept
characteristic of all these processes is the cat- free of such well-known catalyst poisons as flu-
alytic gas-phase oxychlorination at temperatures orine and sulfur compounds.
between 200 and 300 ◦ C and pressures of 0.1 to In most processes, air is used as an oxy-
1.0 MPa, usually at 0.4 – 0.6 MPa. HCl and eth- gen source. Microfiltration prior to compres-
ylene conversions of 93 – 97 % are achieved at sion is employed to exclude particulate matter.
contact times between ca. 0.5 – 40 s with selec- In oxygen-based processes, pure oxygen is sup-
tivities to EDC of 91 – 96 % [180]. plied by a nearby air liquefaction and separation
38 Chlorinated Hydrocarbons

process and is used without additional process- Due to the highly exothermic oxychlorina-
ing. tion reaction, temperature control is a problem
Catalyst. Copper(II) salts, usually cupric in fixed-bed systems. It is achieved by proper di-
chlorides, are used as standard catalysts lution of the catalyst with inactive diluents such
[183 – 185]. In many cases, alkali, alkaline as undoped alumina [184], graphite [184, 191],
earth or aluminum chloride are added to re- silicon carbide [184, 192], or nickel [193]. Thus,
duce volatilization of the cupric salt. These salts catalyst activity at the reactor inlet is normally
form eutectic mixtures, which reduce the melt- low and increases to its maximum at the outlet.
ing point. The reduction of the melting point, on In order to make catalyst charging not too
the other hand, seems to be beneficial to the re- complicated, several blends of active catalysts
action rates. Furthermore, the addition of alkali and inactive diluent are prepared and sequen-
salts suppresses direct addition reactions such as tially charged. One patent [191] claims to use
monochloroethane formation. four different catalyst zones containing from the
Some patents claim rare-earth salts (didy- reactor inlet to the outlet active catalyst concen-
mium salts) as promoters [185, 186] or use trations of 7, 15, 40, and 100 vol%, respectively.
sodium/ammonium hydrogen sulfates [187] or The active catalyst consists of 8.5 wt % CuCl2 on
tellurium salts [188]. alumina. The inert diluent is made of graphite.
High-surface-area alumina (150 – 300 m2 /g) In another process [194], highly concentrated
is preferred as a support, because its produc- active catalyst is deposited at the top to start the
tion process allows the control of such impor- reaction followed by an inactive zone for tem-
tant parameters as surface area, pore volume, perature control. In the following zones, the ac-
and pore size distribution. Its high attrition re- tive catalyst concentration increases and reaches
sistance makes it very suitable for fluidized-bed 100 % in the last zone near the outlet.
reactors. Other support materials like graphite, Catalyst dilution requires exact mixing tech-
silica, pumice, or kieselguhr are of minor impor- niques and appropriate charging procedures in
tance. order to avoid demixing, i.e., segregation of dilu-
For fluidized-bed reactors, alumina powder ent from active catalyst when different materials
or microspheres (ca. 10 – 200 µm diameter) are are used. This can lead to a rapid pressure drop
used [189], whereas for fixed-bed reactors, cata- buildup across the reactor.
lyst tablets, extrudates, or spheres with a narrow Another approach is to vary catalyst activ-
size distribution (ca. 1/8 – 1/4 diameter) are ap- ity through the catalyst particle size, which is
plied. not very practical, however [195]. More recent
The catalyst is prepared to the support by the developments [194] favor staged catalysts, con-
imbibition method using aqueous solutions of sisting of three to four different catalysts with
the catalyst salts followed by drying steps, or by varying amounts of CuCl2 and KCl. The use of
special spray techniques [177]. such catalyst systems, as offered by some manu-
Cupric chloride is usually added in concen- facturers, does not require mixing and may offer
trations of 3 – 12 wt % (of the total catalyst). Al- advantages in some cases.
kali salts are added in nearly double amounts to Fixed-bed technology is used by Dow Chem-
obtain molar alkali/copper ratios of 2 : 1 [190] ical, Stauffer, Toyo Soda and Vulcan. The size
and rare-earth salts in concentrations of 1 –10 of the tubular reactors varies from 2 to 5 m in
wt %. diameter and 4 to > 10 m in length. They may
The fine adjustment of the catalyst composi- comprise several thousand tubes for the cata-
tion as well as the selection of the appropriate lyst with diameters up to 2 . Dow Chemical and
support material and preparation procedure is a Vulcan usually use one reactor, whereas Stauffer
well kept secret of the individual technology and and Toyo Soda prefer successive oxychlorina-
closely related to the reactor design. tion systems with up to three reactors and split
Reactor Design. Theoretically, two basic re- addition of oxygen. This latter method allows the
actor designs are in service: formation of explosive mixtures at the reactor in-
let to be more easily avoided, and it is claimed
1) fixed-bed reactors
that fewer oxidation products are formed.
2) fluidized-bed reactors
 Chlorinated Hydrocarbons 39

Nickel alloys are used for the construction ternal cooling coils positioned in the fluidized
of the tube section. Because of hot-spot forma- bed.
tion, Alloy 200 may be prone to intergranular One major advantage of the fluidized-bed re-
embrittlement, so that higher resistance may be actor is that the reaction can be carried out within
obtained with Alloy 201 with a lower carbon the explosive limit, which makes feed control
content [167]. The tube sheet and the reactor less critical.
head are lined with nickel on steel. For the reac- Reactor-integrated cyclones are used at the
tor shell, carbon steel is primarily used. outlet to retain catalyst fines and to return them
Proper heat tracting for the interconnecting to the reaction zone.
piping to the quench or absorber system is re- Time – space yields may average 150 – 200
quired to avoid corrosion. kg of EDC m−3 h−1 [199].
The equipment for further processing such as Fluidized-bed reactors are more widely
the absorber – stripper – phase separator is lined used than fixed-bed systems. Companies using
with either bricks (towers) or teflon (pipes) to fluidized-bed technology are B. F. Goodrich,
withstand the corrosion caused by aqueous HCl. Hoechst, Pittsburgh Plate Glass (PPG), Ethyl
The heat of reaction is either used to generate Corp., Solvay, ICI, and Mitsui Toatsu Chemical.
steam at the side of the reactor shell or is trans- Tokoyama Soda [178] and Pechiney [200]
ferred to a hot oil system, which may supply have combined the advantages of both processes
other plants. by first reacting the gases in an isothermal flu-
Fluidized-bed reactors have the advantage of idized bed and then passing them across a fixed
improved heat transfer and almost isothermal bed for optimal yields and conversions.
operation. However, backmixing, which influ- Process Description (Fig. 16, 17 and 18).
ences conversion and selectivity, cannot be Ethylene and hydrogen chloride are preheated
avoided. Nevertheless, HCl conversions of > and fed with air or oxygen to the reactor. The
98 % have been reported [196]. This is achieved hot reaction gases are quenched in a brick-lined
by feeding stoichiometric excesses of air or oxy- tower and the resulting aqueous HCl is either
gen (10 – 80 %) and ethylene (up to 60 %) [197]. treated together with the combined wastewaters
The temperature range between ca. 220 – 240 or cleaned separately by stripping for further use,
◦
C is somewhat lower than in fixed beds. El- e.g., in a chlor-alkali process. The gases leav-
evated pressure (0.2 – 0.5 MPa) is used to in- ing the quench tower are cooled in a heat ex-
crease conversion. High-surface alumina pow- changer, and the organic phase is washed with
der (ca. 200 m2 /g) [189] or fuller’s earth [198] dilute NaOH in order to remove chloral [201].
are the preferred catalyst supports. The parti- The off-gas is either vented after additional
cle size distribution for representative samples condensation and/or scrubbing or adsorption
shows a maximum at about 40 – 80 µm diameter steps (for air-based systems) or compressed and
[189]. Cupric chloride concentration on the cat- recycled (if pure oxygen is used).
alyst varies from ca. 7 – 20 wt % CuCl2 . Higher In some process modifications, heat exchang-
concentrations are of no advantage, because the ers and separators f and g are placed behind the
reaction rate will not improve and the catalyst NaOH wash. In other processes, the quench step
will cake in the reactor. is performed without addition of water, and a
Because of the lower temperature range, the NaOH wash tower is not always required.
reactor can be made of stainless steel if con- The wet EDC is dried by azeotropic destilla-
densation (formation of aqueous HCl) can be tion.
avoided by means of proper shutdown proce- The bottoms from the azeotropic distillation
dures. Sparging equipment at the entrance of the are sent to the DC section for final purifica-
reactor requires pipes, nozzles, and fittings of tion. The light head products are submitted for
nickel alloys (Alloy 600 and 825) because they further treatment together with the azeotrope
are more resistant to chloride stress corrosion for product recovery (ethylene, monochloro-
[167]. ethane, EDC, chlorinated methanes) or inciner-
Heat from the reaction is used to generate ated. Care must be taken to remain outside of the
steam or is transferred to a hot oil system by in- flammable range during all process steps [202].
40 Chlorinated Hydrocarbons

Figure 16. Oxy – EDC process (fixed bed, simplified)

a) Compressor; b) Preheater; c) Fixed-bed reactor; d) Quench tower; e) Cooler; f) Degasser; g) Separator; h) Wash tower;
i) Azeotropic drying tower; j) Reboiler

plants have become very stringent. The large

amounts of nitrogen in the vent gas, however,
makes the final treatment by incineration pro-
hibitively expensive.

Figure 18. Stauffer oxygen-based Oxy-EDC process

a) Reactor; b) Cooler; c) Separator; d) Compressor

If oxygen is used instead of air [204], the

Figure 17. Oxy – EDC fluidized-bed reactor vent stream becomes 20 – 100 times smaller, al-
lowing vent incineration or catalytic oxidation
Oxygen-based Oxychlorination. Vent gas [205].
from air-based oxychlorination processes is one Airbased systems are more manageable than
of the major emission sources of CHC plants. In others because the nitrogen from the air acts as
spite of intensive cooling and sophisticated ab- diluent and removes heat.
sorber – stripper, adsorber – desorber, and post- In an oxygen-based system, this function is
reaction systems [203], the restrictions on many achieved with an excess of ethylene [206], which
 Chlorinated Hydrocarbons 41

is then recycled. Only a small quantity of the tures of both components have been patented
recycled stream must be drawn off in order to [149, 210].
control the concentration of carbon oxides and A process developed by the Monsanto Com-
other low-boiling byproducts. This slipstream is pany [211] comprises the direct thermal chlori-
either burned or fed to the DC process to recover nation of ethane, yielding monochloroethane. In
ethylene. the next step, the reaction gases are oxychlori-
Since the heat capacity of ethylene in compar- nated to 1,2-dichloroethane. In another variation
ison to nitrogen is considerably higher, oxygen- [212], ethane is oxidized by oxygen in the pres-
based systems can be operated at lower tempera- ence of HCl at 400 – 600 ◦ C to give ethylene.
tures or at higher throughput rates. This capacity The resulting mixture is again oxychlorinated in
increase together with the considerable savings a conventional manner.
for incineration [207] may offset the higher costs This process has similarities with the au-
for oxygen and recycle compression energy. tothermic cracking process [213], where ethyl-
During the past years, the conversion of many ene, chlorine, and oxygen are reacted at 850 –
existing air-based facilities has proven to be fea- 950 ◦ C to form mainly ethylene and hydrogen
sible. chloride. In a further process step, the gases are
Oxychlorination of Ethylene in the Liq- oxychlorinated to 1,2-dichloroethane.
uid Phase. An aqueous liquid-phase process for In both cases, chlorine balancing (HCl) in an
oxychlorination has been developed by the Kel- integrated VCM process seems feasible. How-
log Co. [179, 208]. Ethylene, oxygen, and hy- ever, none of these processes have been imple-
drogen chloride are fed to an aqueous solution of mented on an industrial scale. Compared to the
copper(II) salts (5 – 10 M) at 170 – 185 ◦ C and oxychlorination of ethylene, ethanebased pro-
1.7 – 1.9 MPa. The 1,2-dichloroethane formed cesses are frequently affected by poor conver-
is stripped together with the steam generated sion and selectivity. This necessitates high re-
by the heat of reaction. The gaseous products cycling rates, thereby increasing costs. The lack
are quenched with water and further treated in a of selectivity also requires additional outlets for
manner similar to gas-phase processes. major byproducts (1,1-dichloroethane and tri-
Although time – space yields and selectivi- chloroethane), which may not always exist.
ties are comparable to the gas-phase process and The cost advantage of ethane based processes
feed impurities can be tolerated, the liquid-phase further diminishes if cracker capacity for the eth-
process is not industrially used. The main rea- ylene supply and the infrastructure (loading sta-
son may be the troublesome handling of highly tions, storage tanks, etc.) are already available.
corrosive aqueous solutions at an elevated tem- Research is directed toward the development
perature and high pressure, even though similar of more specific catalysts, e.g, zeolites, and a
problems have not been restrictive for the liquid- direct route for producing VCM from ethane
phase hydrochlorination of methanol (see page without isolating EDC followed by cracking (see
13). Wastewater treatment may also pose more Section 3.1.3.4). Such processes may offer true
problems compared to gas-phase processes, be- cost advantages for plants with easy access to
cause heavy metal contamination occurs. More ethane (U.S. gulf coast) and good integration
information on homogeneously catalyzed oxy- into other CHC plants for economical byproduct
chlorination may be found in the literature [209]. recovery.

1,2-Dichloroethane from Ethane. The sub- Other Processes. The production of 1,2-di-
stantial cost margin between ethane and ethyl- chloroethane from ethanol [214] is not industri-
ene has prompted considerable research on di- ally used. It might be of interest if the cost for
rect ethane oxychlorination. This oxychlorina- ethanol derived from biomass were to become
tion reaction is theoretically possible and pro- competitive [107, 108].
ceeds via the sequence ethane – monochloro- 1,2-Dichloroethane is also a byproduct of
ethane – dichloroethane. oxirane (ethylene oxide) production via the old
Several processes comprising ethane and chlorohydrine route. The EDC yield can be im-
chloroethane oxychlorination or reacting mix- proved up to 50 % by process modifications
[215].
42 Chlorinated Hydrocarbons

Because oxirane (ethylene oxide) is mostly frequently found as an unwanted byproduct in

produced by direct oxidation, this process is not chlorinated hydrocarbon processes.
important for EDC production. The Dow Chemical Co. began commercial
production in the early 1950’s. With the devel-
opment of effective stabilizer systems, 1,1,1-
2.3.4. Uses and Economic Aspects trichloroethane has become one of the ma-
jor solvents for cold and vapor degreasing as
Based on U.S. figures for 1981, ca. 85 % of the well as several other applications. 1,1,1-Tri-
total EDC production is used for the produc- chloroethane is in strong competition with tri-
tion of vinyl chloride. 10 % is used in the pro- chloroethylene (see Section 3.4.4) and has re-
duction of chlorinated solvents such as 1,1,1- placed this solvent in many fields.
trichloroethane and tri- and tetrachloroethylene.
The rest goes into various processes mainly for
the synthesis of ethylenediamines. Its use as 2.4.1. Physical Properties
a solvent (dewaxing, deparaffinizing petroleum
Mr 133.41
fractions, and coating remover) is marginal. mp − 33 ◦ C
EDC is further used in leaded gasoline as a lead bp at 101.325 kPa 74.1 ◦ C
scavenger. With the increasing trend toward un-  at 20 ◦ C 1.325 g/cm3
n20
D 1.4377
leaded fuel, however, this market will decline in Vapor pressure at
future. 0 ◦C 4.900 kPa
In Europe, market figures seem to be com- 20 ◦ C 13.300 kPa
parable to those in the US, if not shifted even 40 ◦ C 32.000 kPa
60 ◦ C 62.700 kPa
more toward vinyl chloride production, because 70 ◦ C 88.000 kPa
almost all European EDC plants are forward in- 80 ◦ C 120.000 kPa
0
tegrated to VCM units. Heat of formation (liquid) ∆H298 − 170 kJ/mol
Specific heat (liquid 20 ◦ C) 1.004 kJ kg−1 K−1
Production in 1985 is estimated at ca. 7 × 106
Heat of evaporation at 298 K 32 kJ/mol
t for US, 8 × 106 t in Europe, and 2.5 × 106 t in Critical temperature 585 K
Japan. Critical pressure 4500 kPa
Installed capacity is ca. 10 × 106 t in North Viscosity at 20 ◦ C 0.86 × 10−3 Pa s
Surface tension at 20 ◦ C 25.6 × 10−3 N/m
America, 10 × 106 t in Western Europe, and 3.5 Coefficient of cubical expansion
× 106 t in Japan. (0 – 30 ◦ C) 0.0013 K−1
The future average growth rate is difficult to Dielectric constant at 20 ◦ C 7.5
predict, since EDC production depends heavily Flash point (closed cup) none
Ignition temperature (air) 537 ◦ C
on the big PVC consumers, the automotive in- Explosive limits in air at 25 ◦ C 8.0 – 10.5 vol%
dustry and the construction business, and has, 1,1,1-trichloroethane
therefore, been subjected to severe fluctuations Solubility in water at 20 ◦ C 0.095 wt %
in the past. The growth rate may be estimated at Solubility of water in
1,1,1-trichloroethane at 20 ◦ C 0.034 wt %
ca. 2 – 5 % for the decade 1985 – 1995.
New EDC plants in construction or in the 1,1,1-Trichloroethane is a clear liquid at am-
planning phase will preferentially be located in bient temperature with a characteristic ethereal
developing countries to increase autonomy from odor. It is soluble in all common organic solvents
imports and in oil-producing countries to for- and is a very good solvent for fats, paraffins, and
ward integrate refineries and basic chemicals al- other organic compounds.
ready produced. Some binary azeotropes are shown in Ta-
ble 15.

2.4. 1,1,1-Trichloroethane
2.4.2. Chemical Properties
1,1,1-Trichloroethane [71-55-6] was first syn-
thesized in the mid-19th century. It was not used Pure 1,1,1-trichloroethane is very unstable and
industrially for more than 100 years and was tends to undergo dehydrochlorination. Non-
catalyzed pyrolytic decomposition is almost
 Chlorinated Hydrocarbons 43

complete at 300 – 400 ◦ C [216]. When cat- based on the 1,1-dichloroethane route, and ca.
alyzed by metal salts [217], aluminum fluo- 10 % is made by direct ethane chlorination. In
ride [218], alumina [219], or others [220], this Europe too, the 1,1-dichloroethane route is used
reaction proceeds at considerably lower tem- by the largest producers.
peratures. Dehydrochlorination yields dichloro- Compared to the latter process, the produc-
ethylenes and hydrogen chloride. High mo- tion from 1,1-dichloroethylene has the disadvan-
lecular mass products may also be obtained tage that more expensive chlorine is required, be-
by polymerization of dichloroethylene [219]. cause one-fourth of the total chlorine required
Phosgene formation at elevated temperature in is lost as inorganic chloride. In addition, this
the presence of air is marginal [221]. Com- route requires an aqueous system because di-
pared to olefinic chlorination solvents (tri- and lute NaOH is used for the 1,1,2-trichloroethane
tetrachloroethylene) used in similar applica- dehydrochlorination (see page 68), which may
tions, 1,1,1-trichloroethane shows better stabil- cause environmental problems. Furthermore,
ity against oxidation [222]. Photochemical ox- 1,2-dichloroethane as feedstock for the 1,1-di-
idation yields phosgene, carbon monoxide, and chloroethane route is more readily available
hydrogen chloride [223]. Hydrolysis with wa- than 1,1,2-trichloroethane. The HCl generated
ter and aqueous acid yields acetyl chloride and by 1,1-dichloroethane chlorination can be used
acetic acid [224]. Under normal conditions, this in other processes such as Oxy-EDC (see page
reaction proceeds slowly. Dehydrochlorination 37) or methanol hydrochlorination (see page
to 1,1-dichloroethylene takes place in alkaline 11).
solutions. In other words, the first route is a source of
HCl, whereas the second route consumes HCl.
Table 15. Binary azeotropes formed by 1,1,1-trichloroethane
These aspects may have been also decisive for
wt % Component Azeotrope the implementation of the various processes in
boiling point
(101.3 kPa),
integrated CHC plants.
◦
C Even though photochemical reactions are
rarely used for industrial purposes because re-
4.3 water 65.0
23.0 methanol 55.5 actor design and operation is somewhat trouble-
17.4 ethanol 64.4 some, the photochemical reaction is preferred
17.0 isopropanol 68.2 for 1,1,1-trichloroethane preparation from 1,1-
17.2 tert-butanol 70.2
dichloroethane because of its higher selectivity
compared to thermal chlorination.
1,1,1-Trichloroethane is extremely corrosive The direct chlorination of ethane is the least
to aluminum. Inhibitors must be used inevitably. used route because of its lack of selectivity.
Dry 1,1,1-trichloroethane moderately corrodes Besides the three routes mentioned above,
iron and zinc. Corrosion, however, increases several other processes have been proposed, but
with the water content. are not used on an industrial scale.
1,1,1-Trichloroethane from 1,1-Di-
chloroethane. This process uses 1,2-dichloro-
2.4.3. Production ethane (EDC) as feedstock which is rearranged
to 1,1-dichloroethane via cracking to vinyl chlo-
For the industrial production of 1,1,1-tri- ride (see Section 3.1.3.2) followed by the addi-
chloroethane, three different routes are in use: tion of HCl in the presence of a catalyst.
1) From 1,1-dichloroethane by thermal or pho- During the final step, 1,1-dichloroethane is
tochemical chlorination thermally or photochemically chlorinated.
2) From 1,1,2-trichloroethane via 1,1-dichloro-
ethylene and consecutive hydrochlorination
3) From ethane by direct chlorination
In the United States, more than 70 % of the
1,1,1-trichloroethane is produced by the 1,1-
dichloroethane process. An additional 20 % is
44 Chlorinated Hydrocarbons

Photochemical Chlorination. Photochemi- Double-well UV lamps with external cooling

cal chlorination is used mostly, because this [231] are used to prevent coking and to keep the
reaction can be carried out at a lower temper- shutdown frequency tolerable.
ature, which increases the selectivity toward Process Description (Fig. 19). Finely dis-
1,1,1-trichloroethane [225]. persed 1,1-dichloroethane is fed together with
Preferred temperatures range between 80 and chlorine into an adiabatic reactor equipped with
160 ◦ C and the reactor pressure may average an actinic light source (300 – 550 nm). Di-
0.1 – 0.4 MPa. Reactor design for photochemical chloroethane is fed in excess up to 10 M to dis-
chlorination is a compromise: although selectiv- sipate the heat of reaction through evaporation
ity is increased in a plug-flow reactor [226], the and to suppress consecutive chlorination reac-
systems in use resemble back-mixed tank reac- tions. Reactor temperature averages between 80
tors (CSTR-characteristic) due to the need for – 100 ◦ C at pressures of 0.1 – 1.0 MPa.
sufficient actinic light radiation. The reaction products are separated by distil-
Typical byproducts are 1,1,2-trichloroethane, lation. In the first step, 1,1-dichloroethane is dis-
1,1,1,2- and 1,1,2,2-tetrachloroethane, and pen- tilled together with hydrogen chloride and unre-
tachloroethane, which may represent up to 30 % acted chlorine. HCl is then separated in a second
of the yield. tower. Dichloroethane and chlorine are recycled
To minimize the formation of tetra- and more to the reactor.
highly chlorinated byproducts and to dissipate The high-boiling components of the sump
the heat of formation, excess 1,1-dichloroethane phase from the first tower are separated in at
is fed (3 – 10 M) to chlorine. least two more steps yielding the crude prod-
In order to maintain the formation of un- ucts, which are then further purified.
wanted 1,1,2-trichloroethane as low as possi- Thermal Chlorination [232 – 234]. Fluidized-
ble, the photochemical reaction is preferably bed reactors offer the best technical solution
carried out in the vapor phase, because liq- for thermal chlorination because their uniform
uid-phase chlorination favors the synthesis of temperature profile minimizes the cracking re-
1,1,2-trichloroethane. Maximum selectivity to- actions of 1,1,1-trichloroethane and reactor cok-
ward 1,1,1-trichloroethane is ca. 90 % [227], ing. Sand or silica [234], which must be free of
which may, however, not be achieved in in- iron, is used as a bed material.
dustrial processes. Catalytic traces of iodine or Preheating of the reactants is required to
iodine-containing compounds were also found maintain a reaction temperature of 350 – 450 ◦ C,
to increase the selectivity [228]. which is necessary to start the radical chain re-
After separation from 1,1,1-trichloroethane, action.
1,1,2-trichloroethane can be used for the produc- Excess 1,1-dichloroethane is again added in
tion of 1,1-dichloroethylene (vinylidene chlo- proper dilution to avoid product losses (heavies
ride see Section 3.2). The tetrachlorinated prod- formation).
ucts may be used either in the production of tri- Equipment and processing is quite similar to
chloroethylene (see Section 3.4.3) or, without the photochemical system.
separation together with pentachloroethane, as Although 1,1,1-trichloroethane yields of up
feed for the perchloroethylene process. to 82 % have been reported [233], actual yields
Care must be taken to exclude traces of iron, may be considerably lower or poor conversions
which is a well-known promoter for the forma- with higher energy requirements for dichloro-
tion of 1,1,2-trichloroethane through a cracking ethane recycling must be accepted. As far as
– addition sequence. Monel or other copper – product yield, selectivity, and specific energy
nickel alloys are the preferred construction ma- consumption are concerned, this process is in-
terials for reactor and distillation equipment. ferior to photochemical chlorination.
Special distillation processes using stabiliz- Other Processes. Catalytic liquid-phase chlo-
ers [229] or thin-film evaporations [230] have rination of 1,1-dichloroethane using phosphorus
been patented to avoid decomposition of 1,1,1- catalysts (PCl5 ) [235] as well as the highly selec-
trichloroethane during cleanup. tive chlorination by chlorine monoxide [236] are
not industrially used. Either selectivity (PCl5 ) or
 Chlorinated Hydrocarbons 45

Figure 19. 1,1,1-Trichloroethane process (photochlorination)

a) Preheater; b) Photoreactor; c) Lights – heavies separation; d) Reboiler; e) Cooler; f) HCl tower; g) 1,1,1-Trichloroethane
tower; h) 1,1,2-Trichloroethane tower

technical problems (Cl2 O) do not allow large- The reaction is carried out at 80 – 120 ◦ C in a
scale production. packed tower or recirculation reactors. Because
1,1,1-Trichloroethane from 1,1,2-Tri- alkaline brine is used, nickel is applied as a con-
chloroethane. The overall reaction sequence struction material. Crude 1,1-dichloroethylene
again begins with 1,2-dichloroethane, which is is withdrawn by live steam injection or flash
chlorinated to form 1,1,2-trichloroethane. 1,1- evaporation and distilled.
Dichloroethylene is obtained by dehydrochlori- In order to avoid polymerization of 1,1-di-
nation and is then hydrochlorinated to 1,1,1-tri- chloroethylene, all feed streams should be free
chloroethane: of oxygen (< 1 mg/kg), or stabilizers (radical
scavengers like phenols or amines) should be
used.
The hydrochlorination of 1,1-dichloroethyl-
ene is carried out in a manner similar to the pro-
duction of 1,1-dichloroethane from vinyl chlo-
ride at temperatures between 40 – 80 ◦ C and in
As with the 1,1-dichloroethane route, an in- the presence of a Lewis acid catalyst (FeCl3 )
terim rearrangement via dehydrochlorination is [242]. Reactant ratios are almost stoichiomet-
again required. However, pyrolytic gas-phase ric or with a slight excess of HCl. The 1,1,1-
dehydrochlorination of 1,1,2-trichloroethane trichloroethane formed can be used as solvent,
does not have the required selectivity toward 1,1- but others such as 1,1,2-trichloroethane and
dichloroethylene — the favored product is 1,2- perchloroethylene have also been mentioned
dichloroethylene (see Section 3.3) — to be in- [243]. Care must be taken to avoid entrainment
dustrially attractive [237]. A yield increase to of catalyst traces during purification. Remain-
more than 90 % is only possible in aqueous sys- ing traces of catalyst and hydrogen chloride can
tems using calcium hydroxide [238] or ammonia be removed by addition of ammonia [244] and
[239] and some of its derivatives [240]. Aqueous distillation or by careful filtration of the distilled
NaOH is primarily used for dehydrochlorination 1,1,1-trichloroethane over partially deactivated
[241]. NaOH flake beds or weak ion-exchange resins.
The NaCl-containing NaOH (8 – 10 wt % Overall yields of more than 90 % are obtainable.
NaOH, 15 – 20 wt % NaCl) from diaphragm In a special process carried out by Atochem
cells can be used directly without further evap- (France), 1,1-dichloroethylene is produced as
oration. The use of an aqueous system however, byproduct from the high-temperature chlorina-
results in loss of chlorine, which is discarded as tion of ethylene for the production of vinyl chlo-
a salt (CaCl2 and NaCl). ride [245] (see Section 3.1.3.4). After separation
46 Chlorinated Hydrocarbons

from other byproducts, it can be hydrochlori- The photochemical chlorination of mono-

nated as usual to give 1,1,1-trichloroethane as a chloroethane has also been described [250].
valuable byproduct. All of these processes have no distinct ad-
A similar process has been patented by the vantages over the two basic methods that be-
FMC Corp. [243]. In this case ethylene is fed gin with 1,2-dichloroethane because of a lack
to the hydrochlorination stage forming mono- of selectivity. They are, therefore, currently of
chloroethane, which is then subjected to high no importance for the industrial production of
temperature chlorination to give 1,1-dichloro- 1,1,1-trichloroethane.
ethylene.
1,1,1-Trichloroethane from Ethane. The
direct synthesis of 1,1,1-trichloroethane has 2.4.4. Uses and Economic Aspects
been patented by the Vulcan Materials Company
and is mainly used in the United States: 1,1,1-Trichloroethane is used as a solvent in nu-
merous industrial applications such as cold and
CH3 −CH3 +3Cl2 →CH3 −CCl3 +3HCl hot cleaning and vapor degreasing. Formulations
0
∆H298 = −330kJ/mol are used as solvent for adhesives and metal cut-
ting fluids [251].
The highly exothermic reaction can be con-
New applications have been found in tex-
trolled by recycling the chloroethane byprod-
tile processing and finishing and in dry clean-
ucts (monochloroethane, 1,1-, and 1,2-dichloro-
ing, where 1,1,1-trichloroethane can replace the
ethane), which consume some of the reaction
widely used perchloroethylene.
heat by endothermic dehydrochlorination reac-
Special grades are used for the development
tions, so that an adiabatic reactor can be used.
of photoresists in the production of printed cir-
Hot spot temperatures of ca. 440 ◦ C are ob-
cuit boards. Because of its lower toxicity, 1,1,1-
tained. Mean residence times of 10 – 20 s at re-
trichloroethane has replaced trichloroethylene in
actor pressures of 0.3 – 0.5 MPa are found in the
many fields, especially in the United States. In
patent literature [246].
Europe, however, trichloroethylene has main-
Due to the rigorous reaction conditions and
tained its leading position.
the long reaction sequence, numerous byprod-
Further advantages of 1,1,1-trichloroethane
ucts are formed which require extensive equip-
are its graduated solvency, which allows it to be
ment for postprocessing after quenching of the
used even in very sensitive areas, its good evap-
reactor gas. Even extractive distillation steps
oration rate, and the fact that it has no fire or
have been considered [247].
flash point.
Both 1,1- and 1,2-dichloroethane are recy-
Because it readily reacts with aluminum and
cled. Vinyl chloride and vinylidene chloride
other metals, inhibitors must be added prior
are hydrochlorinated. 1,1-Dichloroethane from
to industrial use. The inhibitor systems, which
vinyl chloride hydrochlorination is added to the
may account for 3 – 8 % of the formulation,
recycle and 1,1,1-trichloroethane resulting from
mainly comprise such acid acceptors as ep-
the vinylidene chloride is drawn off.
oxides, ethers, amines, and alcohols as well as
At optimal conditions, the reaction product
such metal stabilizers as nitro- and cyano-organo
contains 60 – 70 mol% 1,1,1-trichloroethane and
compounds, which build complexes, thereby de-
20 mol% vinylidene chloride. Overall ethane
activating metal surfaces or catalytic salt traces.
yields of 60 % and chlorine yields of 93 % are
Several formulations for proprietary grades of
obtained.
1,1,1-trichloroethane have been filed and are in
The advantage of the cheaper raw material
use [252].
ethane is, at least partially, offset by the higher
U.S. producers are The Dow Chemical Co.,
equipment costs and the lower overall yields.
Pittsburgh Plate Glass Inc., and the Vulcan Ma-
Other Processes. Other patents use mono- terials Co. In Europe, 1,1,1-trichloroethane is
chloroethane as feedstock for the thermal chlo- produced by The DOW Chemical Co., ICI Ltd.,
rination [231, 248] or monochloroethane is Atochem, and Solvay.
formed in situ by feeding additional ethylene to European and U.S. capacities together
the reactor under mild conditions [249]. amount to ca. 600 000 t. Production in 1984 was
 Chlorinated Hydrocarbons 47
Table 16. Binary azeotropes formed by 1,1,2-trichloroethane
estimated to be ca. 450 000 t (Europe ca. 150
000 t). In Europe, 1,1,1-trichloroethane strongly wt % Component Azeotrope boiling
competes with trichloroethylene and may re- point (101.3 kPa),
◦
C
place this solvent in several applications, which
could affect the future growth rate. 97 methanol 64.5
57 perchloroethylene 112.0
However, more stringent regulations in many 70 ethanol 77.8
industrialized countries requiring the reduction 15 water 85.3 (at 97.300 kPa)
of losses from vapor degreasing units and other
equipment may adversely affect future demand.
Present capacity seems to be sufficient to sup- For some binary azeotropes, see Table 16.
ply the market for the next decade.
2.5.2. Chemical Properties
2.5. 1,1,2-Trichloroethane
At an elevated temperature (400 – 500 ◦ C),
1,1,2-Trichloroethane [79-00-5] is primarily an 1,1,2-trichloroethane is easily dehydrochlori-
unwanted byproduct of several chlorination pro- nated to give a mixture of cis- and trans-1,2-
cesses such as the production of 1,2-dichloro- dichloroethylene, 1,1-dichloroethylene, and hy-
ethane and the chlorination of ethane or 1,1-di- drogen chloride [253].
chloroethane to 1,1,1-trichloroethane. Addition of alumina catalysts or an increase
It has a very high solvency, but the relatively in temperature favors 1,2-dichloroethylene for-
high toxicity limits its uses. mation. In aqueous alkaline solution, 1,1,2-tri-
1,1,2-Trichloroethane is only important as an chloroethane is selectively dehydrochlorinated
intermediate in the production of 1,1-dichloro- to 1,1-dichloroethylene [254]. This reaction pro-
ethylene and to some extent for the synthesis of ceeds faster than that with 1,1,1-trichloroethane.
tetrachloroethanes. In water, hydrolysis takes place, especially un-
der reflux conditions. Hydrolysis, however, pro-
ceeds slower than with the 1,1,1-isomer.
2.5.1. Physical Properties 1,1,2-Trichloroethane is highly corrosive to
aluminum, iron, and zinc. Addition of water in-
Mr 133.41 creases the rate of corrosion.
mp − 37 ◦ C If chlorinated, a mixture of the isomeric tetra-
bp at 101.325 kPa 113.5 ◦ C
 at 20 ◦ C 1.4432 g/cm3
chloroethanes is formed.
n20
D 1.4711
Vapor pressure at
30 ◦ C 4.800 kPa 2.5.3. Production
90 ◦ C 49.200 kPa
100 ◦ C 67.300 kPa
110 ◦ C 90.600 kPa The industrial production of 1,1,2-tri-
114 ◦ C 101.800 kPa chloroethane proceeds by two routes:
0
Heat of formation (liquid) ∆H298 − 188 kJ/mol
Specific heat (liquid, 20 ◦ C) 1.113 kJ kg−1 K−1 1) Selective chlorination of 1,2-dichloroethane:
Heat of evaporation at 298 K 39.1 kJ/mol−1
Viscosity at 20 ◦ C 1.20 × 10−3 Pa s
Surface tension at 20 ◦ C 32.5 × 10−3 N/m
Coefficient of cubical expansion
(0 – 25 ◦ C) 0.001 K−1
Autoignition temperature (air) 460 ◦ C 2) Addition of chlorine to vinyl chloride:
Solubility in water at 20 ◦ C 0.45 wt %
Solubility of water in CH2 = CHCl+Cl2 →CH2 Cl−CHCl2
1,1,2-trichloroethane at 20 ◦ C 0.05 wt % 0
∆H298 = −224kJ/mol

1,1,2-Trichloroethane is a clear liquid at am-

The liquid-phase 1,2-dichloroethane route is
bient temperature with a sweet smell. It is not
most often used in industrial processes when
flammable and easily miscible with most organic
solvents.
48 Chlorinated Hydrocarbons

1,1,2-trichloroethane is needed for the produc-

tion of 1,1-dichloroethylene (see Section 3.2.3)
and 1,1,1-trichloroethane (see Section 2.4.3).
The vinyl chloride route plays a minor role
because of the more expensive feedstock and
overall higher energy requirements.
A large portion of the current demand for
1,1,2-trichloroethane can be satisfied by the use
of 1,1,2-trichloroethane obtained as a byprod-
uct from the production of 1,1,1-trichloroethane.
Because the latter is mostly produced by pho-
tochemical chlorination of 1,1-dichloroethane
(see page 43), substantial amounts of 1,1,2-tri-
chloroethane are obtained as a byproduct. Figure 20. Process for the production of 1,1,2-tri-
1,1,2-Trichloroethane is also one of the ma- chloroethane by ethylene-induced liquid-phase chlorina-
tion [256]
jor byproducts in the production of 1,2-dichloro- a) Reactor; b) Preheater for priming; c) Light-ends
ethane (see Section 2.3.3) and can be distilled tower (1,2-dichloroethane); d) Cooler (brine); e) 1,1,2-
from the heavy ends of these processes. Trichloroethane finishing tower; f) Cooler (water);
Thus, 1,1,2-trichloroethane is deliberately g) Reboiler; h) Condenser; i) Knock-out drum; j)
1,2-Dichloroethane wash tower
produced only when 1,1,1-tri- or 1,2-dichloro-
ethane sources are unavailable or for the balanc-
ing of feedstocks. Even at low conversion rates, the heat of re-
action is sufficient to maintain the reaction. Pre-
1,1,2-Trichloroethane from 1,2-Di- heating of the recycled stream is, therefore, only
chloroethane. This process was patented by the required for startup.
Pittsburgh Plate Glass Co. [255] and by the Toa The liquid phase from the reactor is first dis-
Gosei Chemical Industries [256]. It comprises tilled to separate the excess 1,2-dichloroethane,
the noncatalytic chlorination of 1,2-dichloro- which is then recycled to the reactor.
ethane. The reaction is carried out in the liquid The crude 1,1,2-trichloroethane is then sep-
phase at temperatures between 100 – 140 ◦ C. arated from the higher chlorinated byproducts,
The addition of ethylene induces the reaction. mainly tetrachloroethanes, by further distilla-
The reaction mechanism has been intensively tion.
studied but is not yet clearly and fully under- The gaseous reaction phase is cooled and
stood [257]. Radical chlorination is very likely high-boiling components are condensed. The re-
because metal salts, which support ionic reac- maining 1,2-dichloroethane in the HCl gas is
tions, must be excluded. The reactants should washed out with crude 1,1,2-trichloroethane and
be free of radical-scavenging oxygen. Because recycled to the reactor.
consecutive chlorination to tetrachloroethanes Other catalysts such as azodiisobutyronitrile
and pentachloroethane takes place, the conver- (ADIB) or peroxides [258], actinic light [159,
sion per pass must be kept at 10 – 20 % for 256, 259] (liquid-phase photochlorination of
an optimum trichloroethane yield [256]. Since 1,2-dichloroethane favors 1,1,2-trichloroethane,
backmixing also favors the formation of higher whereas by gas-phase photochlorination, 1,1,1-
chlorinated products, adiabatic plug-flow reac- trichloroethane is preferentially obtained and
tors are preferred. phosphoros chloride have been proposed instead
Nickel alloys or nickel-clad steel is preferred of ethylene [260]. Gas-phase chlorination cat-
as a structural material. As with most chlorina- alyzed by metal chlorides has also been patented
tion reactions, water must be removed to mini- [261].
mize corrosion. All these processes, however, are commer-
Process Description (Fig. 20). Ethylene, cially more demanding and offer no real advan-
chlorine, and fresh and recycled 1,2-dichloro- tage over the ethylene-induced reaction.
ethane are fed to a tubular reactor. Instead of chlorinating 1,2-dichloroethane,
ethylene can be used as a starting material. Either
 Chlorinated Hydrocarbons 49

liquid-phase chlorination with chlorine [262] 2.6. 1,1,1,2-Tetrachloroethane

(see DC – EDC, page 35) or catalytic gas-phase
oxychlorination with HCl in fixed- or fluidized- 1,1,1,2-Tetrachloroethane [630-20-6] was first
bed reactors [263] (see Oxy – EDC, page 37) synthesized by A. Mouneyrat in 1898. Today
can be used. The selectivity toward 1,1,2-tri- it is a byproduct in many industrial chlorination
chloroethane is generally lower with this pro- reactions of C2 hydrocarbons. It is, however, not
cess. Especially in gas-phase oxychlorination, produced on an industrial scale.
substantial yield losses by “deep oxidation” (CO If recovered from such industrial processes
and CO2 formation) may occur. as the production of 1,1,1- and 1,1,2-tri-
1,1,2-Trichloroethane from Vinyl Chlo- chloroethane, it can be used as feedstock for
ride. The reaction is carried out similar to the the production of trichloroethylene (see Section
DC-EDC process (see page 35) in liquid phase 3.4.3) and perchloroethylene (see page 76 ).
(trichloroethane) at temperatures between 50 Because of its high toxicity, it is not used as
and 90 ◦ C. As with other addition reactions, a solvent.
Lewis-acid catalysts like FeCl3 , AlCl3 or SbCl5
are used, but actinic light catalysis also seems
possible [264]. Yields of more than 90 % are ob- 2.6.1. Physical Properties
tainable. Mr 167.86
Catalytic oxychlorination of vinyl chloride mp − 68.7 ◦ C
with hydrogen chloride [265] or oxychlorina- bp at 101.325 kPa 130.5 ◦ C
tion of mixtures of ethylene and vinyl chloride  at 20 ◦ C 1.5468 g/cm3
n20
D 1.4822
in fixed or fluidized beds [266] is also possible. Viscosity at 20 ◦ C 1.50 × 10−3 Pa s
Conditions are very similar to those for the Oxy Surface tension at 20 ◦ C 32.1 × 10−3 N/m
– EDC process (see page 37). Instead of vinyl Solubility of water in
chloride, acetylene can also be used as a feed- 1,1,1,2-tetrachloroethane at 20 ◦ C 0.06 wt %

stock [267]. In this case, the catalyst must be 1,1,1,2-Tetrachloroethane is a colorless, non-
doped with mercury salts in order to achieve ad- flammable heavy liquid.
equate conversion.
Hydrochlorination of 1,2-dichloroethylene
[268] may be of interest only for the recovery 2.6.2. Chemical Properties
of an unusable byproduct.
In general, 1,1,1,2-tetrachloroethane is more sta-
ble than its symmetrically substituted isomer.
2.5.4. Uses and Economic Aspects. Thermal decomposition at 500 – 600 ◦ C yields
trichloroethylene and hydrogen chloride. Tetra-
As previously mentioned, 1,1,2-trichloroethane chloroethylene can be formed by disproportion-
only plays a role as an intermediate for the ation [269]. The thermal decomposition is cat-
production of 1,1,1-trichloroethane and 1,1-di- alyzed by numerous compounds [270], mainly
chloroethylene. Lewis acids such as FeCl3 and AlCl3 .
The relatively high toxicity, which is typical Dichloroacetyl chloride is obtained through
for all 1,2-substituted chloroethanes, does not oxidation [271].
allow general use as a solvent.
Based on production figures for 1,1,1-tri-
chloroethanes and 1,1-dichloroethylene, West- 2.6.3. Production
ern World production of 1,1,2-trichloroethane is
estimated to be at 200 000 –220 000 t/year for 1,1,1,2-Tetrachloroethane is not produced on
1984. an industrial scale. It is an undesired byprod-
In Western Europe, approx. 40 000 t was pro- uct mainly from the production of 1,1,1-tri-
duced in 1984. chloroethane from 1,1-dichloroethane, 1,1,2-
trichloroethane and 1,1,2,2-tetrachloroethane
from 1,2-dichloroethane. The most economical
50 Chlorinated Hydrocarbons
Dielectric constant at 20 ◦ C 8.00
use is its conversion to tetrachloroethylene in the Solubility in water at 20 ◦ C 0.3 wt %
chlorinolysis process (see page 76 ). Solubility of water in 1,1,2,2-
It can be prepared in highly purified form by tetrachloroethane at 20 ◦ C 0.03 wt %
isomerization of 1,1,2,2-tetrachloroethane or by
chlorination of 1,1-dichloroethylene at approx. 1,1,2,2-Tetrachloroethane is a clear heavy,
40 ◦ C in the liquid phase. Aluminum chloride is nonflammable liquid with a sweetish odor. It is
used in both reactions as a Lewis-acid catalyst well miscible with all common organic solvents
[272]. and exhibits the highest solvency of all aliphatic
chlorohydrocarbons.
1,1,2,2-Tetrachloroethane does not form
2.7. 1,1,2,2-Tetrachloroethane explosive mixtures with air. Some binary
azeotropes are shown in Table 17.
1,1,2,2-Tetrachloroethane [79-34-5] was first
Table 17. Binary azeotropes formed by 1,1,2,2-tetrachloroethane
synthesized by M. Berthelot and E. Jungfleisch [273]
in 1869. Based on experiments by A.
wt % Component Azeotrope boiling
Mouneyrat, the first industrial scale production
point (101.3 kPa),
process was developed by A. Wacker in 1903. ◦
C
Thus, 1,1,2,2-tetrachloroethane became the first
68.0 formic acid 99.3
chloroethane to be produced in large quantities. 55.0 cyclohexanone 159.1
For almost 70 years this process, which con- 9.0 ethylene glycol 145.1
sists of the catalytic chlorination of acetylene, 7.0 isobutyric acid 144.8
1.8 monochloroacetic acid 146.3
was the basis for the production of such im-
60.0 propionic acid 140.4
portant solvents as trichloroethylene (Tri) and 45.0 styrene 143.5
tetrachloroethylene (Per). 31.1 water 93.2 (at 97.300 kPa)
However, with the continuing replacement of
trichloroethylene by 1,1,1-trichloroethane and
the development of more economical processes 2.7.2. Chemical Properties
for the production of perchloroethylene, 1,1,2,2-
tetrachloroethane has become less important for If moisture, air, and light are excluded, 1,1,2,2-
the production of chlorinated solvents. tetrachloroethane is sufficiently stable and can
be stored without adding stabilizers. At elevated
temperatures (> 400 ◦ C), it is cracked to tri-
2.7.1. Physical Properties chloroethylene and hydrogen chloride. Tetra-
chloroethylene may also be formed via dispro-
Mr 167.86 portionation [269, 270, 274]. The thermal crack-
mp − 42.5 ◦ C ing reaction can be promoted by a variety of cat-
bp at 101.325 kPa 146.5 ◦ C alysts [270].
 at 20 ◦ C 1.5958 g/cm3
n20 1.4942 To avoid cracking during distillation, vacuum
D
Vapor pressure at distillation is recommended. One patent claims
0 ◦C 0.180 kPa soft, nondecompositional evaporation by means
20 ◦ C 0.680 kPa
60 ◦ C 5.330 kPa
of a fluidized-bed evaporator [275].
91 ◦ C 18.700 kPa In weak alkali solutions, dehydrochlorination
118 ◦ C 46.700 kPa to trichloroethylene occurs. In strong alkali so-
138 ◦ C 82.700 kPa lutions, explosive dichloroacetylene is formed.
0
Heat of formation (liquid) ∆H298 − 195 kJ/mol−1
Specific heat (liquid, 20 ◦ C) 1.122 kJ kg−1 K−1
Decomposition in the presence of air can lead to
Specific heat (vapor, 146.5 ◦ C) 0.92 kJ kg−1 K−1 small quantities of phosgene.
Heat of evaporation at 298 K 45.2 kJ/mol−1 Chlorination under mild conditions (eventu-
Critical temperature 688 K ally induced by UV light or catalysts) yields
Critical pressure 4000 kPa
Viscosity at 20 ◦ C 1.77 × 10−3 Pa s
hexachloroethane via the pentasubstituted inter-
Surface tension at 20 ◦ C 35.0 × 10−3 N/m mediate [276]. Under more rigorous conditions
Coefficient of cubical expansion 0.00098 K−1 and more thermodynamic control (chlorinoly-
sis reaction, see Section 3.5.3), tetrachloroethyl-
 Chlorinated Hydrocarbons 51

ene and tetrachloromethane are formed as main In the Atochem process [245] (see Figure25),
products. Chlorination at 400 ◦ C in the presence 1,1,2,2-tetrachloroethane is produced from 1,2-
of charcoal favors cleavage which gives primar- dichloroethylenes by chlorination as an interme-
ily tetrachloromethane and hydrogen chloride diate for trichloroethylene synthesis.
[277]. Strong acids may hydrolyze 1,1,2,2-tetra- Several other processes have been patented,
chloroethane to glyoxal. but all of them are only of minor importance.
With hydrogen, hydrodechlorination to 1,2- 1,1,2,2-Tetrachloroethane from Acetylene.
dichloroethylenes occurs. The technical principle of carrying out this re-
Oxidation in air yields dichloroacetyl chlo- action has not changed much since the develop-
ride. ment of this process [278]. It is similar to the DC
– EDC process (see page 35) and other common
liquid-phase chlorination or hydrochlorination
2.7.3. Production reactions.
The reaction is carried out in the liquid phase
Industrial processes for the production of (tetrachloroethane) at 60 – 90 ◦ C. The reactor
1,1,2,2-tetrachloroethane consist of two main pressure is reduced to ca. 20 kPa in order to
routes: prevent the explosion of the chlorine – acety-
1) Addition of chlorine to acetylene: lene mixtures. Lewis-acid catalysts [278], pri-
marily FeCl3 , are dissolved in the tetrachloro-
ethane solvent from the reactor sump phase.
Gaseous acetylene and chlorine are fed to the
reactor sump. The highly exothermic reaction
2) Liquid-phase chlorination of ethylene or 1,2- provides enough heat to distill the tetrachloro-
dichloroethane ethane [279].
C2 H4 +3Cl2 →CHCl2 −CHCl2 +2HCl The upper part of the reactor is therefore
0
∆H298 = −436kJ/mol a distillation tower. Tetrachloroethane is with-
drawn from appropriate trays, and the overheads
CH2 Cl−CH2 Cl+2Cl2 →CHCl2 −CHCl2 +2HCl consisting mainly of 1,2-dichloroethylenes and
0
∆H298 = −216kJ/mol acetylene can be recycled to the reactor sump.
To control the heavies concentration in the sump
The acetylene route was used primarily in phase, a slipstream is withdrawn. Partial evapo-
the past. The ethylene-based process was de- ration for tetrachloroethane recovery followed
veloped during the late 1960s, when the hy- by high-temperature incineration with subse-
drocarbon feedstocks shifted toward ethylene. quent flue gas scrubbing is the best treatment
However, the acetylene process is still in use for this stream containing the spent catalyst.
— mainly in the Federal Republic of Germany Carbon steel can be used as a construction
— where acetylene is readily available as a by- material. Water and moisture should be strictly
product form naphtha crackers. Furthermore, the avoided in order to minimize corrosion and rapid
acetylene route has the distinct advantage of deactivation of the catalyst.
preferentially yielding the 1,1,2,2-isomer, which Chlorine and acetylene yields of 90 – 98 %
can easily be cracked to trichloroethylene. The have been reported.
ethylene-based process produces both isomers A similar process, using crude crack gas in-
in an approximately equimolar ratio because of stead of pure acetylene, has been patented [280].
its radical nature. Besides 1,1,2,2-tetrachloroethane, this process
1,1,2,2-Tetrachloroethane is also an inciden- also produces 1,2-dichloroethane from the eth-
tal byproduct of other production processes for ylene fraction of the crack gas feedstream.
chlorinated hydrocarbons, such as the produc- 1,1,2,2-Tetrachloroethane from Ethylene
tion of 1,1,1- and 1,1,2-trichloroethane. If nec- and from 1,2-Dichloroethane. Liquid-phase
essary, it is separated together with the unsym- chlorination of ethylene or the ethylene-induced
metric isomer and used for the production of chlorination of 1,2-dichloroethane is the same
trichloroethylene. process as that used for the production of 1,1,2-
52 Chlorinated Hydrocarbons

trichloroethane (see page 43). By increasing the as solvent for the production of chlorinated PVS
chlorine : ethylene or chlorine: dichloroethane [292]), it is very rarely used as a solvent because
ratios and optimizing the residence time, an al- of its high toxicity.
most equimolar mixture of 1,1,2,2- and 1,1,1,2- Production figures for 1,1,2,2-tetrachloro-
tetrachloroethane is obtained as the main prod- ethane cannot be estimated.
uct [256, 281].
Several kinetic studies have been performed
to determine the individual relative rate con- 2.8. Pentachloroethane
stants and to optimize the yield [281, 282].
At a temperature between 80 and 130 ◦ C, Pentachloroethane [76-01-7] was first synthe-
chlorine conversion as high as 100 % and max- sized by V. Regnault in 1839 – 1840 by chlori-
imum ethylene conversions of 95 – 98 % can be nation of monochloroethane.
achieved. Low-substituted products such as 1,2- In the past, pentachloroethane was produced
dichloroethane and 1,1,2-trichloroethane can as an intermediate for the tetrachloroethylene
be recycled [283], so that yield losses occur process (pentachloroethane pyrolysis). How-
only through the formation of penta- and hex- ever, it is an unwanted byproduct of many pro-
achloroethane. With some minor modifications, duction processes for chlorinated hydrocarbons
the process is carried out as described earlier (see and is mostly converted to tetrachloroethylene
page 43). Instead of 1,2-dichloroethane, 1,2-di- and tetrachloromethanes by chlorinolysis be-
chloroethylenes may be fed to the reactor, which cause other uses have almost disappeared.
favors the formation of the symmetric isomer
[284].
Similarly, the liquid-phase chlorination of 2.8.1. Physical Properties
mixtures containing a variety of chloroethanes
and chloroethylenes has been patented [285]. Mr 202.31
mp − 29.0 ◦ C
Other Processes. The liquid-phase chlori- bp at 101.325 kPa 162 ◦ C
nation of vinyl chloride or 1,1,2-trichloroethane  at 20 ◦ C 1.678 g/cm3
in the presence of AlCl3 as catalyst yields n20
D 1.5035
Vapor pressure at
1,1,2,2-tetrachloroethane with high selectivity 20 ◦ C 0.470 kPa
[286]. 60 ◦ C 3.470 kPa
Specific catalysts made from graphite- 80 ◦ C 7.860 kPa
intercalated copper or iron salts, alumina, and 100 ◦ C 17.330 kPa
120 ◦ C 33.330 kPa
organopolysiloxanes specifically yield 1,1,2,2- 140 ◦ C 60.000 kPa
tetrachloroethane by gas-phase chlorination (ca. 0
Heat of formation (liquid) ∆H298 − 188.4 kJ/mol
200 ◦ C, 0.1 – 1.0 MPa) of mixtures comprising Density of vapor
monochloroethane, 1,1- and 1,2-dichloroethane, (162 ◦ C, 101.325 kPa) 5.68 g/L
Specific heat (liquid, 20 ◦ C) 0.9 kJ kg−1 K−1
and 1,1,2-trichloroethane [287]. Heat of evaporation at 298 K 45.6 kJ/mol
The catalytic gas phase oxychlorination of Viscosity at 20 ◦ C 2.49 × 10−3 Pa s
1,2-dichloroethane, ethylene, vinyl chloride, Surface tension at 20 ◦ C 34.7 × 10−3 N/m
Coefficient of cubical expansion 0.0009 K−1
and 1,2-dichloroethenes has also been described
Dielectric constant at 20 ◦ C 3.6
[288]. Solubility in water at 20 ◦ C 0.05 wt %
Other processes use gas phase chlorination Solubility of water in
of 1,2-dichloroethane in a fluidized-bed [289] or pentachloroethane at 20 ◦ C 0.03 wt %
liquid-phase photochlorination of 1,2-dichloro-
Pentachloroethane is a colorless, heavy,
ethane [290] or 1,2-dichloroethylenes [291].
nonflammable liquid with a sweetish odor. It is
miscible in most common organic solvents and
2.7.4. Uses and Economic Aspects does not form explosive mixtures with air.
Some binary azeotropes are shown in Ta-
1,1,2,2-Tetrachloroethane is almost always used ble 18.
as an intermediate in the production of trichloro-
ethylene. Although it has a high solvency (e.g.,
 Chlorinated Hydrocarbons 53
Table 18. Binary azeotropes formed by pentachloroethane
irradiation can also be used. Stepwise chlo-
wt % Component Azeotrope boiling rination in a cascade system is also possible
point (101.3 kPa), [294].
◦
C
2) Ethylene-induced chlorination of 1,2-di-
3 acetamide 160.5 chloroethane [256]:
36 cyclohexanol 157.9
28 cyclohexanone 165.4
15 glycol 154.5
43 isobutyric acid 152.9
9.5 phenol 160.9
43.4 water 95.1 (at 97.300 kPa) This reaction is similar to that of 1,1,2-
trichloroethane (see page 43). Pen-
tachloroethane is obtained with lighter chlo-
2.8.2. Chemical Properties rinated products, which can be rechlorinated.
To avoid decomposition, pentachloroethane
If moisture and air are eliminated, pen- should be distilled at reduced pressure.
tachloroethane shows good stability even at el-
By oxychlorination of ethylene, 1,2-di-
evated temperatures (> 100 ◦ C). Pyrolysis at a
chloroethane, or other chlorinated C2 hydrocar-
temperature above 350 ◦ C yields tetrachloroeth-
bons, pentachloroethane is also obtained.
ylene and hydrogen chloride [293]. The dehy-
The main industrial source, however, is
drochlorination reaction is catalyzed by Lewis
the photochemical production of 1,1,1-tri-
acids and activated alumina. Dehydrochlorina-
chloroethane (see page 43) and the liquid-phase
tion also occurs in the presence of weak alkali
chlorination process for 1,1,2-trichloroethane
solution. Chlorination in the liquid phase in the
production (see page 43). Pentachloroethane
presence of a catalyst or induced by ethylene
formed in these processes is frequently not iso-
(see page 43) yields hexachloroethylene. Dry
lated but fed together with the tetrachloroethanes
pentachloroethane does not corrode iron; if it is
to the chlorinolysis process.
stored over longer periods of time, however, the
addition of amine stabilizers is recommended.
Dichloroacetyl chloride is formed with fum-
2.8.4. Uses and Economic Aspects
ing sulfuric acid. Air oxidation in the presence
of UV light gives trichloroacetyl chloride.
Because of its low stability and toxicity, uses for
In the presence of hydrogen fluoride and
pentachloroethane as a solvent (cellulose deriva-
Lewis acids such as SbCl5 – chlorine, substitu-
tives, rubbers, and resins) are insignificant.
tion occurs.
About 10 000 – 20 000 t/a (1984) of pen-
tachloroethane may be produced as a byprod-
2.8.3. Production uct in the Western World. Most of it is used for
the production of tetrachloroethylene and car-
Since tetrachloroethylene is more economically bon tetrachloride.
produced by the chlorinolysis process (see page
76 ), industrial production of pentachloroethane
has become unimportant and is presently no 2.9. Hexachloroethane
longer used.
If required, the synthesis can be performed Hexachloroethane [67-72-1] is at ambient tem-
by two routes: perature the only solid compound of all chlori-
nated ethanes and ethylenes. Because it has spe-
1) Chlorination of trichloroethylene: cific properties, such as a tendency to sublime
and a very high chlorine content, it has some
specific applications, which are limited, how-
ever, for toxicological and ecological reasons.
The reaction is best carried out in the liquid
phase. FeCl3 is used as a catalyst, but UV
54 Chlorinated Hydrocarbons

2.9.1. Physical Properties 2.9.3. Production

Mr 236.74
mp (closed capillary, as sublimes) 185 ◦ C
Limited industrial uses of hexachloroethane do
bp at 101.325 kPa 185 ◦ C not justify large-scale production processes.
Crystal structure: rhombic < 46 ◦ C A primary source for hexachloroethane is
triclinic 46 – 71 ◦ C from the production of tetrachloroethylene and
cubic > 71 ◦ C
Specific density at 20 ◦ C 2.094 g/cm3
carbon tetrachloride by chlorinolysis of hydro-
Vapor density at 185 ◦ C 6.3 g/L carbons and chlorinated hydrocarbon residues
Vapor pressure at (see page 76 ). It can be separated from the
20 ◦ C 0.290 kPa
residues by distillation and fractionated crystal-
40 ◦ C 1.330 kPa
80 ◦ C 2.400 kPa lization.
120 ◦ C 11.600 kPa For the intentional production of hex-
160 ◦ C 45.320 kPa achloroethane, tetrachloroethylene is chlori-
180 ◦ C 86.650 kPa
Heat of formation (liquid) ∆H2980
− 203.4 kJ/mol
nated batchwise in presence of iron chloride. The
Specific heat at 20 ◦ C 0.615 kJ kg−1 K−1 hexachloroethane crystallizes from the mother
Heat of sublimation at 298 K 59 kJ/mol liquor and is isolated. The mother liquor is re-
Cryoscopic constant 5.6 cycled and again chlorinated [296].
Solubility in water at 22 ◦ C 50 mg/kg
The photochemical chlorination of tetra-
Hexachloroethane forms white crystals with chloroethylene is performed similarily [297].
a camphor-like odor. It is not flammable.
Some binary azeotropes of hexachloroethane
2.9.4. Uses and Economic Aspects
are shown in Table 19.
Table 19. Binary azeotropes formed by hexachloroethane
Industrial uses of hexachloroethane are dimin-
wt % Component Azeotropic ishing, so that most hexachloroethane is either
boiling point recycled or incinerated with HCl — or chlorine
(101.3 kPa),
◦
C recovery depending on the individual technol-
ogy applied.
34 aniline 176.8
12 benzylic alcohol 182.0
Smaller quantities are used for the synthesis
25 monochloroacetic acid 171.2 of metal chlorides or for the production of fluo-
28 o-cresol 181.3 rocarbons.
30 phenol 173.7 Hexachloroethane is one of the more toxic
15 trichloroacetic acid 181.0
chloroethanes. Its use in plasticizer or rubber
formulations is, therefore, decreasing.
2.9.2. Chemical Properties Since no significant applications exist, pro-
duction figures cannot be estimated.
Hexachloroethane is fairly stable and sublimes Analysis, quality control, storage, and
without decomposition. At temperatures above transportation of the chloroethanes are
250 ◦ C, especially at 400 – 500 ◦ C, it is cracked treated with the chloroethylenes in Sections
(disproportionated) [295]: 3.6 and 3.7
2C2 Cl6 →C2 Cl4 +2CCl4
Small amounts of chlorine are also formed.
With metals like iron, zinc, and aluminum, chlo- 3. Chloroethylenes
rination reactions start at a higher temperature,
forming metal chlorides and tetrachloroethyl- The class of chloroethylene comprises:
ene. This reaction can be used for the synthesis Vinyl chloride (monochloroethylene, VCM)
of pure metal chlorides and for ultrapurification 1,1-Dichloroethylene (vinylidene chloride)
of metals. cis- and trans-1,2-Dichloroethylene
At moderate temperature hexachloroethane Trichloroethylene (Tri)
is stable against aqueous alkali and acids. At Tetrachloroethylene
temperatures above 200 ◦ C, hydrolysis to oxalic (perchloroethylene, Per, Perc).
acid occurs.
 Chlorinated Hydrocarbons 55

3.1. Vinyl Chloride (VCM) ride presently produced in the Western World is
based exclusively on ethylene.
In addition to ethylene and NaOH, vinyl chlo- In addition to its use as an intermediate in the
ride [75-01-4] is one of the world’s most impor- production of trichloroethane (1,1,1- and 1,1,2-
tant commodity chemicals. The 1984 worldwide trichloroethane), most vinyl chloride is used for
consumption averaged 12 – 15 million t/a. About polymerization to PVC.
25 % of the world’s total chlorine production is With the use of plasticizers and because of
required for its production. its high energy efficiency, PVC has become one
The importance of vinyl chloride results from of the most important industrial polymers. Even
the widespread use of poly(vinyl chloride), one though it is one of the oldest polymers, its ready
of the most important polymers. availability, relatively inexpensive production
The first synthesis of vinyl chloride dates by large plants, and the continuing development
back to 1830 – 1834 when V. Regnault ob- of new formulations [300] with widespread uses
tained it by dehydrochlorinating 1,2-dichloro- secure its attractiveness in the future.
ethane with alcoholic potash. In 1902, it was Several VCM plants were under construction
obtained by Biltz during thermal cracking of in 1986. Due to the feedstock and market situ-
the same compound. ation, the new plants will be preferentially lo-
However, at that time, the state of the art in cated either in oil-producing or in developing
polymer science and technology was not very countries.
sophisticated, and this discovery did not lead to
industrial or commercial consequences.
The basic work of F. Klatte [298] on the 3.1.1. Physical Properties
polymerization of vinylic compounds gave rise
to the industrial production of vinyl chloride in Mr 62.5
mp − 153.8 ◦ C
the 1930s. bp at 101.325 kPa − 13.4 ◦ C
Vinyl chloride was obtained by Klatte in  at − 14.2 ◦ C 0.969 g/cm3
1912 through catalytic hydrochlorination of at 20 ◦ C 0.910 g/cm3
acetylene [299]. This route was almost exclu- n20
D 1.445
Vapor pressure at
sively used for nearly 30 years. Because of the − 30 ◦ C 51.000 kPa
high energy requirements for acetylene produc- − 20 ◦ C 78.000 kPa
tion, its replacement by a cheaper substitute was − 10 ◦ C 115.000 kPa
0 ◦C 165.000 kPa
a challenge for a long time.
10 ◦ C 243.000 kPa
From 1940 – 1950 on, acetylene could be par- 20 ◦ C 333.000 kPa
tially replaced by ethylene, from which vinyl 30 ◦ C 451.000 kPa
chloride was produced by direct chlorination 40 ◦ C 600.000 kPa
50 ◦ C 756.000 kPa
to 1,2-dichloroethane and subsequent thermal Heat of formation (gaseous) ∆H 0298 + 35.2 kJ/mol
cracking. The first large production units for this Specific heat (liquid, 20 ◦ C) 1.352 kJ kg−1 K−1
route were first constructed by Dow Chemical (vapor, 20 ◦ C) 0.86 kJ kg−1 K−1
Co., Monsanto Chemical Co. and the Shell Oil Heat of evaporation (259.8 K) 20.6 kJ/mol
Critical temperature 429.8 K
Co. In these plants, the balance of HCl gener- Critical pressure 5600 kPa
ated by dichloroethane cracking, however, was Viscosity at − 40 ◦ C 0.34 × 10−3 Pa s
still achieved by acetylene hydrochlorination. at − 10 ◦ C 0.25 × 10−3 Pa s
The complete changeover to the exclusive at 20 ◦ C 0.19 × 10−3 Pa s
Dielectric constant at 17.2 ◦ C 6.26
use of ethylene as a feedstock became possible Flash point (open cup) − 78 ◦ C
when the large-scale oxychlorination of ethyl- Autoignition temperature 472 ◦ C
ene to 1,2-dichloroethane (see page 37) had been Explosive limits in air 4 – 22 vol%
Solubility in water at 20 ◦ C 0.11 wt %
proven to be technically feasible (Dow Chemi- Solubility of water in
cal, 1955 – 1958). vinylchloride at − 15 ◦ C 300 mg/kg
Since then, most plants use integrated,
balanced DC – EDC – Oxy – EDC – VCM pro- Vinyl chloride is a colorless, flammable gas
cesses and more than 90 % of the vinyl chlo- at ambient temperature with a sweetish odor. It
56 Chlorinated Hydrocarbons

is soluble in most common organic liquids and 2) Thermal cracking of 1,2-dichloroethane:

solvents. Cl−CH2 −CH2 −Cl→CH2 = CHCl+HCl
0
∆H298 = −100.2kJ/mol

3.1.2. Chemical Properties All other reactions yielding vinyl chloride are
industrially unimportant at present.
If oxygen and air are excluded, dry, purified Acetylene hydrochlorination was mainly
vinyl chloride is highly stable and noncorrosive. used in the past, when acetylene — produced
Above 450 ◦ C, partial decomposition oc- via calcium carbide from coal — was one of the
curs yielding acetylene and hydrogen chlo- most important basic feedstocks for the chemi-
ride. Trace amounts of 2-chloro-1,3-butadiene cal industry.
(chloroprene) may also be formed by acetylene- With the large-scale production of ethylene-
precursor dimerization. derived polymers, such as polyethylene and
Air combustion products of vinyl chloride are polystyrene, and the general trend toward nat-
carbon dioxide and hydrogen chloride. Under ural gas (United States), naphtha, and gas oil
oxygen deficient combustion, traces of phosgene (Europe) as basic feedstocks, the cracker capac-
may be formed. In oxidation reactions sensitized ity increased substantially and ethylene became
by chloride, monochloroacetaldehyde and car- readily available at very competitive prices.
bon monoxide are obtainable from vinyl chlo- Besides the economic disadvantage of the
ride [301]. higher priced hydrocarbon feed, the acetylene
In the presence of water, hydrochloric acid, hydrochlorination has the drawback of not being
which attacks most metals and alloys is formed. balanced on the chlorine side because it requires
This hydrolysis most probably proceeds via a only hydrogen chloride as a chlorine source.
peroxide intermediate [302]. With increasing demand for vinyl chloride
With air and oxygen, very explosive perox- and technical progress, the first balanced pro-
ides can be formed. cesses were established in the 1940s and 1950s,
Because of the vinylic double bond, the most when acetylene was partially replaced by ethyl-
important reactions are polymerization reactions ene, which was converted to vinyl chloride by di-
(co- and homopolymerization, → Poly(Vinyl rect chlorination to 1,2-dichloroethane and sub-
Chloride)) and electrophilic or radicalic addition sequent thermal cracking. The hydrogen chlo-
reactions — mainly chlorination or hydrochlori- ride from cracking could then be used for acety-
nation — to yield 1,1,2-trichloroethane or 1,1- lene hydrochlorination:
dichloroethane .
The substitution of the chlorine atom is
more difficult to achieve. Vinyl anion addition
reactions offering interesting synthetic routes
are possible via the vinylmagnesium [303] and
vinyllithium compounds [304]. By direct use of crack gas, without separa-
Catalytic halogen exchange by hydrogen flu- tion of ethylene and acetylene, this process is
oride gives vinyl fluoride [305]. still pursued with some modifications.
With the introduction of the first large-scale
Oxy – EDC plant (see page 37) by The Dow
3.1.3. Production Chemical Co. in 1958, a balanced process based
only on inexpensive ethylene became available
The industrial production of vinyl chloride is and found rapid acceptance within the chemical
based on only two reactions: industry.
Using this balanced process, vinyl chloride is
1) Hydrochlorination of acetylene: made only by thermal cracking of 1,2-dichloro-
C2 H2 +HCl→CH2 = CHCl ethane, which in turn is produced by direct chlo-
0
∆H298 = −99.2kJ/mol rination or oxychlorination of ethylene. The lat-
ter process balances hereby the hydrogen chlo-
ride formed during cracking:
 Chlorinated Hydrocarbons 57

the feed because they may clog and inactivate

the catalyst upon polymerization [307]. The hy-
drogen chloride must be free of chlorine to avoid
explosion and should not contain chlorinated hy-
drocarbons, which could also act as catalyst poi-
sons.
Presently, more than 90 % of the vinyl chlo-
Water must be entirely excluded to avoid cor-
ride produced is based on this route.
rosion on structural materials. Because of gas-
Since ca. 1960, considerable efforts were un-
phase reaction and anhydrous conditions, most
dertaken to replace ethylene by ethane as the
equipment is made from carbon steel. If water
basic feedstock. All ethane-based processes de-
is used for quenching or HCl absorption, either
veloped so far, however, lack selectivity, which
brick-lined or polymer-made equipment is used
causes increased recycle rates and losses by side
for these parts.
reactions and requires higher capital expendi-
Although fluidized-bed reactors have been
tures, so that the cost advantage even for grass-
patented [308], fixed-bed, multitubular reactors
root plants is marginal.
(tube size 1 – 4 inside diameter, 10 – 20 ft) are
The ethylene-based processes have been im-
almost exclusively used. To avoid volatilization
proved considerably by numerous process mod-
of the catalyst (tube side), temperature control
ifications which resulted in higher yields and
and near to isothermal operation of the reac-
lower energy requirements.
tor is achieved by external cooling using a hot
However, with the development and avail-
oil system or water. The heat of reaction can be
ability of new catalysts, the ethane route may
transferred and used in the reboilers of the down-
become more attractive in the future.
stream purification equipment [309]. A special
Due to sharply increasing energy costs, chlo-
reactor design has been patented for use of di-
rine has also become a very important cost fac-
luted hydrogen chloride from incineration pro-
tor in vinyl chloride production. This explains
cesses [310]. Mercury(II) chloride on activated
the research and development on an electroly-
carbon is used primarily as a catalyst in con-
sis-free route to vinyl chloride.
centrations of 2 – 10 wt %. Several other metal-
lic catalysts [311] as well as 1 – 3 vol% chlorine
[312] have been proposed or patented. However,
3.1.3.1. Vinyl Chloride from Acetylene
the mercury salt had proven to be the most effec-
tive. The reaction rate is first order with respect
The catalytic hydrochlorination of acetylene is
to acetylene [311, 313].
possible in either the gaseous or the liquid phase.
Activated carbon with specific properties is
The gas-phase reaction dominates in industrial
preferentially used as support [314]. Several
processes.
patents deal with appropriate pretreatment pro-
In this process the gaseous reactants are
cedures, such as oxidation and thermal activa-
brought into contact with the catalyst at slightly
tion, to improve these properties [315].
increased pressure (0.1 – 0.3 MPa) and 100 –250
◦ Zeolites and molecular sieves were also
C (contact time 0.1 – 1 s) and then quenched
found to be suitable support materials [316].
and partially liquified. The reaction products are
Because the volatility of mercury is a very
separated, recycled, or submitted to final purifi-
limiting factor for reactor operation and through-
cation.
put, additives such as cerium chloride [317], tho-
The molar feed ratios, varying from almost
rium [318] and copper chloride [319], as well
equimolar to a 10-fold excess of HCl, depend
as polymers [320], have been proposed to re-
heavily on catalyst performance. Acetylene con-
duce volatility. Mercury chloride – graphitein-
versions of 95 – 100 % at almost quantitative
tercalated catalyst is also thought to possess only
yields are achieved.
a very low sublimation tendency [321]. Because
The acetylene fed to the reactor has to be free
volatization of the mercury catalyst cannot be
of common catalyst poisons such as sulfur, phos-
completely avoided, the loss of catalyst activity
phorus and arsenic compounds [306]. Unsatu-
by moving hot spots must be minimized by op-
rated hydrocarbons must also be minimized in
erational means e.g. reversal of the flow through
58 Chlorinated Hydrocarbons

the reactor. Other possibilities are the adjustment from the heavies treatment (acetylene and vinyl
of the reactor load depending on the catalyst chloride) are recirculated to the compressor suc-
activity [322], operating two reactors in series, tion for optimal product recovery.
using fresh catalyst in the second to complete Other processes separate the heavy byprod-
conversion from the less active first reactor at ucts during the first distillation stage [327] or
reduced heat load [323], or the fine tuning of use water for HCl scrubbing [328, 329]. The re-
catalyst activity and heat transfer liquid flow in sultant concentrated hydrochloric acid obtained
a two-reactor system [324]. can then be used for the final drying of the acety-
With fixed-bed reactor systems, time – space lene feed, which can contain significant amounts
yields up to 300 kg m−3 h−1 are possible. An of moisture when produced by calcium carbide
average of 70 – 80 kg m−3 h−1 is achieved over hydrolysis [329].
the lifetime of the catalyst. All process modifications attempt to achieve
The mercury is removed from the spent cata- maximum recovery of the expensive acetylene
lyst by either thermal (pyrolytic) treatment [325] and to avoid high pressures and temperatures,
or steam desorption [326]. The mercury-free car- which may cause losses through polymerization
bon can be incinerated or reactivated. [327, 330].
Process Description (Fig. 21). Acetylene Vinyl Chloride from Crack Gases
and hydrogen chloride are mixed and fed with (Fig. 22). In the crack gas processes for vinyl
recycle gas to the reactor. The gases leaving the chloride manufacture, unpurified acetylene pro-
reactor are compressed and fed to a first tower, duced by high-temperature cracking of naphtha
where most of the vinyl chloride is withdrawn [307, 331, 332] or methane [333, 334] is used.
as a liquid from the bottom. Most of the over- These processes are adventageous in that they
head product (HCl, C2 H2 and C2 H3 Cl) is recy- do not require the cost-intensive separation of
cled to the reactor. For removal of inert matter, a acetylene –ethylene mixtures [335].
small part of this recycle stream is drawn off and The crack gas is fed directly to the hydrochlo-
washed with heavies — preferably 1,1-dichloro- rinator, and the acetylene is converted to vinyl
ethane formed by competitive addition of HCl to chloride which is then separated from the re-
vinyl chloride — to recover vinyl chloride and maining constituents. Because all of the acety-
acetylene. lene is consumed, the remaining ethylene is
more easily separated or it can be introduced
to a direct chlorination stage, where it is chlo-
rinated to 1,2-dichloroethane, which is subse-
quently cracked to vinyl chloride [307, 331].
Since almost equimolar amounts of ethylene
and acetylene can be achieved in the crack gas,
the process can be balanced for chlorine.
Higher pressures (1.0 – 3.0 MPa) must be ap-
plied for the hydrochlorination stage in order to
keep the reactor size reasonable. Because the
acetylene is very diluted, hot spots are a smaller
Figure 21. Production of vinyl chloride from acetylene and problem than with the pure acetylene process.
hydrogen chloride (schematic)
a) Reactor; b) Lights column; c) VCM column; d) Heavies For the chlorination and the cracking stage, stan-
stripper; e) Vent wash tower; g) Cooler; h) Knock-out drum; dard technology can be used.
i) Reboiler In a process developed by Solvay [332], hy-
drochlorination and chlorination are carried out
In the second tower, the crude vinyl chloride together. The patent claims high yields without
is purified and withdrawn at the head section. substantial formation of 1,1,2-trichloroethane,
The heavy bottoms are submitted to a final strip- which can be formed by the addition of chlo-
ping in the heavies column with the underflow rine to vinyl chloride.
of the washing tower and removed at the bottom Another process modification [334] uses the
for further use or for incineration. The overheads quenching of the crack gases with chlorine at ca.
 Chlorinated Hydrocarbons 59

Figure 22. Balanced process for the production of vinyl chloride from crack gases

400 ◦ C, which leads directly to vinyl chloride in Mitsui Toatsu, Monsanto, Stauffer), whereas
yields up to 60 %. An acetylene-based process only a few producers (e.g., Wacker) use catalytic
uses HCl generated from magnesium chloride cracking.
hydrate by pyrolysis [336]. Improved furnace designs for the non-
All acetylene-based processes, however, have catalytic reaction have made conversions and
the distinct drawback of using, at least partially, yields comparable to those obtained by catalytic
the more expensive hydrocarbon feed. Com- cracking.
pletely ethylene-based processes are econom- Because of the time-consuming catalyst
ically superior and in only a few cases is the removal, shutdown periods are considerably
acetylene route still competitively pursued. longer for catalytic furnaces and the catalyst is
an additional cost factor, so that pure thermal
cracking may be currently the more economical
3.1.3.2. Vinyl Chloride from process.
1,2-Dichloroethane Noncatalytic Gas-Phase Reaction. The re-
action occurs via a first-order free radical chain
The cracking reaction of 1,2-dichloroethane can mechanism [253, 338], which starts with the ho-
be carried out in the liquid or gas phase. molytic cleavage of a C – Cl bond
The liquid-phase dehydrochlorination of 1,2-
dichloroethane is industrially unimportant be- 1) ClCH2 – CH2 Cl → ClCH2 – C·H2 + Cl ·
cause expensive chlorine is lost as a salt when 2) Cl · + ClCH2 – CH2 Cl → ClCH2 – C·HCl + HCl
1,2-dichloroethane is treated with alkaline solu- 3) ClCH2 – C·HCl → CH2 = CHCl + Cl ·
tions: Cl · + ClCH2 – CH2 Cl → ClCH2 – C·HCl + HCl
etc.
CH2 Cl−CH2 Cl+NaOH→CH2 = CHCl+NaCl+H2 O
The intermediate dichloroethane radical is
In addition, the aqueous process stream to stabilized by elimination of a chlorine radical,
be discarded poses severe environmental prob- which propagates the chain.
lems or requires extensive pretreatment. Even The radical chain is terminated by recombi-
though a good dehydrochlorination reaction can nation (reverse reaction to initiation) or wall col-
be achieved by using phase-transfer catalysts lisions, as it is usual for this type of reaction.
[337], this process is not suitable or economi- Since chlorine or other radical species are
cal for large-scale production. important for the chain propagation, chlo-
The gas-phase dehydrochlorination is the rine, [339 – 341] or chlorine delivering com-
most important route and industrially used for pounds such as tetrachloromethane [342] or hex-
the production of vinyl chloride. achloroethane [340], as well as other radicals
It can be carried out as a pure pyrolytic reac- like oxygen [340] and nitrous oxide [340, 343]
tion or in the presence of catalysts. or other halogens (bromine and iodine) [341] can
The noncatalyzed process is used by the ma- be added as initiators and promoters. The use of
jority of the vinyl chloride producers (e.g., Dow oxygen, however, is controversial because oxy-
Chemical, Ethyl, B. F. Goodrich, Hoechst, ICI, gen was also found to enhance coking of the
60 Chlorinated Hydrocarbons

furnace walls [344]. Because chlorine is readily Although several furnace designs have been
available in vinyl chloride plants and because of patented [347] and the basic principles are quite
its minimal interference, chlorine is primarily similar, most vinyl chloride producers have de-
used as a promoter. Promoter concentration in veloped their proprietary furnace technology
the 1,2-dichloroethane feed may vary between a for optimal yield and low shutdown frequency
few hundred mg/kg and up to 5 %. Good results for pipe decoking. After leaving the reactors,
were achieved when chlorine was fed at differ- the gases must be cooled down immediately to
ent points to the reaction zone [339], which may, avoid yield losses by formation of heavy prod-
however, be difficult to realize. When nitrometh- ucts. In most processes, this is achieved by a
ane was used as a promoter, high yields have quench tower, where condensed and cooled 1,2-
been reported [345]. The addition of 1,1,2-tri- dichloroethane is recirculated at high rates. The
chloroethane was found to inhibit coke forma- heat withdrawn from the quench tower can be
tion [346]. used for the reboilers of downstream distilla-
Even though 1,1-dichloroethane is more dif- tion stages [348]. It is also possible to quench
ficult to crack, good conversions are obtainable in two stages, first by indirect cooling (transfer
if the 1,1-dichloroethane concentration does not line heat exchanger) and then by direct quench-
exceed 10 % in the feed [143]. The crack re- ing [349]. Thus, substantial heat recovery is pos-
action is industrially carried out at tempera- sible, which can be used by a hot oil system in
tures between 400 and 650 ◦ C, preferably, how- other process stages. Only indirect cooling at the
ever, between 500 and 550 ◦ C. Reactor pres- furnace tail pipe bears an increased risk of plug-
sure may vary from 0.1 to 4.0 MPa. How- ging the heat exchanger with coke and heavy
ever, high-pressure processes (2.0 – 3.0 MPa) byproducts.
are preferred because high pressure reduces fur- For the downstream separation of the main
nace size, improves heat transfer, and makes the constituents of the reaction gases, vinyl chlo-
downstream separation easier, due to increased ride, hydrogen chloride, and 1,2-dichloro-
boiling points. Mean residence time is about 10 – ethane, many processing possibilities have been
20 s. The 1,2-dichloroethane conversion is kept patented [350]. However, a common principle is
at 50 – 60 % per pass to control byproduct forma- to first separate hydrogen chloride and then vinyl
tion and coking, which significantly increases at chloride from the reaction mixture by distilla-
higher conversion rates and causes yield losses. tion. 1,2-Dichloroethane is then distilled from
At these conversion rates, vinyl chloride yields the remaining heavies or the whole stream is
of 95 – 99 % are obtainable. High-purity 1,2- sent without separation to the DC – EDC section
dichloroethane should be used because most [351] (see page 35), where it can be economi-
impure technical-grade dichloroethane reduces cally purified.
conversion. The byproducts of 1,2-dichloroethane crack-
The crack furnace has a plug-flow reactor de- ing can be theoretically divided into two groups:
sign with one or more tubes (1 – 10 diameter, 1) Volatile impurities such as ethylene, acety-
up to 4000 feet long) being placed in the con- lene, vinylacetylene, 1,3-butadiene, 2-chloro-
vection zone of the furnace. The furnace may 1,3-butadiene, benzene, chlorobenzene,
be equipped with a single burner or have multi- 1,2- and 1,1-dichloroethylene, 1,1-dichloro-
burner design. In most cases, natural gas is used ethane, 1,1,1- and 1,1,2-trichloroethane,
as a burner feed; however, some plants use hy- methyl and methylene chloride, chloroform,
drogen-driven furnaces, using hydrogen from and tetrachloromethane.
on-site chlor-alkali plants. Feed evaporation at 2) Tars and coke. To remove these, special filters
ca. 200 ◦ C and cracking at a much higher tem- are used [352].
perature is often carried out in the same furnace
to make the best use of the fuel gas. Evapora- 2-Chloro-1,3-butadiene (chloroprene) forms
tion is preferably carried out in the upper, cooler tarry polymerization products, which plug the
part of the convection zone, whereas the crack- equipment when separated from 1,2-dichloro-
ing must take place in the lower, hotter part. ethane together with other light products. If this
Chromium –nickel alloys are the best construc- separation is not performed with the DC – EDC
tion materials [167]. process, chlorination of the heavies is used to
 Chlorinated Hydrocarbons 61

improve separation and to avoid excessive plug- In integrated processes (see page 62), the
ging of the equipment [353, 354]. last two stages are more economically combined
Other volatile impurities must also be re- with the purification of 1,2-dichloroethane from
moved by posttreatment because they cannot be the DC and Oxy train.
completely separated from the main products by If high temperature DC processes are used
distillation. (see page 35), 1,2-dichloroethane can be puri-
Acetylene, which codistills with the hydro- fied in the DC reactor.
gen chloride, is either converted to vinyl chlo- Catalytic Gas-Phase Reaction. The cat-
ride by catalytic hydrochlorination [355] or se- alytic gas-phase dehydrochlorination is only
lectively hydrogenated to ethylene [356], which used by a minority of vinyl chloride produc-
does not interfere when the hydrogen chloride is ers [306, 307, 370]. Higher selectivities toward
used in the Oxy-EDC-process (see page 37. 1,3- vinyl chloride and less formation of coke, which
Butadiene, which mostly contaminates the vinyl is mainly due to the lower temperatures (200 –
chloride fraction, can be removed by polymer- 450 ◦ C), are often claimed as advantages.
ization during extended residence time [357] or 1,2-Dichloroethane conversions, however,
with Lewis-acid catalysts [358] by chlorination are not much improved compared to the non-
[353, 359], hydrochlorination [360], hydrogen- catalytic process. On the average, 60 – 80 % but
ation [361], or by reaction with chlorosulfuric mostly 60 – 70 % conversion per pass is ob-
acid [362]. tained.
The vinyl chloride obtained by distillation In addition to activated carbon [371], which
is suitable for polymerization. If necessary, re- can be doped with ammonium salt promoters
maining impurities can be removed by extractive [372], a variety of other materials has been
distillation with acetonitrile [363], distillation in patented as catalysts, consisting of silicates
the presence of alcohols [364], or orthoesters [373], metal-promoted alumina [374], sodium
[365] as acid scavengers, or treatment with cal- chloride [375], and zeolites [376]. The dehy-
cium oxide [366] or zinc [367]. Removal of ionic drochlorination of 1,2-dichloroethane by melts
species by an electrostatic field was also pro- containing copper or other metals has also been
posed [368]. Remaining traces of 1,3-butadiene described [377] (see also Transcat process, Sec-
can be removed by clay adsorbents [369]. tion 3.1.3.4).
Process Description (Fig. 23). Pure 1,2-di- With the development of improved noncat-
chloroethane is fed to the evaporator in the up- alytic gas-phase processes, the catalytic route
per part of the cracking furnace. The gas phase has lost most of its economic attractiveness. The
is separated from the remaining liquids and higher costs of catalytic processes for catalyst
fed to the cracking zone. After having passed and extended shutdown periods no longer com-
the cracking zone in the furnace, the gases are pensate the slightly higher energy requirements
cooled and quenched. of modern yield- and energy-optimized noncat-
Hydrogen chloride is removed from the re- alytic processes.
action mixture in the first distillation tower and
sent back to the Oxy – EDC process or used for Photochemically Induced Gas-Phase De-
other purposes (e.g., methanol hydrochlorina- hydrochlorination. Considerable improve-
tion). Vinyl chloride is distilled in the second ments in conversion and product quality were
tower and drawn off as a head product. It can obtained by combining the thermal noncatalytic
be washed with diluted caustic in order to re- gas-phase reaction with a photochemical postre-
move the last traces of hydrogen chloride and action [378]. Either polychromatic actinic light
1,2-dichloroethane. from mercury, thallium, or tungsten lamps or,
The bottoms of the vinyl chloride column are preferably, monochromatic light from suitable
purified in two more distillation stages. First, the lasers is used as a light source for the excitation
low-boiling impurities are removed in the light of 1,2-dichloroethane. The excited molecules
ends column, followed by 1,2-dichloroethane then liberate chlorine atoms, which in turn start
separation from the heavy ends in the last tower. the free radical chain reaction:
The purified 1,2-dichloroethane is recycled to
the cracking furnace.
62 Chlorinated Hydrocarbons

Figure 23. Schematic flow sheet for production of vinyl chloride by thermal cracking of 1,2-dichloroethane
a) Crack furnace; b) Transfer pipe heat exchanger; c) Quench tower; d) HCl distillation tower; e) VCM purification tower;
f) VCM wash tower; g) Light-end tower; h) EDC – heavy end tower; i) Cooler; j) Knock-out drum; k) ReboilerA Process
Modification

Figure 24. Ethylene-based integrated balanced process for the production of vinyl chloride

C2 H4 Cl2 + hν → (C2 H4 Cl2 )* excited

state
integrated, balanced processes comprising three
(C2 H4 Cl2 )* → C2 H4 Cl · + Cl · units [179, 379].
Cl · + C2 H4 Cl2 → C2 H3 Cl2 · + HCl
C2 H3 Cl2 · → C2 H3 Cl + Cl ·
1) direct ethylene chlorination
2) ethylene oxychlorination
A photochemical postreactor implemented in 3) 1,2-dichloroethane cracking
existing thermal processes allows higher conver- Ethylene and chlorine are basic feedstocks
sion rates at increased selectivity and decreased which are reacted in the direct chlorination unit
energy consumption. to yield 1,2-dichloroethane. Additional 1,2-di-
This, however, has not yet been proven on an chloroethane is produced in the oxychlorination
industrial scale. process. The combined streams are fed to the
Combined Process (Fig. 24). Most of the cracking train, where vinyl chloride is obtained.
vinyl chloride is presently produced in so-called The hydrogen chloride formed during cracking
 Chlorinated Hydrocarbons 63

is recycled and consumed in the oxychlorination The amine hydrochloride is regenerated by

process. Thus, the process is balanced on hydro- sodium chloride and carbon dioxide.
gen chloride. Integrated processes are not only
(CH3 )3 N +CO2 +NaCl+H 2 O
advantageous due to lower energy requirements,
→(CH3 )3 N ·HCl+NaHCO3
due to the fact that energy-consuming steps can
be combined with exothermic reactions, but they The driving force for this reaction is — quite
also allow variations in the chlorine distribution similar to the Solvay soda ash process — the
of manufacturing sites producing other chlori- poor solubility of the hydrogen carbonate, which
nated hydrocarbons and convert the largely un- can be removed and calcined, whereby some car-
usable byproduct hydrogen chloride into a valu- bon dioxide is recovered.
able product.
Differences in process technology used by the 2NaHCO3 →Na2 CO3 +CO2 +H2 O
individual vinyl chloride producers are mainly The overall process yields 1,2-dichloro-
due to the different technologies applied in the ethane and soda ash from ethylene, oxygen, car-
processes, such as high- or low-temperature di- bon dioxide, and sodium chloride. The dichloro-
rect chlorination, fixed- or fluidized-bed oxy- ethane must then be conventionally converted to
chlorination, which determine the needs for pu- vinyl chloride by cracking:
rification equipment and the energy require-
ments. C2 H4 +1/2O2 +2NaCl+CO2 →C2 H4 Cl2 +
The most important processes presently used Na2 CO3 C2 H4 Cl2 →C2 H3 Cl+HCl
are described in detail elsewhere [175]. The ma-
jor unit ratios for a balanced, air-based process Hydrogen chloride from the cracking reac-
are given in Table 20. tion can be used to form aminohydrochloride so
that balancing with sodium chloride or hydrogen
chloride is possible.
Table 20. Major unit ratios for an integrated, balanced vinyl
chloride process [380] (oxychlorination is air-based)
(CH3 )3 N +HCl→(CH3 )3 N ·HCl
Component Unit ratio
(kg/kg VCM) Whether this process will be able to replace
Raw materials:
the present route will depend primarily on the
Ethene 0.4656 feasibility of its overall industrial verification.
Chlorine 0.5871 Financial requirements for a grass root plant,
Air 0.7322
however, may be considerably lower than for
Water 0.0171
a conventional plant if the required chlorine ca-
Byproducts: pacity is added. The requirement for inexpensive
Lights 0.0029 energy instead of expensive electrical power is a
Heavies 0.0023
Vents 0.6727
further advantage. The byproduct soda ash, even
(0.5779 of this is N2 ) though readily available from natural sources,
Aqueous streams 0.1218 should not be very limiting if one considers
the fact that the conventional process also pro-
New Developments. A new route was devel- duces NaOH byproduct during brine electroly-
oped [381] which allows chlorine-free produc- sis. However, plans by Akzo to built a commer-
tion of vinyl chloride by bringing ethylene in cial scale plant have been abandoned in 1986
contact with an aqueous solution containing cop- [382].
per(II) chloride and iodine:
4CuCl2 +I2 +3C2 H4 →3C2 H4 Cl2 +Cu2 Cl2 +Cu2 I2 3.1.3.3. Vinyl Chloride from Ethylene by
The copper salts are reoxidized after di- Direct Routes
chloroethane stripping by oxygen and an amine
hydrochloride acting as a chlorine source: Because ethylene chlorination and oxychlorina-
tion are both highly exothermic reactions, nu-
3/2O2 +6(CH3 )3 N ·HCl+Cu2 Cl2 +Cu2 I2 merous attempts have been made to combine one
→4CuCl2 +I2 +6(CH3 )3 N +3H2 O
64 Chlorinated Hydrocarbons

or both reactions with the endothermic crack- limited the industrial implementation of direct
ing reaction for 1,2-dichloroethane, i.e., not iso- processes.
lating the intermediate, but directly producing In a process, however, which is carried out
vinyl chloride by high-temperature chlorination on an industrial scale (approx. 150 000 t/a vinyl
or oxychlorination of ethylene. Several pro- chloride) by Atochem, France, the byproducts
cesses have been patented which claim direct are integrated and several other usable hydro-
synthesis of vinyl chloride from ethylene and carbons in addition to vinyl chloride are inten-
chlorine or hydrogen chloride at temperatures tionally produced (Fig. 25) [245, 391].
between 300 and 600 ◦ C. The process consists of high temperature
In direct chlorination processes an excess of chlorination of ethylene. The reaction products
ethylene is often used to minimize byproduct are separated, yielding vinyl chloride, dichloro-
formation [383]. Other processes use two reac- ethylenes, chloroethanes, and hydrogen chlo-
tion zones [384] or make use of an inert flu- ride. Excess ethylene together with hydrogen
idized bed for heat transfer [384]. The hydro- chloride is oxychlorinated in a fluidized-bed
gen chloride formed can be consumed in a sepa- reactor to give primarily 1,2-di- and 1,1,2-tri-
rate oxychlorination unit [385]. Additional pro- chloroethane, which can be drawn off or recy-
cesses have been proposed [386]. cled to the hot chlorination reactor.
If the oxychlorination of ethylene is carried Dichloroethylenes can be treated differently.
out at a temperature above 350 ◦ C, substantial 1,1-Dichloroethylene can be hydrochlorinated
amounts of vinyl chloride are obtained. As with to give 1,1,1-trichloroethane (see page 46). Tri-
the Oxy-EDC process (see page 37), polyva- chloroethylene is produced via noncatalytic cold
lent metals are used as catalyst. However, low- chlorination of dichloroethylenes and subse-
surface area supports (e.g., α-alumina) are pre- quent cracking of the tetrachloroethanes ob-
ferred [387, 388] because high-surface-area cat- tained. Heavy byproducts accounting for ca. 3 %
alysts tend to ward rapid coking and deactivation of the total production are incinerated and aque-
by polymer formation at higher temperatures. ous HCl is recovered. However, they can also be
The high temperature required can also cause used for perchloroethylene synthesis. The pro-
considerable yield losses by “deep” oxidation cess is said to allow considerable fluctuations in
of ethylene to CO and CO2 . Oxygen feed be- production ratios, ranging from 2.5 : 1 to 0.8 : 1
low the stoichiometric ratio may be required to (VCM : chlorinated solvents) allowing good re-
control these unwanted side reactions [388]. sponsiveness to market demands. Overall carbon
Feeding the excess ethylene to the high-tem- yields of 94.5 % are obtained.
perature oxychlorination reactor and converting
the surplus to 1,2-dichloroethane in a second DC
stage, which is then recycled and cracked in the 3.1.3.4. Vinyl Chloride from Ethane
Oxy reactor may be another possibility [389].
Numerous attempts have been made to convert
Further possibilities comprise contacting ethyl-
ethane directly to vinyl chloride because this
ene with melts containing copper(II) chloride.
would save the processing costs for ethylene.
Vinyl chloride is formed and the reduced cop-
Ethane is readily available, particularly on the
per salt can be regenerated by chlorination or
U.S. golf coast, and used as a feedstock for ethyl-
oxychlorination and then be recycled [390].
ene crackers. The direct feed of ethane to VCM
Common to all direct routes is the fact that
plants could, thus, considerably decrease the raw
the processes are difficult to control and operate
material costs and make the plants less depen-
and are characterized by poor selectivities be-
dent on cracker capacity.
cause ethylene, vinyl chloride, chlorine, and hy-
Conversion of ethane to vinyl chloride can be
drogen chloride undergo considerable addition
performed by various routes:
and elimination reactions at elevated tempera-
tures. Typical byproducts of direct high-tempe- 1) High-temperature chlorination:
rature processes are dichloroethylenes and tri- C2 H6 +2Cl2 →C2 H3 Cl+3HCl
and tetrachloroethylene. The low yield of vinyl 2) High-temperature oxychlorination:
chloride together with the need to dispose of
high quantities of byproducts has considerably C2 H6 +HCl+O2 →C2 H3 Cl+2H2 O
 Chlorinated Hydrocarbons 65

Figure 25. Schematic principle of the Atochem process for the production of vinyl chloride and other chlorinated hydrocyrbons

3) High-temperature oxidative chlorination because thermodynamic conditions would lead

(combines 1 + 2) to stable products like tetrachloroethylene. Con-
sequently, however, high recycle rates of un-
2C2 H6 +3/2O2 +Cl2 →C2 H3 Cl+3H2 O converted ethane and byproducts such as ethyl
chloride and dichloroethanes must be accepted.
A major drawback of ethane, however, is its With special catalysts and at optimized condi-
lack of molecular functionality. In contrast to tions, however, ethane conversions of > 96 %
ethylene, which easily undergoes chlorine ad- have been reported from oxychlorination reac-
dition, ethane must first be functionalized by tions [392]. Vinyl chloride yields average 20 –
substitution reactions, which gives rise to a va- 50 % per pass. Ethylene, ethyl chloride, and 1,2-
riety of consecutive and side-chain reactions dichloroethane are obtained as major byprod-
(Fig. 26). ucts. The formation of carbon oxides can be
controlled with carbon yield losses of 3 – 10 %.
The ethylene formed can either be recycled or
oxychlorinated and cracked in a conventional
manner. Some special processes have been sug-
gested to purify and concentrate the aqueous hy-
drochloric acid obtained [393].
Another patent comprises the chlorination of
ethylene – ethane mixtures with staged addition
of chlorine to avoid an explosive reaction. Ad-
dition of ethylene is thought to suppress the for-
mation of higher chlorinated byproducts [394].
Conversion and yields are comparable to the
oxychlorination reactions mentioned above.
Some balanced ethane-based processes have
Figure 26. Ethane chlorination pathways been developed according to the following reac-
tion schemes:
The reaction must, therefore, be kinetically 1) Hot ethane chlorination → VCM separation
controlled in order to obtain a maximal vinyl → oxychlorination of residual ethylene and
chloride yield. Conversion must be sacrificed chloroethane to yield additional VCM [395].
66 Chlorinated Hydrocarbons

2) Thermal chlorination of ethane to ethyl chlo- used to recover vinyl chloride from a major
ride → oxychlorination without separation byproduct when there is no demand for 1,1,2-
from hydrogen chloride to vinyl chloride trichloroethane. The electrochemical dechlori-
[396]. nation of 1,1,2-trichloroethane is also possible
3) Ethane chlorodehydrogenation to ethylene [407].
and hydrogen chloride → oxychlorination Some ethylene-based processes comprise the
to 1,2-dichloroethane → thermal cracking to production of vinyl chloride during brine elec-
vinyl chloride [397]. trolysis in the presence of ethylene [408], ethyl-
Another balanced ethane-based process was ene oxychlorination by nitrosyl chloride (NOCl)
developed by The Lummus Co. [163, 398]. In [409], and a bromine-based process which con-
the final version of this so-called Transcat pro- verts vinyl bromide into vinyl chloride by reac-
cess, ethane and chlorine, as well as the recycle tion with hydrogen chloride [410]. Ethane sul-
products ethylene, ethyl chloride, and hydrogen fochlorination has been proposed as a very ex-
chloride are fed to a melt of copper(II) chlo- otic route similar to oxychlorination, but using
ride and potassium chloride. Vinyl chloride is sulfur instead of oxygen [411].
formed and separated. The reduced melt is trans-
ferred by an airlift system and regenerated with 3.1.4. Uses and Economic Aspects
air, chlorine, or hydrogen chloride. It is then fed
back together with the recycle products, which About 95 % of the world production of vinyl
may also contain 1,2- and 1,1-dichloroethane, to chloride is used for the production of poly(vinyl
the oxychlorinator. Even though the process has chloride) (PVC). Thus, vinyl chloride is very
been operated on a pilot-plant scale, it has not dependent on the major processors of PVC as
been accepted by the vinyl chloride producers. well as the housing and automotive industry
More ethane-based processes for chlorina- with its frequent fluctuations. The rest of the
tion [399] and oxychlorination [400] can be vinyl chloride production goes into the produc-
found in the literature. Because 1,1-dichloro- tion of chlorinated solvents, primarily 1,1,1-tri-
ethane is preferably formed by ethane chlori- chloroethane.
nation or oxychlorination, its thermal cracking
reaction has been intensively studied [401]. The Table 21. World wide vinyl chloride capacity and production
photochemical chlorination of ethane at 250 – (1985, estimated) [412]
400 ◦ C yields ethyl chloride and the dichloro- Capacity, Production,
ethanes (preferably the 1,1-isomer) as major 103 t/a 103 t/a
products [402]. Only small amounts of vinyl North America 4 900 4 000
chloride are formed. South America 500 400
Western Europe 5 700 5 000
Eastern Europe/USSR 2 100 1 500
Middle/Far East 3 000 2500
3.1.3.5. Vinyl Chloride by Other Routes Rest 350 180
16 550 13 580
Vinyl chloride can be obtained as a valu-
able byproduct in the synthesis of such im-
portant fluorocarbons as tetrafluoroethylene Total world capacity of vinyl chloride is about
(F-1114) and chlorotrifluoroethylene (F-1113) 17 million t/a. As shown in Table 21, more
when saturated chlorofluorocarbons are catalyt- than half of the world’s total capacity (64 %) is
ically dechlorinated by ethylene [403]. concentrated in Western Europe and the United
Oxidative condensation of chloromethane States. The annual growth rate is estimated bet-
derived from methane or methanol can also form ween 1 and 5 %, depending on the economic sit-
vinyl chloride [404]. uation. However, capacity utilization presently
The catalytic dehydrochlorination of 1,1,2- averages only 70 – 80 % [413], which may not be
trichloroethane [405] or its catalytic dechlo- sufficient to make production of vinyl chloride
rination with ethylene [406] both yield vinyl profitable. Several new vinyl chloride plants are
chloride. Although both processes are not suit- being planned or are under construction in East-
able for large-scale production, they could be ern Europe and in developing and oil-producing
 Chlorinated Hydrocarbons 67
0
Heat of formation (liquid) ∆H298 − 24.5 kJ/mol
countries (see Table 22)[414]. This significant
Specific heat (liquid, 25 ◦ C) 1.15 kJ kg−1 K−1
increase in capacity outside of the traditional (gas, 25 ◦ C) 0.69 kJ kg−1 K−1
VCM –PVC countries and its consequences may Heat of evaporation at 25 ◦ C 26.5 kJ/mol
in the longrun cause a geographical shift of VCM Heat of fusion at − 122.6 ◦ C 6.51 kJ/mol
Heat of polymerization at 25 ◦ C − 75.4 kJ/mol
production. Critical temperature 494 K
Critical pressure 5200 kPa
Table 22. Vinyl chloride plants Viscosity at 20 ◦ C 3.3 × 10−4 Pa · s
Dielectric constant at 16 ◦ C 4.67
Country Capacity, Technology source Flash point (open cup) − 30 ◦ C
103 t/year Autoignition temperature + 460 ◦ C
Explosive limits in air 6 – 16 vol%
Argentina 130 B. F. Goodrich
Solubility in water at 20 ◦ C 2200 mg/kg
Brazil 150 B. F. Goodrich
Solubility of water in vinylidene
China (P.R.) 200 Mitsui Toatsu
chloride at 20 ◦ C 320 mg/kg
China (P.R.) 200 Mitsui Toatsu
Egypt 100 Mitsui Toatsu
Egypt 100 – 1,1-Dichloroethylene is a colorless clear liq-
India 103 – uid with a sweetish odor. It is soluble in most
Iran 150 Toyo Soda organic solvents.
Nigeria 145 –
Poland 205 PPG Ind.
Portugal 110 Mitsui Toatsu
Saudi Arabia 300 B. F. Goodrich 3.2.2. Chemical Properties
Turkey 117 Solvay-ICI
USSR 270 Hoechst-B.F. Goodrich
Vinylidene chloride belongs to the less stable
chloroethylenes because it is very susceptible
to both oxidation and polymerization. To avoid
3.2. 1,1-Dichloroethylene (Vinylidene these reactions, oxygen scavengers such as ami-
Chloride, VDC) no and sulfur compounds or phenol derivatives
must be added as stabilizers [415]. Most stabi-
1,1-Dichloroethylene [75-35-4] is important for lizers prevent autoxidative polymerization. They
upgrading 1,1,2-trichloroethane, which is very must not be removed, however, before vinyli-
often an unwanted byproduct. Thus, 1,1-di- dene chloride is industrially polymerized. When
chloroethylene is an intermediate in the pro- pyrolyzed above 400 – 450 ◦ C, chloroacetylene
duction of 1,1,1-trichloroethane from 1,1,2-tri- and hydrogen chloride are obtained.
chloroethane (see page 45). It is also used as a With copper and other heavy metals or their
monomer for the production of poly(vinylidene salts, highly explosive acetylenes are formed.
chloride) (PVDC) and its copolymers, which are Therefore, copper and its alloys should not be
important barrier materials in the food packing used as a construction material if contact with
industry. Of all important chloroethanes and - vinylidene chloride is anticipated. Combustion
ethylenes, vinylidene chloride has presently the with an excess of air yields carbon dioxide and
smallest sales volume. Because of its unique hydrogen chloride. Traces of phosgene may be
applications in polymers for food containers, formed under oxygen deficient conditions.
longterm demand will grow, however. Vinylidene chloride can be easily chlorinated
at a slightly elevated temperature to give 1,1,1,2-
3.2.1. Physical Properties tetrachloroethane.
The most important reaction, however, is
Mr 96.94 hydrochlorination in the presence of a Lewis-
mp − 122.6 ◦ C
acid catalyst for the production of 1,1,1-tri-
bp at 101.325 kPa 31.6 ◦ C
 at 20 ◦ C 1.214 g/cm3 chloroethane (see page 45).
n20
D 1.42468
Vapor pressure at
− 60 ◦ C 0.782 kPa
3.2.3. Production
− 40 ◦ C 3.320 kPa
− 20 ◦ C 10.850 kPa
0 ◦C 28.920 kPa 1,1-Dichloroethylene is almost exclusively pro-
20 ◦ C 66.340 kPa duced from 1,1,2-trichloroethane. This allows
68 Chlorinated Hydrocarbons

the recovery of valuable hydrocarbon and chlo- Monochloroacetylene in crude vinylidene chlo-
rine from a byproduct, which is obtained in large ride can also be removed by hydrochlorination
quantities during the production of 1,2-dichloro- in aqueous Cu2 Cl2 – HCl solutions [423].
ethane and 1,1,1-trichloroethane (see Sections 1,1,2-Trichloroethane can be crude [419],
2.3.3 and 2.4.3). even heavy ends from the Oxy – EDC process
1,1,2-Trichloroethane is converted to vinyli- (see page 37) can be used [424, 425]. However,
dene chloride by dehydrochlorination, which washing of the feed with water is beneficial to
can be carried out by two routes: the finished product quality [426]. To avoid poly-
merization during purification, the feed streams
1) Liquid-phase dehydrochlorination in the pres-
should be free of oxygen. Stabilizers are added
ence of alkali, e.g., NaOH:
during distillation or even to the reaction mixture
CHCl2 −CH2 Cl+NaOH→ [417] to inhibit polymerization.
CCl2 = CH2 +NaCl+H2 O The reaction proceeds at temperatures bet-
2) Pyrolytic gas-phase cracking at elevated tem- ween 80 and 100 ◦ C at an acceptable rate. With
peratures: promoters such as charcoal, alumina, and silica
[428] or quaternary ammonium salts [425], high
selectivity is obtainable at even lower tempera-
tures (≤ 40 ◦ C).
This process is carried out continuously in
packed-bed reactors to allow thorough contact.
The latter route has the advantage that valu-
Life steam is injected to distill the vinylidene
able chlorine is recovered as hydrogen chloride,
chloride. Unconverted 1,1,2-trichloroethane is
which can be used again for oxychlorination pro-
recycled from the appropriate sections. A plug-
cesses. By this route, however, vinylidene chlo-
flow type reactor with consecutive flash distilla-
ride selectivity is low, since the formation of 1,2-
tion has also been described [418].
dichloroethylenes is favored [416].
Due to the alkaline conditions, nickel and
In the liquid phase reaction, vinylidene chlo-
some of its alloys are the best suited construction
ride selectivity is well above 90 %; however, hy-
materials. This minimizes the risk of acetylide
drogen chloride is lost as a salt.
formation.
At present, the liquid-phase reaction is dom-
In order to obtain polymer grade vinylidene
inant. The development of new catalysts with
chloride, the stripped product is washed with al-
increased selectivity and high stability could
kali and water, dried, and fractionally distilled.
change this situation in the future.
Azeotropic distillation with methanol (6 wt %)
Liquid-Phase Reaction. The liquid-phase and subsequent washing with water is also pos-
reaction is carried out with aqueous solutions sible [429]. Even if purified, vinylidene chloride
of alkali or alkaline earth hydroxides. As with should be used directly and not stored for more
the low solubility of alkaline earth hydroxides, than two days.
the free concentration is small, NaOH (10 – 15 The use of aprotic polar solvents like di-
wt %) is widely preferred to increase the reaction methylsulfoxide and dimethylformamide in-
rate. At optimum conditions [417], vinylidene stead of aqueous alkali has been patented [430].
chloride yields of 94 – 96 % are obtained. The The high cost of solvents, however, may not jus-
higher alkali concentration, however, bears the tify the large-scale production.
risk of formation of chloroacetylenes, which
tend toward explosive decomposition. Different Gas-Phase Reaction. The noncatalyzed
methods have been patented and are used to thermal decomposition yields cis- and trans-1,2-
minimize this reaction. These include thorough dichloroethylene together with 1,1-dichloroeth-
mixing [418], adjustment of proper feed ratios ylene in molar ratios of ca. 0.7 (1,1-/1,2-isomer).
[419], the addition of amines [420], the addition Radical chain as well as unimolecular mecha-
of calcium and magnesium hydroxides as emul- nisms have been proposed for the decomposition
sifiers and buffers [421], and the use of sodium reaction [416]. Radical chain sequences are very
chloride containing NaOH [422] (cell effluent likely because the reaction rate can be increased
from brine electrolysis can be used directly).
 Chlorinated Hydrocarbons 69

by chain initiators such as chlorine and chlo- When methanol is added to trichloroethane, the
rine-releasing compounds [431]. hydrogen chloride is consumed by the alcohol
By photochemically induced reactions, the and vinylidene chloride is obtained with methyl
formation of the 1,1-disubstituted isomer is chloride [446].
slightly improved [432]. Although excellent vinylidene chloride selec-
For industrial purposes, two routes are used tivities have been reported, catalytic gas-phase
to overcome the problems related to the forma- dehydrochlorination is still in the developmental
tion of unusable 1,2-substituted isomers. stage. A major drawback is the marked tendency
The first route comprises pure, noncatalytic, of vinylidene chloride to polymerize on cata-
thermal cracking of 1,1,2-trichloroethane with lyst surfaces [447] which requires frequent shut
selectivity of ca. 30 – 40 % for vinylidene chlo- downs and catalyst turnarounds. This offsets its
ride. The 1,2-dichloroethylenes are separated advantages over the noncatalytic gas phase or
and further chlorinated to tetrachloroethane, liquid-phase reaction. The latter two methods
which can be recycled and cracked in the same are both used in industrial scale processes.
reactor to yield trichloroethylene. This pro- Other Methods. If required, vinylidene
cess can be performed by feeding 1,1,2-tri- chloride can be obtained from thermal cracking
chloroethane and chlorine together with the re- of 1,1,1-trichloroethane [448], which is, how-
cycled 1,2-dichloroethylene [433]. It can be ever, not always economical. Other routes use
combined with the production of 1,1,1-tri- vinyl chloride oxychlorination [449] or tetra-
chloroethane by direct ethane chlorination [434] chloroethane dehydrochlorination [450] and
or with a direct chlorination processes for eth- high temperature reaction of methane with chlo-
ylene to yield vinyl chloride [245, 435], as is rinating agents [451]. All of these methods are
the case in the Atochem process (see Section presently of little interest, because the basic
3.1.3.4). feedstock for the conventional route, 1,1,2-tri-
The second route makes use of specific cata- chloroethane, is easily available.
lysts to increase selectivity. Besides simple cat-
alysts like sodium chloride [375], barium chlo-
ride [436], and alumina or silica, which can 3.2.4. Uses and Economic Aspects
be activated by steam treatment [437, 438],
numerous other catalysts have been patented. Vinylidene chloride (VDC) is often captively
These catalysts mainly consist of alkali metal used for the production of 1,1,1-trichloroethane.
salts [439 – 441], alkali metal hydroxides [442], Apart from this, VDC is a basic material
metal fluorides [443], and nitrogen-containing for poly(vinylidene chloride) (PVDC) or its
compounds [444] on appropriate supports such copolymers with vinyl chloride, acrylonitrile,
as alumina and silica gels. methacrylonitrile, and methacrylate. With these
The use of alkaline catalysts seems to be im- materials, barrier layers for food packaging are
portant because basic centers on the catalysts formed as well as laminated and polymer sand-
are mandatory for high vinylidene chloride se- wich type films.
lectivity [442], whereas acidic centers favor the The annual production rate for the Western
formation of the 1,2-isomers. Because the activ- World amounts to about 150 000 – 200 000 t, of
ity increases with the increasing atomic mass of which ca. 120 000 t are used for PVDC and its
the metal atom [442], cesium salts are preferred copolymers. The rest is converted to 1,1,1-tri-
[439 – 441]. chloroethane.
Additional doping with other metals may be Because of the unique properties of PVDC,
beneficial for further selectivity and prolonged the long-term demand will probably increase. It
catalyst lifetime [440, 441]. The role of the sup- could easily be satisfied because the 1,1,2-tri-
ports pore structive has also been investigated chloroethane feedstock is available from other
[445]. chlorinated hydrocarbon processes.
For increased selectivity, the feed is fre-
quently diluted with inert gases such as nitrogen.
Industrially more important, however, is the pos-
sibility of using vinyl chloride as a diluent [441].
70 Chlorinated Hydrocarbons

3.3. 1,2-Dichloroethylene cis-1,2-Dichloroethylene

Mr 96.94
Dichloroethylenes (cis: [156-59-2]; trans: [156- mp − 81.47 ◦ C
60-5]) often occur as an isomeric mixture dur- bp at 101.325 kPa 60.2 ◦ C
 at 20 ◦ C 1.282 g/cm3
ing the production of chlorinated hydrocar- n20 1.4490
D
bons, where they are produced by sidereac- Vapor pressure at
tions, e.g., by thermal decomposition of 1,1,2- − 20 ◦ C 2.700 kPa
trichloroethane or from acetylene by chlorine − 10 ◦ C 5.100 kPa
0 ◦C 8.700 kPa
addition. 10 C◦
14.700 kPa
Because there are scarcely any industrial uses 20 ◦ C 24.000 kPa
for these two compounds, they are often con- 30 ◦ C 33.300 kPa
40 ◦ C 46.700 kPa
verted to trichloro- and tetrachloroethylene. 0
Heat of formation (liquid) ∆H298 − 26.8 kJ/mol
◦
Specific heat (liquid, 20 C) 1.176 kJ kg−1 K−1
Heat of evaporation (boiling point) 30.2 kJ/mol
3.3.1. Physical Properties Critical temperature 544.2 K
Critical pressure 6030 kPa
trans-1,2-Dichloroethylene Viscosity at 20 ◦ C 0.467 × 10−3 Pa · s
◦
Surface tension at 20 C 28 × 10−3 N/m
Mr 96.94
Coefficient of cubical expansion
mp − 49.44 ◦ C
(15 – 45 ◦ C) 0.00127 K−1
bp at 101.325 kPa 48.5 ◦ C
Dielectric constant at 20 ◦ C 9.31
 at 20 ◦ C 1.260 g/cm3
Dipole moment 0.185 esu
n20 1.4462
D
Flash point 6 ◦C
Vapor pressure at
For autoignition temperature and explosive limits in air, see
− 20 ◦ C 5.300 kPa
trans-1,2-dichloroethylene
− 10 ◦ C 8.500 kPa
Solubility in water at 25 ◦ C 0.35 wt %
0 ◦C 15.100 kPa
Solubility of water in cis-
10 ◦ C 24.700 kPa
1,2-dichloroethylene at 25 ◦ C 0.55 wt %
20 ◦ C 35.300 kPa
30 ◦ C 54.700 kPa
40 ◦ C 76.700 kPa cis-1,2-Dichloroethylene is a colorless, light
0
Heat of formation (liquid) ∆H298 − 24.3 kJ/mol liquid with a sweetish odor. It forms an
Specific heat (liquid, 20 ◦ C) 1.158 kJ kg−1 K−1 azeotropic mixture with ethanol (9.8 wt % eth-
Heat of evaporation (boiling point) 28.9 kJ/mol
anol, bp 57.7 ◦ C), methanol (13 wt % metha-
Critical temperature 516.5 K
Critical pressure 5510 kPa nol, bp 51.5 ◦ C) and water (3.35 wt % water, bp
Viscosity at 20 ◦ C 0.404 × 10−3 Pa · s 55.3 ◦ C). A ternary azeotrope with ethanol/water
Surface tension at 20 ◦ C 25 × 10−3 N/m (6.55/ 2.85 wt %) has a bp of 53.8 ◦ C.
Coefficient of cubical expansion
(15 – 45 ◦ C) 0.00136 K−1
The industrial product always contains both
Dielectric constant at 20 ◦ C 2.15 isomers and has a boiling range of 45 – 60 ◦ C.
Dipole moment 0 esu If required, both isomers can be separated by
Flash point 4 ◦C fractional distillation.
Autoignition temperature 460 ◦ C
Solubility in water at 25 ◦ C 0.63 wt %
Solubility of water in trans-
1,2-dichloroethylene at 25 ◦ C 0.55 wt % 3.3.2. Chemical Properties

trans-1,2-Dichloroethylene is a colorless, Of the two isomers, the trans isomer is more

light liquid with a sweetish odor. It forms ex- reactive than the cis isomer. At higher tempera-
plosive mixtures with air (9.7 – 12.8 vol% 1,2- tures and in the presence of bromine or alumina,
dichloroethylene). isomerization is possible. Thermodynamically,
trans-1,2-Dichloroethylene forms azeotropic the cis isomer is more stable.
mixtures with ethanol (6 wt % ethanol, bp 46.5 If oxygen and moisture are excluded, 1,2-
◦
C) and water (1.9 wt % water, bp 45.3 ◦ C). A dichloroethylenes are sufficiently stable. With
ternary azeotrope of all three components (1.4 oxygen or peroxides, dimerization to tetra-
wt % ethanol, 1.1 wt % water) has a bp of 44.5 chlorobutene occurs. Upon oxidation, an inter-
◦
C. mediate epoxide is formed, which then under-
goes rearrangement to give chloroacetyl chlo-
ride [452]. Combustion with air yields carbon
 Chlorinated Hydrocarbons 71

oxides and hydrogen chloride. Under oxygen de- 3.3.4. Uses and Economic Aspects
ficient conditions, phosgene may be formed.
In the presence of water, hydrolysis occurs to The 1,2-dichloroethylenes are commercially
yield hydrochloric acid. Corrosion of construc- unimportant, because they do not polymerize,
tion material can be avoided by such stabilizers have relatively low boiling points, and can form
as amines and epoxides. explosive mixtures with air.
With weak alkali, 1,2-dichloroethylene is not In applications where dichloroethylenes
attacked; concentrated alkali, however, induces could be used as solvents and for low tem-
dehydrochlorination to explosive monochloro- perature extraction processes, they have been
acetylene. With copper or its compounds, ex- replaced by methylene chloride, which has a
plosive acetylides can be formed. higher solvency, is readily available, and is based
In the presence of Lewis-acid catalysts, 1,2- on less expensive feedstocks.
dichloroethylene can be chlorinated to 1,1,2,2- 1,2-Dichloroethylenes obtained as byprod-
tetrachloroethane or hydrochlorinated to 1,1,2- ucts from manufacturing processes for other
trichloroethane. chlorinated hydrocarbons are often used as feed
Polymerization is difficult because very high stock for the synthesis of tri- or perchloroethyl-
pressures are required. It is not carried out in- ene.
dustrially.

3.4. Trichloroethylene
3.3.3. Production
E. Fischer first obtained trichloroethylene [79-
Because 1,2-dichloroethylenes are industrially 01-6] in 1864 from hexachloroethane by re-
unimportant, they are not deliberately produced ductive dehalogenation with hydrogen. An
in large quantities. They occur as byproducts in acetylene-based process was developed in Aus-
some processes, such as the production of vinyl tria, and the first plant became operational
chloride and trichloroethylene, and can be with- in Jajce/Yugoslavia in 1908, a plant still pro-
drawn and purified if required. ducing tri- and tetrachloroethylene [455]. Be-
Synthetic routes are possible via cause of its high solvency and a growing de-
1) thermal cracking of 1,1,2-trichloroethane mand for degreasing solvents, trichloroethylene
2) chlorination of acetylene. achieved rapid growth rates in the past. Since the
late 1960s, however, the production rates have
In the thermal dehydrochlorination of 1,1,2- strongly declined as more stringent environmen-
trichloroethane, the 1,2-dichloroethylenes are tal regulations became effective. Trichloroeth-
obtained together with the 1,1-isomer. With ylene is also in strong competition with other
increasing temperature, formation of the 1,2- solvents such as 1,1,1-trichloroethane.
isomers increases. The trans isomer is preferen- The acetylene-based process has been par-
tially formed. With catalysts, the individual ra- tially replaced mainly in the United States
tios (1,2/1,1 and trans/cis) can be varied to some by ethylene chlorination and oxychlorination
extent. routes. A considerable amount of trichloroeth-
The chlorination of acetylene with activated ylene is still produced from acetylene, which,
carbon catalyst yields almost exclusively the cis however, is not made from carbide, but is ob-
isomer. An excess of acetylene is required to tained from ethylene crackers as a byproduct.
suppress the formation of tetrachloroethane. In-
stead of carbon, mercury and iron salts can be
used [453]. 3.4.1. Physical Properties
Other routes use liquid-phase acetylene oxy-
chlorination [454] or synthesis from 1,1,2,2- Mr 131.4
tetrachloroethylene which can be dehydrochlo- mp − 87.1 ◦ C
bp at 101.325 kPa 86.7 ◦ C
rinated and dehydrochlorinated by steam and  at 20 ◦ C 1.465 g/cm3
iron in one reaction. n20
D 1.4782
72 Chlorinated Hydrocarbons
Vapor pressure at
− 20 ◦ C 0.720 kPa
and dichloroacetyl chloride. This decomposi-
0 ◦C 2.680 kPa tion is enhanced by elevated temperatures (>
20 ◦ C 5.780 kPa 100 ◦ C), air or oxygen, sunlight, and moisture
40 ◦ C 7.700 kPa and causes corrosion on construction materials.
60 ◦ C 42.500 kPa
80 ◦ C 82.800 kPa
Trichloroethylene further reacts with alu-
Heat of formation (liquid) ∆H298 0
− 42.0 kJ/mol minum to form pentachlorobutadiene and higher
Specific heat (liquid, 20 ◦ C) 1.01 kJ kg−1 K−1 molecular mass polymers.
Heat of evaporation (boiling point) 31.5 kJ/mol Atmospheric photooxidative degradation has
Vapor density (boiling point) 4.45 g/L
Critical temperature 544.2 K also been studied [456]. Hydrolysis is less pro-
Critical pressure 5020 kPa nounced. With diluted hydroxides, glycolic acid
Thermal conductivity (liquid) 0.14 W m−1 K−1 is formed. Strong hydroxides eliminate hydro-
Surface tension (20 ◦ C) 26.4 × 10−3 N/m
gen chloride to give highly explosive dichloro-
Viscosity (20 ◦ C) 0.58 × 10−3 Pa · s
Coefficient of cubical expansion acetylene. Acidic hydrolysis with sulfuric acid
(0 – 40 ◦ C) 0.001185 K−1 gives monochloroacetic acid.
Dielectric constant (20 ◦ C) 3.41 Trichloroethylene can be chlorinated to pen-
Dipole moment 0.9 × 10−18 esu
Ignition temperature 410 ◦ C
tachloroethane or hydrochlorinated to give
Explosive limits in air at 25 ◦ C 7.9 – 10.5 vol% 1,1,2,2-tetrachloroethane [457].
at 100 ◦ C 8.0 – 52 vol% Although trichloroethylene can be copoly-
Solubility in water at 20 ◦ C 0.107 wt % merized with a variety of other monomers, it is
Solubility of water in
trichloroethylene at 20 ◦ C 0.025 wt %
used in commercial polymer applications only
in the production of poly(vinyl chloride), where
Trichloroethylene is a light, colorless liquid it allows the control of molecular mass distribu-
with a sweetish smell. It is miscible with most tion.
organic solvents and has a high solvency for
natural and synthetic rubbers and various other
polymers. Some binary and ternary azeotropes 3.4.3. Production
formed by trichloroethylene are shown in Ta- For the production of trichloroethylene either
ble 23. acetylene or ethylene is used as a feedstock.
The acetylene route which is still used in Eu-
Table 23. Azeotropes formed by trichloroethylene rope — the entire production of trichloroethyl-
wt % Component Azeotropic ene in the Federal Republic of Germany is based
boiling point on acetylene — comprises acetylene chlorina-
(101.3 kPa), tion to 1,1,2,2-tetrachloroethane followed by de-
◦
C
hydrochlorination to trichloroethylene:
18 1,2-dichloroethane 82.9
36 methanol 60.2
27 ethanol 70.9
17 1-propanol 81.8
30 2-propanol 75.5
2.5 1-butanol 86.9 In the ethylene-based processes, which are
33 tert-butanol 75.8 widely used in the United States and Japan,
6.6 water 72.9 ethylene or ethylene based chlorohydrocarbons,
3.8 acetic acid 87.0
preferably 1,2-dichloroethane, are chlorinated
or oxychlorinated and dehydrochlorinated in the
The ternary azeotropes contain 23.8 wt % eth- same reactor. Perchloroethylene is obtained as a
anol and 6.8 wt % water, bp 67.4 ◦ C; or 12 wt % byproduct in substantial amounts.
propanol and 7 wt % water, bp 71.7 ◦ C. Instead of using pure starting materials, these
processes can also be carried out very econom-
ically with residues from other chlorinated hy-
3.4.2. Chemical Properties drocarbon processes, e.g., from the production
of vinyl chloride.
Trichloroethylene decomposes slowly to yield Trichloroethylene from Tetrachloroethane.
hydrogen chloride, carbon oxides, phosgene, Because the chlorination of acetylene yields
 Chlorinated Hydrocarbons 73

1,1,2,2-tetrachloroethane, this isomer is prefer- A pure anhydrous liquid-phase process (170

ably used in the production of trichloroethylene. – 200 ◦ C), (0.3 – 0.6 MPa) for the dehydrochlo-
It dehydrochlorinates also more easily than the rination of mixtures also containing the 1,1,1,2-
1,1,1,2-substituted isomer. tetrachloroethane isomer has been patented
Dehydrochlorination can be carried out in the [465]. Iron chloride formed in situ from the con-
liquid and gas-phase. struction material acts as a catalyst, but activated
The liquid-phase process uses diluted aque- carbon can also be used [466]. The latter reac-
ous calcium hydroxide (10 – 20 %) for cracking tion, however, is important for ethylene-derived
[458]. The use of NaOH is not recommended tetrachloroethanes, which are obtained by chlo-
because explosive dichloroacetylene could be rination of 1,2-dichloroethane [467] (see page
formed. The heat of the highly exothermic re- 43).
action can be used for overhead distillation of Trichloroethylene from Ethylene or 1,2-
the trichloroethylene as an aqueous azeotrope. Dichloroethane. The synthesis of trichloroeth-
The calcium chloride solution is continuously ylene from ethylene or 1,2-dichloroethane is
withdrawn from the bottom of the reactor and possible by various routes, either by ethylene
can be further purified from the remaining or- or 1,2-dichloroethane chlorination and subse-
ganics by steam or vacuum stripping. Although quent dehydrochlorination or by oxychlorina-
this process can be carried out with high selec- tion of 1,2-dichloroethane.
tivity, it is rarely used because hydrogen chlo- The chlorination – dehydrochlorination re-
ride is lost by salt formation. In carbide-derived action is either carried out in sequence [467,
acetylene processes, however, it offers an out- 468] or, preferably, performed in one reactor.
let for the calcium oxide obtained from carbide Although ethylene can be used as a starting
decomposition. material [468], 1,2-dichloroethane is the pre-
Gas-phase dehydrochlorination of 1,1,2,2- ferred feedstock because selectivities and yields
tetrachloroethane is an endothermic reaction. can be increased.
CHCl2 −CHCl2 →CHCl = CCl2 +HCl The highly exothermic reaction is carried
0
∆H298 = +61kJ/mol out at temperatures between 200 and 500
◦
C. Numerous catalysts such as activated car-
It can be carried out as a pure thermal re- bon, silicates, graphite, and others have been
action at temperatures between 300 – 600 ◦ C in patented [469]. For optimum temperature con-
tubular reactors. However, because this reaction trol, fluidized-bed reactors are used [469]. Even
forms substantial amounts of heavy byproducts, at the optimum chlorine : dichloroethane ratio of
catalytic dehydrochlorination is industrially pre- 2 : 1, substantial amounts of perchloroethylene
ferred. are formed. This causes problems in the purifica-
Since catalyst activated carbon silica or tion section because tetrachloromethane formed
porcelain are used [459], barium chloride has from perchloroethylene is difficult to separate
been patented as promoter [460]. The feed mate- from trichloroethylene. To solve this problem,
rial must be thoroughly cleaned from iron chlo- a tandem process has been suggested [470].
ride traces (catalyst from acetylene chlorination) However, the chlorination — dehydrochlorina-
to avoid poisoning of the catalyst [461]. The re- tion process has the principal disadvantage of
action can be carried out in either fixed or flu- producing large amounts of hydrogen chloride,
idized bed reactors [462] at temperatures bet- which may not fit into site balances.
ween 250 and 400 ◦ C. The trichloroethylene Aside from ethylene and 1,2-dichloro-
yield ranges between 90 and 95 %. Catalytic ethanes, other chlorinated ethane residues may
traces of chloride were found to promote the re- also be used as feed [471].
action [463]. The oxychlorination process for the produc-
In addition to the acetylene chlorina- tion of trichloroethylene was developed by PPG
tion –tetrachloroethane dehydrochlorination se- Ind. [472]. It has the advantage of consuming hy-
quence, a direct synthesis by means of acetylene drogen chloride formed during chlorination dur-
oxychlorination to trichloroethylene, is also pos- ing the Deacon reaction, and only small amounts
sible [464]. of aqueous hydrochloric acid are obtained.
74 Chlorinated Hydrocarbons

In the oxychlorination process, ethylene, Other Processes. Trichloroethylene is one

1,2-dichloroethane, or chloroethane mixtures — of the major byproducts of the Atochem pro-
which can be residues from other processes — cess (see Section 3.1.3.3), where it is obtained
are fed together with oxygen and chlorine to a from dichloroethylene chlorination and subse-
fluidized-bed reactor. quent cracking [245]. Other routes not industri-
The catalyst used contains potassium chlo- ally used are ethane chlorination [474], the pyro-
ride and cupric chloride on fuller’s or diatoma- lysis of tri- and tetrachloromethane mixtures
ceous earth or silica. At reaction temperatures of [475], and the hydrodehalogenation of tetra-
420 – 460 ◦ C, the feed is converted by a series chloroethylene [476].
of substitution, crack, and Deacon reactions to
trichloroethylene and tetrachloroethylene:
C2 H4 +Cl2 →C2 H4 Cl2
3.4.4. Uses and Economic Aspects

C2 H4 Cl2 +2Cl2 →C2 H2 Cl4 +2HCl The major use for trichloroethylene is as a sol-
vent for vapor degreasing in the metal industry.
C2 H2 Cl4 +Cl2 →C2 HCl5 +HCl
Because it can undergo hydrolysis, decomposi-
C2 HCl5 +Cl2 →C2 Cl6 +HCl tion, and reaction with metals, it is stabilized
with acid acceptors such as amines, alcohols
C2 H4 Cl2 →C2 H3 Cl+HCl [477], epoxides, and metal stabilizers.
Trichloroethylene is further used for degreas-
C2 H3 Cl+Cl2 →C2 H3 Cl3
ing in the textile industry, as an extraction
C2 H3 Cl3 →C2 H2 Cl2 +HCl solvent, in solvent formulations for rubbers,
elastomers [478], paintstrippers, and industrial
C2 H2 Cl2 +Cl2 →C2 H2 Cl4 paints. In the production of poly(vinyl chloride),
C2 H2 Cl4 →C2 HCl3 +HCl
it serves as a chain-transfer agent to control the
molecular mass distribution.
C2 HCl5 →C2 Cl4 +HCl Since it was first produced on an industrial
scale, trichloroethylene production rates have
C2 Cl6 →C2 Cl4 +Cl2
steadily increased with a peak in 1970, when
4HCl+O2 →2Cl2 +2H2 O 280 000 t was produced in the United States and
130 000 t in the Federal Republic of Germany.
The chlorine yields average 90 – 98 %, carbon
Since then, however, the production rate of tri-
yields range between 85 – 90 %. Carbon losses
chloroethylene has declined not only because of
occur by oxidation to carbon oxides and for-
reduced losses by improved degreasing systems,
mation of tarry byproducts which cannot be re-
but also because of strong competition and re-
cycled. Temperature control is very important
placement by 1,1,1-trichloroethane.
because at a too low temperature (< 420 ◦ C),
Production for 1984 is estimated at approx.
the cracking reactions diminish whereas at a too
110 000 t for the United States, 80 000 t for
high temperature (> 480 ◦ C), the oxidation to
Japan, and ca. 200 000 t for Western Europe
carbon oxides increases.
(FRG: 30 000 t).
The products are separated and purified by
The annual decline of 5 – 7 % observed in
distillation and azeotropic distillation. Tri- and
1983 and 1984 will probably continue because
perchloroethylene are withdrawn, the light frac-
the more stringent environmental regulations in
tions and high boiling products are recycled to
most countries will further reduce emissions
the reactor, and tarry byproducts can be inciner-
from degreasing units and enforce reclaiming
ated.
[479].
Variation of the trichloroethylene : tetra-
chloroethylene ratio within a wide range (1.4
− 0.25) is possible by changing the feed ratios.
Instead of using a fluidized bed, the oxy-
chlorination of C2 residues in a melt of cupric
iron and alkali metal chlorides has been patented
[473].
 Chlorinated Hydrocarbons 75
Table 24. Azeotropes formed by tetrachloroethylene
3.5. Tetrachloroethylene
wt % Component Azeotropic
Tetrachloroethylene [127-18-4] (perchloroeth- boiling point
(101.3 kPa),
ylene, Perc) was first obtained by M. Faraday by ◦
C
the thermal decomposition of hexachloroethane.
15.9 water 87.1
Industrial acetylene-based production began 63.5 methanol 63.8
during the first decade of this century. In the 63.0 ethanol 76.8
1950s, perchloroethylene became the most im- 48.0 1-propanol 94.1
portant drycleaning solvent. 70.0 2-propanol 81.7
29.0 1-butanol 109.0
Most producers have replaced the old acety- 40.0 2-butanol 103.1
lene route by ethylene or 1,2-dichloroethane 50.0 formic acid 88.2
feedstocks or by the chlorinolysis process, 38.5 acetic acid 107.4
which uses chlorinated hydrocarbon residues as 8.5 propionic acid 119.2
3.0 isobutyric acid 120.5
starting material. 2.6 acetamide 120.5
19.5 pyrrole 113.4
43.0 1,1,2-trichloroethane 112.0
51.5 1-chloro-2,3-epoxypropane 110.1
3.5.1. Physical Properties 6.0 glycol 119.1

Mr 165.8
mp − 22.7 ◦ C
bp at 101.325 kPa 121.2 ◦ C 3.5.2. Chemical Properties
 at 20 ◦ C 1.623 g/cm3
 at 120 ◦ C 1.448 g/cm3 Perchloroethylene is the most stable derivative
n20
D 1.5055
Vapor pressure at of all chlorinated ethanes and ethylenes. It is
0 ◦C 0.590 kPa stable against hydrolysis and corrosion on con-
20 ◦ C 1.900 kPa struction materials is less pronounced than with
40 ◦ C 5.470 kPa
60 ◦ C 13.870 kPa
other chlorinated solvents.
80 ◦ C 30.130 kPa Tetrachloroethylene reacts with oxygen or air
100 ◦ C 58.500 kPa and light to give trichloroacetyl chloride and
120 ◦ C 100.000 kPa phosgene. This autoxidation can be suppressed
0
Heat of formation (liquid) ∆H298 − 51.1 kJ/mol
Specific heat (20 ◦ C) 0.86 kJ kg−1 K−1
by such stabilizers as amines or phenols. Liquid-
Heat of evaporation (boiling point) 34.7 kJ/mol phase oxidation with oxygen, however, can be
Vapor density (boiling point) 5.8 kg/m3 used for the deliberate synthesis of trichloro-
Critical temperature 620.3 K acetyl chloride [480].
Critical pressure 9740 kPa
Thermal conductivity (liquid) 0.13 W K−1 m−1
Hexachloroethane is obtained on chlorina-
Surface tension at 20 ◦ C 32.1 × 10−3 N/m tion. The atmospheric degradation of tetra-
Viscosity at 20 ◦ C 0.88 × 10−3 Pa · s chloroethylene has been thoroughly investi-
at 80 ◦ C 0.54 × 10−3 Pa · s gated, since it is often found during air sampling
Coefficient of cubical expansion
(0 – 40 ◦ C) 0.00102 K−1 [456, 481].
Dielectric constant at 20 ◦ C 2.20 Chlorine substitution by fluorine has been
Solubility in water at 25 ◦ C 150 mg/kg studied [482]. Due to the deactivating effect of
Solubility of water in
tetrachloroethylene at 25 ◦ C 80 mg/kg
the chlorine atoms, perchloroethylene cannot be
polymerized under normal conditions.

Tetrachloroethylene is a colorless heavy liq- 3.5.3. Production

uid with a mild odor. It is soluble with most
organic solvents and exhibits high solvency for The production of tetrachloroethylene is theoret-
organic compounds. Tetrachloroethylene is nei- ically possible by high temperature chlorination
ther flammable nor does it form explosive mix- of chlorinated lower molecular mass hydrocar-
tures with air. bons.
Some azeotropes formed by tetrachloroeth- For industrial purposes, three processes are
ylene are shown in Table 24. important:
76 Chlorinated Hydrocarbons

1) Production from acetylene via trichloroethyl- producer of hydrogen chloride, which must be
ene: consumed by other processes.
Depending on the individual site demands
C2 H2 +2Cl2 →C2 H2 Cl4
and on the proprietary technology of the pro-
C2 H2 Cl4 →C2 HCl3 +HCl
ducers, both processes presently play a key role
in modern tetrachloroethylene production.
C2 HCl3 +Cl2 →C2 HCl5 Tetrachloroethylene from Acetylene. Even
though the direct chlorination of acetylene to
C2 HCl5 →C2 Cl4 +HCl tetrachloroethylene is possible [483], most in-
2) Production from ethylene or 1,2-dichloro- dustrial processes use trichloroethylene as an in-
ethane through oxychlorination: termediate.
Chlorination of trichloroethylene in the liq-
CH2 = CH2 +CH2 Cl−CH2 Cl+2.5Cl2 +1.75O2 uid phase (70 – 110 ◦ C) and in the presence of
a Lewis-acid catalyst (0.1 – 1 wt % FeCl3 ) gives
→CHCl = CCl2 +CCl2 = CCl2 +3.5H2 O
pentachloroethane (pentachloroethane can also
3) Production from C1 – C3 hydrocarbons or be obtained from ethylene induced liquid phase
chlorinated hydrocarbons through high tem- chlorination of 1,2-dichloroethane (see Section
perature chlorination 2.8.3). Perchloroethylene is then produced from
The synthesis from acetylene, which is sim- pentachloroethane by either liquid-phase (80 –
ilar to the production of trichloroethylene from 120 ◦ C, Ca(OH)2 ) or catalytic thermal cracking
acetylene, was for many years the most impor- (170 – 330 ◦ C, activated carbon). Overall yields
tant production process. (based on acetylene) of 90 – 94 % are possible.
With increasing prices for the acetylene feed- Because of the long production sequence of
stock, however, this route has become unimpor- four reaction steps and the higher costs for the
tant. starting material acetylene, this process has lost
The first processes based on the high tem- its importance during the past 20 years.
perature chlorination of propene – propane mix- Tetrachloroethylene by Oxychlorination
tures were developed in the 1940s and early of Ethylene, 1,2-Dichloroethane, or Chlori-
1950s. These so-called chlorinolysis processes nated C2 Hydrocarbon Residues. The produc-
(chlorinating pyrolysis) have been further de- tion of tetrachloroethylene by this route has been
veloped and are currently the major source of described earlier (see page 73). This process
tetrachloroethylene. Instead of propene – pro- produces mainly tri- and tetrachloroethylene.
pane mixtures, ethane or C1 – C3 chlorinated hy- Heavy byproducts such as hexachloroethane,
drocarbon residues are nowadays used as feed. hexachlorobutadiene, and chlorinated benzenes
The chlorinolysis process has become an im- must be withdrawn and disposed of or inciner-
portant step in recovering hydrocarbons and ated. The light products can be recycled, which
valuable chlorine from residues of other pro- is important for tetrachloromethane, a major by-
cesses (e.g., from vinyl chloride and 1,1,1-tri- product [484]. For further literature, see [485].
chloroethane production).
Tetrachloroethylene by Chlorination of
With the development of oxychlorination
Hydrocarbons and Chlorinated Hydrocar-
techniques, ethylene or 1,2-dichloroethane oxy-
bons. Theoretically, three process modifications
chlorination has become the second most im-
must be distinguished for this route:
portant route. This process also allows the use
of residues instead of pure feed material. 1) High temperature chlorination of ethylene,
The basic difference between both processes 1,2-dichloroethane, or chlorinated C2 hydro-
is that tri- and tetrachloroethylene are obtained carbons
primarily from oxychlorination, whereas by the 2) Low pressure chlorinolysis
chlorinolysis route, tetrachloromethane is gen- 3) High pressure chlorinolysis
erated as a byproduct. Furthermore, the oxychlo-
rination process is the most balanced on hydro-
gen chloride. The chlorinolysis process is a net
 Chlorinated Hydrocarbons 77

The high temperature chlorination based on increased temperature and reduced chlorine sur-
ethylene or chlorinated C2 hydrocarbons has plus and pressure. However, because industrial
been mainly developed by the Diamond Alkali processes are very rarely thermodynamically
Co. [486] and the Donau Chemie AG [487]. The controlled, the product mix can be widely varied
feed is reacted with chlorine at an elevated tem- in a range of ca. 5 : 1 (tetrachloroethylene : tetra-
perature (200 – 550 ◦ C) in either fluidized (Di- chloromethane), depending on the feed products
amond Alkali) or fixed (Donau Chemie) cata- and ratios and on such physical conditions as
lyst beds. Silica and alumina for fluidized beds temperature and pressure. Besides tetrachloro-
and activated carbon for fixed beds have been ethylene and -methane, hexachloroethane, -
patented as catalysts. butadiene, and -benzene are obtained because
After quenching, hydrogen chloride and of their high stability. The latter three prod-
tetrachloroethylene are withdrawn and purified ucts may account for up to 10 % of the car-
by distillation. The light ends can be recycled bon yield. Hexachloroethane is almost exclu-
to the reactor; heavies like hexachloroethane sively and hexachlorobutadiene frequently recy-
and hexachlorobenzene must be withdrawn. Ma- cled, whereas the hexachlorobenzene recycle is
jor recyclable byproducts are dichloroethylenes, technically more difficult and not so often prac-
tetrachloroethanes, and trichloroethylene. Tri- ticed. It is withdrawn with some hexachlorobu-
chloroethylene can be converted to tetrachloro- tadiene and disposed or incinerated for the gen-
ethylene by separate chlorination and recycled eration of hydrogen chloride or chlorine.
to the reactor, where the pentachloroethane
formed is cracked [487, 488]. Because the pen-
tachloroethane cracking is an endothermic re-
action, the reactor temperature can be con-
trolled by the addition of externally formed pen-
tachloroethane. The carbon yield for tetrachloro-
ethylene from the high temperature chlorina-
tion is about 90 – 92 %. Yield losses result from
the formation of heavies. Chlorine conversions
range between 95 and 98 %.
Because separation of tetrachloroethylene
from 1,1,1,2-tetrachloroethane is difficult to
achieve, ethylene derivatives may be added
to the quench tower, which are more easily
hydrochlorinated as trichloroethylene, the tetra-
chloroethane precursor [489].
In the chlorinolysis process, hydrocarbons or
chlorinated hydrocarbons are chlorinated and
pyrolyzed to give mainly tetrachloromethane
and tetrachloroethylene. Figure 27. Thermodynamic equilibrium constants for the
Kinetically, the reaction consists of a whole systems CCl4 – C2 Cl4 + Cl2 and C2 Cl6 – C2 Cl4 + Cl2 as
function of temperature [490]
series of radical crack and substitution reactions
which lead to the most stable products.
Thermodynamically, the reaction is governed Presently, two modifications of the chlorinol-
by two basic equilibria: ysis process are in use: the low pressure chlori-
nolysis and the high pressure chlorinolysis.
2CCl4
C2 Cl4 +2Cl2 The low pressure chlorinolysis process is
used by most producers. Feedstock for this pro-
C2 Cl6
C2 Cl4 +Cl2 cess are C1 – C3 , preferably C2 and C3 hydrocar-
The thermodynamic equilibrium constants of bons and chlorinated hydrocarbons.
this reaction are plotted as a function of the re- Historically, this process dates back to the
ciprocal temperature in Figure 27 [490]. The for- 1940s. It was first used by Dow Chemical [491]
mation of tetrachloroethylene is favored by an and somewhat later by Stauffer [492]. Originally
78 Chlorinated Hydrocarbons

designed for substitution of acetylene by cheaper chlorine. In most plants, therefore, quenching
feedstocks such as ethane and propane, it was in- is achieved by a high recirculation rate of con-
creasingly used for the conversion of unwanted densed reaction gases. The heat of reaction is
byproducts, mainly from chlorinated hydrocar- removed by air coolers and heat exchangers or
bon (vinyl chloride, allyl chloride, 1,1,1-tri- can be used for product distillation [497]. Excess
chloroethane) and chlorohydrin (propylene ox- chlorine is either removed by washing or absorp-
ide, epichlorohydrin) processes, into more valu- tion – desorption with tetrachloromethane [495]
able products. or it can be used for ethylene chlorination to
With the shift of the traditional feedstock 1,2-dichloroethane which is either recycled or
from hydrocarbons toward such byproducts as consumed for the production of vinyl chloride
1,2-dichloropropane, tetrachloroethanes, pen- [498].
tachloroethane, dichloroethylenes, and chlori- Process Description (Fig. 28). Hydrocar-
nated propanes and propenes, the chlorinoly- bons (ethane, propylene) or chlorinated hydro-
sis process fulfills an ecologically and econom- carbon residues are preheated and fed together
ically important function for integrated chlo- with vaporized chlorine to the reactor (material:
rinated hydrocarbon sites. If the demand for Ni-alloys or brick lined carbon steel). After the
perchloroethylene or carbontetrachloride ex- reaction, the hot reaction gases are quenched
ceeds the available residual feedstock capacity, and chlorine and hydrogen chloride are distilled
the process can be carried out with ethylene, overhead. Hydrogen chloride is purified by frac-
ethane, propene, and propane, of which the latter tional distillation, and the remaining chlorine is
three products are preferred because of the cost removed by absorption with carbon tetrachloride
advantage. or other light ends and recycled to the reactor.
The reaction is carried out at a reactor temper- If carbon tetrachloride is used for absorption,
atures between 600 and 800 ◦ C and a pressure the chlorine can be stripped in a second tower
between 0.2 and 1.0 MPa. The slightly increased to avoid recycling of the solvent [495]. After
pressure makes the anhydrous purification of the degassing, the quench bottoms are submitted to
formed hydrogen chloride easier. Adiabatic as fractional distillation. Light ends and medium
well as isothermal reactors are used [491 – 493]. boilers are recycled, and perchloroethylene and
Most processes use empty tubular or backmixed carbon tetrachloride are withdrawn and can be
tank reactors, but fluidized-bed reactors have further purified. The heavy byproducts are fur-
also been patented [494]. In this reactor type, re- ther treated to recover hexachloroethane and
action temperatures are about 500 ◦ C, which re- hexachlorobutadiene, both of which can be re-
sults in higher hexachloroethane formation and cycled to the reactor. Hexachlorobenzene is ei-
increased recycle. Mean residence times range ther disposed or incinerated to generate hydro-
between 1 and 10 s. gen chloride or chlorine.
If chlorohydrin residues containing oxy- Maximum yield may be as much as 95 %
genated compounds are used, these feedstreams tetrachloroethylene [499]; in industrial scale
must be pretreated (water wash) because most processes, however, ca. 90 % is achieved [500].
chlorinolysis processes are very sensitive to oxy- In a process modification by Progil Elec-
gen. Oxygen containing feed can lead to the for- trochimie, a reactor cascade with two reactors is
mation of phosgene, carbon oxides, and water, used instead of one reactor [501]. The reaction
which may contaminate the products or cause temperature is kept below 600 ◦ C by external
corrosion. A process designed and carried out cooling.
by Chemische Werke Hüls, however, is capable Another modification consists of liquid phase
of also handling oxygenated compounds in the chlorination at 160 – 200 ◦ C followed by cat-
feed [495]. alytic gas phase chlorinolysis at 450 – 600 ◦ C.
Rapid quenching of the gases is important to Molybdenum pentachloride was patented as a
avoid excessive formation of hexachloroethane. catalyst [502].
Modern processes avoid the aqueous quench The high pressure chlorinolysis process was
systems used in old plants [496] because cor- developed by Hoechst AG [503]. The chlorinol-
rosion is difficult to control and complicated ysis reaction is non-catalytic at a pressure up to
drying systems are required to recover excess 20.0 MPa and a temperature of about 600 ◦ C. It
 Chlorinated Hydrocarbons 79

Figure 28. Schematic flow diagram of the chlorinolysis process

a) Reactor; b) Quench tower; c) Cooler; d) and e) HCl tower; f) Degasser; g) Heavies tower; h) Light-end tower; i) Carbon
tetrachloride tower; j) Medium-boilers tower; k) Perchloroethylene tower

is claimed that this process can also use higher 3.5.4. Uses and Economic Aspects
molecular mass feed, which may contain aro-
matic and alicyclic compounds. A nickel-plated The major use for tetrachloroethylene is as a
steel reactor is used. solvent for dry cleaning (ca. 60 % of the total
A 50 000 t/a plant was installed at the Frank- consumption). It has replaced almost all other
furt site. solvents in this field because it is non-flamma-
However, apart from the tolerance against ble and allows safe operation of drycleaning
higher molecular mass feed and the easier sepa- units without special precautions. Because tetra-
ration of hydrogen chloride and chlorine due to chloroethylene is very stable, it contains only
the increased pressure, this process offers no ma- low concentrations of stabilizers, preferably al-
jor advantages over the low pressure process. kylamines and morpholine derivatives. Because
Other Processes. A process to produce of its high stability, it is also used in addition
tetrachloroethylene from carbon tetrachloride to trichloroethylene and 1,1,1-trichloroethane
and carbon monoxide has been developed [504], for metal degreasing. Particularly for aluminum
but has not gained any importance. The conven- parts, it is superior to other degreasing formula-
tional chlorinolysis process allows broad vari- tions.
ations between tetrachloroethylene and carbon Other uses are textile finishing and dyeing
tetrachloride production to accommodate vary- and extraction processes.
ing market demands without being limited by In smaller quantities, tetrachloroethylene is
the second product. used as an intermediate for the production of tri-
chloroacetic acid and some fluorocarbons.
Because more than half of the Western
World’s tetrachloroethylene production is based
80 Chlorinated Hydrocarbons

on the chlorinolysis process, which coproduces is achieved with non-polar to medium polar sta-
carbon tetrachloride in varying ratios, capacity tionary phases such as OV-1, OV-101, OV-17,
and output are difficult to estimate. OV-1701, and FFAP. The flame ionization de-
U.S. production capacity was estimated at tector (FID) is used for detection in concentrated
380 000 t/a for 1985. In Europe the installed ca- substances. For low concentrations, the electron
pacity is ca. 450 000 t/a. Total capacity of the capture detector (ECD), together with capillary
Western World may average 1 000 000 t/a. columns and direct on-column injection, offers
Even though the consumption of tetrachloro- excellent sensitivity down to the pg-level.
ethylene has been declining since the late sev- Unequivocal identification of chlorinated
enties, the annual rate of decline is very mod- compounds in mixtures is possible by GC/MS
erate [505] compared to that of trichloroethyl- analysis. For very diluted aqueous samples, head
ene because a replacement of tetrachloroethyl- space, purge-and-trap or closed loop stripping
ene in its main use in dry cleaning is difficult to techniques may be used to further enhance the
achieve without sacrificing safety. Thus, the re- sensitivity.
duced consumption is mainly due to improved Analysis of air samples can be achieved by
dry-cleaning units with reduced solvent losses adsorption on activated carbon or other con-
to the atmosphere. This trend will continue for venient materials, followed by thermal or liq-
many years because more stringent environmen- uid (CS2 ) desorption and consecutive analysis.
tal regulations have been passed in most coun- To eliminate matrix effects, vapor distillation or
tries, which may cause an even steeper decline hexane extraction has been proven to be versatile
in the future. The production of tetrachloroeth- for aqueous or solid samples. The water content
ylene in 1993 is estimated to be 123 000 t in is best determined by the Karl-Fischer method.
the United States and 74 000 t in the Federal For the determination of the acidity and al-
Republic of Germany. Assuming a similar ca- kalinity, titrations with methanolic or ethanolic
pacity utilization for the entire Western World, sodium hydroxide or hydrogen chloride can be
the 1993 production may be 600 000 – 700 000 used.
t. With the poor capacity utilization and de- Free chlorine can be detected by iodometric
creased consumption, new plants cannot be jus- analysis.
tified since the mid 1980s. The construction of a Some typical values are given in Table 25.
new unit however, was announced in Poland in
1985 [506]. For such typical solvents as 1,1,1-tri-
chloroethane, trichloroethylene, and tetra-
chloroethylene, the specifications are standard-
3.6. Analysis and Quality Control of ized in some countries, and standard methods
Chloroethanes and Chloroethylenes for analysis (ISO, ASTM) have been developed.

Standard methods are used for the analysis of

chlorinated ethanes and ethylenes. A typical 3.7. Storage and Transportation of
analysis comprises: Chloroethanes and Chloroethylenes
purity
water content Before being stored or transported over longer
acidity/alkalinity periods of time, chlorinated ethanes and ethyl-
free chlorine content enes should be carefully analyzed for water, free
nonvolatile residues acid, and stabilizers because decomposition may
physical parameters such as density, refrac- lead to excessive corrosion.
tive index, boiling point, and color Chlorinated ethanes and ethylenes should not
be brought into contact with tanks, containers,
Because of the high volatility of all chlo-
valves, etc. made of aluminum.
rinated ethanes and ethylenes, gas chromato-
Contact with copper should be avoided un-
graphic analysis is the method of choice for
der all circumstances because dichloroethylenes
purity control. Capillary columns are widely
could form explosive acetylides.
used for high resolution. Excellent separation
 Chlorinated Hydrocarbons 81
Table 25. Typical degree of purity of some chlorinated ethanes and ethylenes

Compound Purity Acidity as HCl Water content Free chlorineResidues

Chloroethane C2 H5 Cl >99 % <200 ppm < 15 ppm n.d.* <100 ppm

1,2-Dichloroethane C2 H4 Cl2 >99 % < 20 ppm <100 ppm n.d.* < 50 ppm
1,1,1-Trichloroethane CH3 CCl3 >99 %*∗ < 10 ppm <100 ppm n.d.* < 50 ppm
Trichloroethylene C2 HCl3 >99 %*∗ < 10 ppm <100 ppm n.d.* < 50 ppm
Tetrachloroethylene C2 Cl4 >99 %*∗ < 10 ppm <100 ppm n.d.* < 50 ppm
∗∗
* n.d. = not detectable; unstabilized

Table 26. Transportation codes and classification for some chlorinated ethanes and ethylenes [507]

Compound UN-No. HAZ CHEM IMDG RID Pollution

category [508]

Chloroethane 1037 3WE class 2 class 2 −

D 2154 201
E 2057 3bt
1,1-Dichloroethane 2362 2YE class 3.2 class 3 B
D 3268 301
E 3069–1 3b
1,2-Dichloroethane 1184 2YE class 3.2 class 3 B
D 3303 301
E 3079 16b
1,1,1-Trichloroethane 2831 2Z class 6.1 class 6.1 B
D 6387 601
E 6178–2 15 C
1,1,2,2-Tetrachloroethane 1702 2XE class 6.1 class 6.1 B
D 6374 601
E 6173 15b
Pentachloroethane 1669 2Z class 6.1 class 6.1 −
D 6322 601
E 6143 15b
Vinyl chloride 1086 2WE class 2 class 2 −
D 2244 201
E 2125 3 ct
1,1-Dichloroethylene 1303 3YE class 3.1 class 3 B
D 3170 301
E 3050 1a
1,2-Dichloroethylene 1150 3 YE class 2 class 3 D
D 3269 301
E 3069 1a
Trichloroethylene 1710 2Z class 6.1 class 6.1 B
E 6179 601
12b
Tetrachloroethylene 1897 2Z class 6.1 class 6.1 B
D 6375 601
E 6173–1 15c

Since 1,1,1-trichloroethane decomposes very 3.8. Environmental Aspects in the

easily, tanks coated with highly solvent resistant Production of Chloroethanes and
phenolic resin should be used. Chloroethylenes
Care must be taken with such high sol-
vency compounds as 1,1,1-trichloroethane and
1,1,2,2-tetrachloroethane because they may at- The environmental impact of production facili-
tack coated or painted equipment. ties can be caused by waste (byproducts), emis-
Some transportation regulations are shown in sions to the air, and emissions to the water. In
Table 26.
82 Chlorinated Hydrocarbons

modern, integrated plants, however, waste prob- In the past, emissions by the Oxy – EDC vent
lems are minimized by proper balancing and a posed the largest problems. With the conversion
proper choice of production processes. to oxygen, however (see page 37), this vent has
Hydrogen chloride generated by crack or become manageable and can be eliminated.
substitution reactions is consumed by oxychlo- For the Lummus Transcat-Process (see Sec-
rination, hydrochlorination, or HCl electrolysis tion 3.1.3.4), a vent treatment system comprising
processes. CO2 absorption followed by ethylene stripping
Organic byproducts can be used as feedstock has been proposed [520].
for another process and converted into valuable Emissions into water were drastically re-
products. Examples are the conversion of 1,1,2- duced in the past since most modern processes
trichloroethane to 1,1-dichloroethylene, the con- for the production of chlorinated ethanes and
version of tetrachloroethanes to trichloroeth- ethylenes avoid the quenching of reaction gases
ylene, and the consumption of a wide range with water to separate hydrogen chloride. By dry
of residues in the production of tri- and tetra- distillation and the use of refrigeration units, this
chloroethylene by oxychlorination or in the potential source for contamination could be ex-
chlorinolysis process for the production of car- cluded by an improved process design.
bon tetrachloride and tetrachloroethylene. Re- In processes in which water is formed dur-
cyclable products can be recovered from tar ing the reaction (e.g., Oxy – EDC) or chlori-
residues by especially designed equipment such nated hydrocarbons must be brought into contact
as rotating double screw heat exchangers [509] with water for other reasons (e.g., production of
or by vapor distillation [510]. Ferric chloride, of- vinylidene chloride from 1,1,2-trichloroethane),
ten used as a catalyst, can be removed from heav- the wastewater in modern plants is stripped with
ies by extraction with hydrochloric acid [511]. air or steam, depending on the nature of contam-
The main disposal method for non-recyclable inants. The gas can be either directly incinerated
products is high temperature incineration [512] or condensed and separated. The aqueous con-
or catalytic incineration [513]. Either hydrochlo- densate is recycled to the stripper, and the or-
ric acid or hydrogen chloride is obtained, which ganics can be reused or incinerated. Thus, only
can be recycled to oxychlorination or used for minor concentrations of chlorinated hydrocar-
other purposes. If incineration is carried out bons are discharged to the biological treatment
with pure oxygen, chlorine is formed by the facilities, from which the emissions are negligi-
Deacon equilibrium and can be separated and ble, and excessive, environmentally problematic
reused [514]. With the highly developed equip- discharge of chlorinated hydrocarbons to rivers
ment presently in use, incineration is carried out and to the sea is avoided.
with very high destruction efficiencies and the
remaining emissions do not cause environmen-
tal problems. 4. Chloropropanes
Other techniques which have been pro-
posed for recovery of chlorinated hydrocarbon 1,2-Dichloropropane is used both as a chem-
residues are destruction by a potassium chloride ical intermediate and as an industrial solvent.
melt to give hydrogen chloride [515] and use for 2-Chloropropane and 1,2,3-trichloropropane are
the production of polysulfides [516] and metal of lesser significance.
chlorides [517]. If appropriately scrubbed, it is
also possible to incinerate mercury-containing
catalysts from acetylene-based processes [518]. 4.1. 2-Chloropropane
Air emissions by tank and process vents can
be collected and incinerated. When incineration Physical Properties. 2-Chloropropane [75-
facilities are unavailable, removal of chlorinated 29-6], isopropyl chloride, CH3 – CHCl –CH3 ,
hydrocarbon impurities in vent streams is possi- M r 78.54, is a colorless liquid.
ble by adsorption units, since they have often mp − 117.2 ◦ C
been described for the removal of vinyl chloride bp 36.5 ◦ C
[519]. Liquid density  at 20 ◦ C 0.8588 g/cm3
 Chlorinated Hydrocarbons 83
Refractive index n20 1.3776
D ketones, as well as with aromatic, aliphatic, and
Dynamic viscosity η at 20 ◦ C 3.2 × 10−4 Pa s
Dielectric constant at 25 ◦ C 9.52 chlorinated hydrocarbons.
Azeotropes with 1.2 wt % water, bp 33.6 ◦ C Chemical Properties. 1,2-Dichloropropane
with 6.0 wt % methanol, bp 33.4 ◦ C
with 43 wt % pentane, bp 31 ◦ C
is stable at room temperature but is dehydrochlo-
rinated by thermal or catalytic cracking to al-
lyl chloride [107-05-1] and 1-chloro-1-propene
Chemical Properties. Prolonged exposure
[590-21-6] [528, 529]. It is incompatible
to heat and light can cause dehydrochlorination,
with strong oxidizers and strong acids. It is
especially in the presence of aluminum, zinc,
dehydrochlorinated by NaOH to give mainly
and iron. Reaction with NaOH or amines occurs
1-chloro-1-propene (45 % cis and 55 % trans
only at elevated temperature.
isomer) [530].
Production. 2-Chloropropane can be syn- Production. 1,2-Dichloropropane is a by-
thesized by addition of hydrogen chloride to product in the synthesis by the chlorohydrin pro-
propene using, e.g., alumina, aluminum chlo- cess of the important chemical intermediate pro-
ride, calcium chloride, or tellurium compounds pylene oxide (1,2-epoxypropane) [75-56-9].
as catalysts [521 – 525]. 2-Chloropropane is 1,2-Dichloropropane is obtained in smaller
also formed by reaction of 2-propanol with hy- amounts as a byproduct in the industrial synthe-
drogen chloride and either zinc chloride or tel- sis of allyl chloride. Direct synthesis (e.g., by the
lurium compounds as catalysts [526, 527]. addition of chlorine to propene) is not currently
Uses. 2-Chloropropane, like other chlori- carried out [531, 532].
nated hydrocarbons, is employed as a solvent. Quality Specifications and Chemical Anal-
ysis. 1,2-Dichloropropane is used both crude
and as a commercial grade product. The crude
4.2. 1,2-Dichloropropane product is used mainly as a chemical intermedi-
ate for the production of perchlorohydrocarbons
Physical Properties. 1,2-Dichloropropane
(see below). The commercial grade product has
[78-87-5], propylene dichloride, CH2 Cl – CHCl
a boiling range of 95 – 99 ◦ C at 101.3 kPa (1013
–CH3 , M r 112.99, is a colorless liquid.
mp − 100.4 ◦ C
mbar) (DIN 53 171, ASTM D 1078) and a wa-
bp 96.5 ◦ C ter content below 0.1 wt % (DIN 51 777, ASTM
Refractive index n20D 1.4394 D 1744). Quality analysis is carried out by gas
Specific heat cp at 30 ◦ C 1.38 kJ kg−1 K−1 chromatography.
Heat of vaporization 34.8 kJ/mol
Critical temperature T c 577 K Storage and Transportation. The usual
Critical pressure pc 4.43 MPa (44.3 bar) precautions for a highly flammable liquid must
Surface tension at 20 ◦ C 3.0 × 10−2 N/m
be observed with 1,2-dichloropropane. The
Dielectric constant 8.96
Solubility in water at 20 ◦ C 0.25 wt % compound can be stored for several months,
Solubility of water in but it should be protected from heat, light, mois-
1,2-dichloropropane at 20 ◦ C 0.16 wt % ture and air. Therefore, it is recommended that
Azeotropes with 12 wt % water, bp 78 ◦ C
with 53 wt % methanol, bp 62.9 ◦ C
the product be blanketed with nitrogen. Carbon
with 57.74 wt % ethanol, bp 74.7 ◦ C steel is a suitable material for storage containers
with 84 wt % cyclohexane, bp 80.4 ◦ C provided that the acid and water concentration of
with 84 wt % tetrachloro- the product is low. Rust may increase the color
methane, bp 76.6 ◦ C
Flash point (Abel-Pensky, number; however, this is a problem which can
DIN 51 755) 13 ◦ C be avoided by using stainless steel. Light metals,
Autoignition temperature such as aluminum, magnesium, and their alloys,
(DIN 51 794) 557 ◦ C
Explosion limits in air:
can react violently with 1,2-dichloropropane.
lower limit 3.4 vol% As material for gaskets Teflon, Hostaflon, or IT
upper limit 14.5 vol% 400-C (DIN 3754) can be used but materials like
PVC, Perbunane, polyethylene, polypropylene,
Table 27 shows data on this compound. and rubber are not suitable.
1,2-Dichloropropane is miscible with most Railway tankcars, tanktrucks, and barrels are
organic solvents, such as alcohols, esters, and used for transportation.
84 Chlorinated Hydrocarbons
Table 27. Vapor pressure (p), liquid density (), and dynamic viscosity (η) as a function of temperature

t, ◦ C
0 20 50 80

p, kPa 1.8 5.1 19.8 59.9

, g/cm3 1.1815 1.1554 1.1161 1.0751
η, Pa s×10−4 12 8.5 5.8 4.4

The EC directive on dangerous substances 1,2-Dichloropropane is applicable as a lead

must be observed in labeling any containers scavenger for antiknock fluids [537], and it is
intended for transporting and handling 1,2-di- used in petroleum refineries in platforming pro-
chloropropane (July 14, 1976, No. 67/548/EC). cesses to adjust the catalyst activity [538].
Hazard symbols F + Xn; R paragraphs 11 –
20; S paragraphs 9–16–29–33; EC no. 602–
020–00–0. UN no. 1279; Rail, RID: 3.1a; Road, 4.3. 1,2,3-Trichloropropane
ADR: 3.1a; Code no. for railcars and tank cars: Physical Properties. 1,2,3-Trichloropro-
33/1279; Sea, IMDG code: 3.2; Air, IATA article pane [96-18-4], trichlorohydrin, CH2 Cl – CHCl
no.: 1507. –CH2 Cl, M r 147.44, is a colorless liquid.
Legal Aspects in the Federal Republic of mp − 14.7 ◦ C
bp 156 ◦ C
Germany and in the European Community. Refractive index n20 1.4834
D
The “Verordnung über gefährliche Arbeitsstoffe Liquid density  at 20 ◦ C 1.388 g/cm3
(ArbStoffV) vom 11. 02. 1982, Anhang I Nr. 1,” Dynamic viscosity η at 20 ◦ C 2.5 × 10−4 Pa s
Surface tension at 20 ◦ C 3.77 × 10−2 N/m
and the “EG-Richtlinie vom 10. 06. 1982” must
Azeotrope with 31 wt %
be observed. cyclohexanol, bp 154.9 ◦ C
The MAK value (FRG, 1984) is 75 ppm (350 with 39 wt % cylcohexanone, bp 160.0 ◦ C
mg/m3 ). with ca. 14 wt % ethylene glycol,
bp ca. 152.2 ◦ C
According to the “Verordnung über brenn- with 65 wt % propionic acid, bp 139.5 ◦ C
bare Flüssigkeiten (VbF)”, 1,2-dichloropropane with 7.5 wt % acetamide, bp 154.4 ◦ C
belongs in the “Gefahrenklasse AI”. The legal Flash point 74.0 ◦ C
aspects cited in the “Vorschriften des Grundwas- Autoignition temperature 304 ◦ C
Explosion limits in air:
serschutzes (VLwF)” must also be considered, lower limit 3.2 vol%
as well as the “Unfallverhütungsvorschriften upper limit [539] 12.6 vol%
der Berufsgenossenschaften”. For safety recom-
mendations, see [533 – 537]. Chemical Properties. 1,2,3-Trichloropro-
Uses. The most important use of 1,2-di- pane forms glycerol upon treatment with steam
chloropropane is as an intermediate in the at 550 – 850 ◦ C, and heating it with aqueous
synthesis of perchloroethylene [127-18-4] and caustic gives rise to 2,3-dichloropropene, 2-
tetrachloromethane [56-23-5] [529]. 1,2-Di- chloroallyl alcohol, and the ether of the latter
chloropropane is a good solvent for fats, oils, [540]. Heating with NaOH may also produce
resins, and lacquers. It is suitable for extraction, dangerous chloropropynes. The MAK value of
cleaning, degreasing, and dewaxing operations 1,2,3-trichloropropane is 50 ppm (300 mg/cm3 )
in the chemical and technical industry. Since it (FRG 1984).
forms an azeotrope with water at 78 ◦ C, it can be Production. 1,2,3-Trichloropropane is pro-
used for removing water from organic solutions. duced by addition of chlorine to allyl chloride
1,2-Dichloropropane dissolves bitumen and [541].
tar asphalt. It is used to promote the adhesion The selectivity of the chlorination of 1,2-di-
of asphalt layers, and it is suitable for the pro- chloropropane to 1,2,3-trichloropropane is not
duction of roofing paper, insulation material, good [542, 543].
and shoe-polish. In combination with 1,3-di- Uses. 1,2,3-Trichloropropane is a solvent for
chloropropene [542-75-6] it can be used as a oils, fats, waxes, chlorinated rubber, and resins.
soil fumigant for nematodes. The reaction with water at high temperature to
 Chlorinated Hydrocarbons 85
Table 28. Physical properties of industrially important chlorinated derivatives of butane

1-Chlorobutane 1-Chloro-2- 2-Chlorobutane 2-Chloro-2-methylpro- 1,4-Di-

methylpropane (optically active pane chlorobutane
form)

Mr 92.57 92.57 92.57 92.57 127.02

mp, ◦ C −123.1 −131.2 −140.5 −25.2 −37.3
bp at 101.3 kPa, ◦ C 78.6 68.4 68.3 50.7 155.0
Density at 20 ◦ C, g/cm3 0.8865 0.8780 0.8721 0.8435 1.1408
n20
D 1.4025 1.3982 1.3966 1.3856 1.4550
Vapor pressure, kPa 2.0 (− 10.5 ◦ C) 16.8 (0 ◦ C) 6.5 (0 ◦ C) 2.7 (− 32 ◦ C) 1.3 (44 ◦ C)
4.0 (1 ◦ C) 10.7 (10 ◦ C) 13.3 (− 1 ◦ C) 2.3 (50 ◦ C)
10.7 (19.7 ◦ C) 17.0 (20 ◦ C) 53.2 (32.6 ◦ C) 5.8 (72 ◦ C)
27.1 (41.1 ◦ C) 25.9 (30 ◦ C) 87.4 (46.6 ◦ C)
66.5 (65.5 ◦ C) 38.0 (40 ◦ C)
Heat of formation ∆H ◦ of
liquid at 298 K, kJ/mol − 180 − 191 − 193 − 212
Heat of vaporization
∆Hv◦ (298 K), kJ/mol 33.1 31.8 31.4 28.9
Viscosity at 20 ◦ C, 10−4 Pa s 4.5 4.6 3.6 (30 ◦ C) 5.1 14.3
Flash point (closed cup), ◦ C − 12 − 20 − 27 52
Autoignition temperature, ◦ C 460 570

give glycerol is not employed commercially. that used for the preparation of isopropyl chlo-
1,2,3-Trichloropropane is used for the synthe- ride (see page 83).
sis of thiokol polysulfide elastomers if some
branching in the polymer structure is required
[544].

5. Chlorobutanes
Chlorobutanes can be prepared from butane by
liquid-phase or thermal chlorination, from the
butenes by addition of elemental chlorine or hy-
drogen chloride, and from butanol by esterifi-
cation. The chlorination of butane with chlorine
proceeds just as with the lower hydrocarbons,
although currently the process has no commer-
cial significance. The reaction has been found
to yield primarily the 1- and 2-chlorobutanes
along with the 1,3- and 1,4-dichlorobutanes (see
Fig. 29) [545 – 547]. For the influence of ini-
tiators and inhibitors on the chlorination of n-
butane, see [548, 549]. Figure 29. Product distribution in the chlorination of n-
Photochemical chlorination in the gas phase butane as a function of the n-butane : chlorine ratio (con-
at 15 – 20 ◦ C leads to a product distribution simi- ditions: reaction temperature 390 ◦ C, residence time 2 s,
pressure 101.3 kPa)
lar to that obtained from the strictly thermal pro-
cess [550].
Table 28 provides an overview of the phys-
ical properties of industrially significant chlo-
rine derivatives of butane. 2-Chlorobutane and 5.1. 1-Chlorobutane
isobutyl chloride are used primarily as starting Physical Properties. 1-Chlorobutane, n-
materials in Friedel-Crafts reactions. They are butyl chloride, CH3 (CH2 )3 Cl, is a colorless,
made exclusively by hydrochlorination of the flammable liquid with excellent solvent prop-
corresponding alcohols, a process analogous to
86 Chlorinated Hydrocarbons

erties for fats, oils, and waxes. For additional when warmed in aqueous alkaline medium.
physical properties, see Table 28. Complete decomposition to isobutylene and hy-
Binary azeotropes are listed in Table 29. drogen chloride commences above 160 ◦ C, par-
ticularly in the presence of such catalytic oxides
Table 29. Azeotropes of 1-chlorobutane as thorium oxide [557].
wt % Component Boiling point Production. tert-Butyl chloride is generally
of the azeo- prepared by reaction of tert-butyl alcohol with
trope, ◦ C
(101.3 kPa) hydrogen chloride. The hydrogen chloride is
passed into the alcohol until the high acid content
25.0 formic acid 69.4
21.5 ethanol 66.2
of the resulting aqueous phase indicates that re-
8.0 2-butanol 77.7 action is complete. The aqueous phase is then re-
28.5 methanol 57.2 moved and the residual product layer is washed
38.0 methyl ethyl ketone 77.0 to neutrality, dried, and, if necessary, distilled.
16.0 n-propanol 75.6
6.6 water 68.1 tert-Butyl chloride can also be prepared by
gas-phase reaction of isobutylene with hydro-
gen chloride over catalytic chlorides and oxides
Chemical Properties. 1-Chlorobutane is
such as Al2 O3 at a temperature below 100 ◦ C
stable if kept dry. In the presence of water, it
[558], as well as by passing hydrogen chloride
will hydrolyze, but more slowly than secondary
into isobutylene at a low temperature [559, 560].
or tertiary chlorides. Of industrial significance
is its reaction with magnesium to give the cor- Uses. tert-Butyl chloride is used in Friedel-
responding Grignard reagent. Crafts reactions (e.g., in the preparation of tert-
Production. 1-Chlorobutane is obtained by butylbenzene or tert-butylphenol) as well as
esterification of n-butanol with hydrogen chlo- for the synthesis of 4-chloro-2,2-dimethylbutane
ride or hydrochloric acid at 100 ◦ C either without (neohexyl chloride), used as a fragrance base.
a catalyst [551] or utilizing the accelerating ef-
fect of zinc chloride [552, 553], tripentylamine
hydrochloride [554], or phosphorus pentachlo- 5.3. 1,4-Dichlorobutane
ride [555]. n-Butyl chloride is also obtained, Physical Properties. The compound is a liq-
along with 2-chlorobutane, by the chlorination uid which is flammable when hot and misci-
of butane over aluminum oxide at 200 ◦ C [556]. ble with numerous organic solvents. For addi-
Uses. n-Butyl chloride is used as a solvent tional physical properties of 1,4-dichlorobutane,
and alkylating agent in reactions of the Friedel- Cl(CH2 )4 Cl, see Table 28.
Crafts type. It is also the starting material for the Chemical Properties. The compound is
synthesis of bis (tributyltin) oxide, (C4 H9 )3 Sn converted to 1,3-butadiene either thermally
–O – Sn(C4 H9 )3 (TBTO), used as an antifoul- at 600 – 700 ◦ C or over alkaline catalysts at
ing agent in marine coatings and as a general 350 ◦ C. Both chlorine atoms are exchange-
fungicide. able. Reaction with sodium sulfide gives tetra-
hydrothiophene, and diacetyl peroxide converts
1,4-dichlorobutane to 1,4,5,8-tetrachlorooctane.
5.2. tert-Butyl Chloride
Physical Properties. 2-Chloro-2-methylpro- Production. 1,4-Dichlorobutane is obtained
pane, tert-butyl chloride, (CH3 )3 CCl, is a color- from butane-1,4-diol and hydrogen chloride in
less liquid. It is miscible with common organic the presence of aqueous sulfuric acid at 165 ◦ C
solvents and forms constant-boiling mixtures [561].
with a number of substances, including metha- It can be prepared in good yield by treatment
nol, ethanol, and acetone. of tetrahydrofuran either with hydrogen chloride
Additional physical properties of 2-chloro-2- or with aqueous hydrochloric acid at 100 –200
◦
butane are listed in Table 28. C and 1 – 2 MPa (10 – 20 bar) [562 – 565]; de-
hydrating agents such as sulfuric acid or zinc
Chemical Properties. tert-Butyl chloride is chloride favor the reaction [564, 566 – 568].
very rapidly hydrolyzed to tert-butyl alcohol
 Chlorinated Hydrocarbons 87

Other suitable reagents for chlorinating tetra- 3,4-dichloro-1-butene, and higher boiling prod-
hydrofuran include phosgene or phosphorus ucts also are formed [573 – 578].
oxychloride in the presence of dimethylform- 3,4-Dichloro-1-butene [760-23-6] can be
amide [569]. converted to 1,4-dichloro-2-butene by isomer-
Uses. 1,4-Dichlorobutane is used as a syn- ization in the presence of copper(I) chloride
thetic intermediate, as, for example, in the pro- and/or zirconium phosphate [579 – 582].
duction of nylon. The two dichlorobutene isomers are also
formed in the oxychlorination of C4 cracking
fractions containing butadiene and isobutene
[583 – 587].
6. Chlorobutenes
Uses. 1,4-Dichloro-2-butene occurs as an in-
The chlorobutenes that have acquired sub- termediate in the production of chloroprene (see
stantial industrial and economic importance Section 6.4.3), as does 3,4-dichloro-1-butene.
include 2-chloro-1,3-butadiene (chloroprene) 1,4-Dichloro-2-butene is a starting material
and also 1,4-dichloro-2-butene, 3,4-dichloro- in the production of adiponitrile [111-69-3]
1-butene, 3-chloro-2-methyl-1-propene, 2,3-di- (adipic acid dinitrile), butane-1,4-diol [110-63-
chloro-1,3-butadiene, and hexachlorobutadiene. 4], and tetrahydrofuran [109-99-9]. Adipic acid
and hexamethylenediamine (starting materials
in the synthesis of nylon-6,6) are obtained from
6.1. 1,4-Dichloro-2-butene adiponitrile by saponification and hydrogen-
ation, respectively.
CH2 Cl – CH = CH – CH2 Cl; Mr 124.96 1,4-Di- Butane-1,4-diol and tetrahydrofuran can be
chloro-2-butene occurs as a low boiling cis form produced according to a process developed by
[1476-11-5] and as a higher boiling trans form Toyo Soda [588] which entails hydrolysis of 1,4-
[110-57-6]. dichloro-2-butene in the presence of sodium for-
Physical Properties. cis form: mate, followed by hydrogenation to butane-1,4-
mp − 48 ◦ C diol. Tetrahydrofuran is obtained by additional
bp at 101.3 kPa 154.3 ◦ C elimination of water. Tetrachlorobutane (R,R:
d25 1.188
4 [14499-87-7], R,S: [28507-96-2]) can also be
n25
D 1.4887
Vapor pressure at 20 ◦ C 0.44 kPa (4.4 mbar) produced from 1,4-dichloro-2-butene [589].

trans form:
mp + 1 ◦C
bp at 101.3 kPa 156.8 ◦ C
6.2. 3,4-Dichloro-1-butene
d25
4 1.183
n25
D 1.4861 CH2 Cl – CHCl – CH = CH2 ; M r 124.96; [760-
Vapor pressure at 20 ◦ C 0.31 kPa (3.1 mbar) 23-6]

Chemical Properties. 1,4-Dichloro-2- Physical Properties.

butene is stable at room temperature. If pro- bp at 101.3 kPa 118.6 ◦ C
d25
4 1.153
longed storage is envisaged, it is advisable to n20 1.4630
D
arrange to do so under nitrogen. Vapor pressure at 20 ◦ C 1.74 kPa (17.4 mbar)
Dehydrochlorination of the compound with
NaOH in the presence of a phase transfer cat- Chemical Properties. 3,4-Dichloro-1-
alyst gives 1-chloro-1,3-butadiene (cis: [10033- butene is stable at room temperature. At elevated
99-5], trans: [16503-25-6]) [570], as does heat- temperatures in the presence of glass or metals,
ing it with KOH to 90 ◦ C. however, it undergoes isomerization to 1,4-di-
Production. 1,4-Dichloro-2-butene is ob- chloro-2-butene. 3,4-Dichloro-1-butene is the
tained in a yield of 93 % by chlorination of bu- starting point in the production of chloroprene
tadiene in the vapor phase at 300 – 350 ◦ C, short (dehydrochlorination in the presence of aqueous
residence times being possible [571, 572]. At sodium hydroxide solution (see Section 6.4.3).
lower temperatures about 40 % of the product is
88 Chlorinated Hydrocarbons

Production. 3,4-Dichloro-1-butene is 2-Chloro-1,3-butadiene, generally known

formed, together with 1,4-dichloro-2-butene as chloroprene, was discovered in 1930 by
(ratio 40 : 60), in the chlorination of butadiene Carothers and Collins [609, 610] during work
[571 – 578]. It is also obtained by isomerization on the synthesis of vinylacetylene. Chloroprene
of 1,4-dichloro-2-butene in the presence of ei- is obtained from vinylacetylene by the addition
ther copper naphthenate [590], a PdCl2 – benzo- of HCl (see Section 6.4.3.2).
nitrile or CuCl –adiponitrile complex [591], or The discovery of chloroprene by Carothers
a catalyst complex consisting of copper(I) chlo- and Collins was based on the chemistry of
ride and an organic quaternary ammonium chlo- acetylenes by Father J. Nieuwlands, in 1925.
ride [592]. Chloroprene exists in four isomeric forms:
Inhibitors such as nitriles [593, 594], thiols 1-Chloro-1,3-butadiene (α-chloroprene or 1-
[595], acid amides, sulfoxides [596], and phos- chloroprene; two isomers: cis [10033-99-5] and
phines [597] are added to prevent isomerization trans [16503-25-6] ), 2-chloro-1,3-butadiene
and polymerization. [126-99-8] (β-chloroprene, also known as 2-
Uses. The only industrial use for 3,4-di- chloroprene or simply chloroprene), and 4-
chlorobutene is in the production of chloroprene. chloro-1,2-butadiene [25790-55-0] (isochloro-
prene). Only 2-chloroprene is economically
important – as a monomer used to produce
polychloroprene, also known as neoprene (the
6.3. 2,3,4-Trichloro-1-butene generic term for polymers of this type), e.g.,
Baypren, (Bayer) Butaclor (Distigugil), Denka
CH2 Cl – CHCl – CHCl = CH2 ; Mr 159.44 chloroprene (Denki-Kagaku).
[2431-50-7].
Physical Properties.
bp at 101.3 kPa 155 ◦ C 6.4.1. Physical Properties
d20
4 1.3430
n20
D 1.4944 Chloroprene is a colorless liquid with a charac-
Vapor pressure at 20 ◦ C 0.25 kPa (2.5 mbar)
Flash point 63 ◦ C
teristic ethereal odor. It is soluble in most organic
Specific heat at 20 ◦ C 1.088 J/g solvents. Its solubility in water at 25 ◦ C is 250
ppm.
Chemical Properties. 2,3,4-Trichloro-1- 2-Chloro-1,3-butadiene (β-chloroprene).
butene is a colorless, stable liquid at room tem- mp − 130 ◦ C
perature. Dehydrochlorination with NaOH in the bp at 101.3 kPa 59.4 ◦ C
presence of a phase transfer catalyst converts it to d 20
20 0.9583
n20 1.4583
2,3-dichloro-1,3-butadiene [1653-19-6] [598]. D
Flash point − 20 ◦ C (ASTM)
Production. 2,3,4-Trichloro-1-butene is Autoignition temperature 320 ◦ C
Limits of inflammability in air 2.1 – 11.5 vol%
produced from vinylacetylene or chloroprene by MAK value 10 ppm (36 mg/m3 )
addition of HCl in the presence of a CuCl com-
plex [599 – 603], followed by chlorination of Vapor pressure vs. temperature:
◦
the resulting 1,3-dichloro-2-butene (cis: [10075- C 0 10 20 30 40 50 59.4
38-4], trans: [7415-31-8]), during which HCl is kPa 10.4 16.3 25.0 37.3 53.3 73.9 101.3
eliminated [604].
Odor threshold 1 mg/L [611]
Uses. 2,3,4-Trichloro-1-butene is used ex- Specific heat at 20 ◦ C 1.314 J g−1 K−1
clusively for the production of 2,3-dichloro-1,3- Latent heat of
butadiene (see Section 6.5) [598, 605 – 608]. vaporization at 20 ◦ C 325 J/g
at 60 ◦ C 302 J/g
Reaction enthalpy
(3,4-dichloro-1-butene
6.4. 2-Chloro-1,3-butadiene → chloroprene) − 83.7 kJ/mol
Heat of polymerization − 711 J/g [612]
Reaction enthalpy of
CH2 = CCl – CH = CH2 ; M r 88.54,[126-99-8]. uninhibited chloroprene − 900 J/g
 Chlorinated Hydrocarbons 89

1-Chloro-1,3-butadiene (α-chloroprene) 1) Vapor phase chlorination of butadiene to a

mp at 101.3 kPa 66 – 67 ◦ C mixture of 3,4-dichloro-1-butene and 1,4-di-
d20
4 0.954 chloro-2-butene:

4-Chloro-1,2-butadiene (isochloroprene) Cl2 + CH2 = CH − CH

bp at 101.3 kPa 88 ◦ C
= CH2 → ClCH2 − CHCl − CH
d20
4 0.9891 = CH2 + ClCH2 − CH
n20 1.4775
D = CH − CH2 Cl

2) Catalytic isomerization of 1,4-dichloro-2-

butene to 3,4-dichloro-1-butene:
6.4.2. Chemical Properties
Chloroprene is a colorless, highly reactive liq-
uid. It undergoes substantial dimerization, even
at room temperature, from which the following
3) Dehydrochlorination of 3,4-dichloro-1-
compounds have been isolated:
butene with alkali to chloroprene (2-chloro-
1,2-Dichloro-1,2-divinylcyclobutane 1,3-butadiene):
(cis: [33817-64-0], trans: [33817-63-9]),
1,4-dichloro-4-vinylcyclohexene [65122-21- ClCH2 −CHCl−CH = CH2 +NaOH
6], →CH2 = CCl−CH = CH2 +NaCl+H2 O
1-chloro-4-(1-chlorovinyl)cyclohexene
[13547-06-3], and 2-chloro-4-(1-
chlorovinyl)-cyclohexene [28933-81-5].
1,6-Dichloro-1,5-cyclooctadiene [29480-42-
0] is formed from the cis-cyclobutane isomer
through rearrangement at elevated temperatures.
In the presence of air, uninhibited chloro-
prene accumulates peroxides, which may cause
it to undergo spontaneous ω-polymerization
to give the so-called “popcorn polymer.” This
process is different from the well-known α-
polymerization which leads to rubber-like prod-
ucts. α-Polymerization inhibitors include phe-
nothiazione and p-tert-butylcatechol. ω-Poly-
merization can be inhibited with nitric ox-
ide, N-nitrosodiphenylamine, N-nitrosophenyl-
hydroxylamine, and other nitroso compounds
[613 – 617].
Due to its polymerization tendency, chloro- Figure 30. Flow diagram for the chlorination of butadiene
prene is stored and transported under inert gas at a) and b) Chlorination reactors; c) Scrubber cooler; d) Heat
temperatures below − 10 ◦ C, with further pro- exchanger for carrying away heat generated by the reaction
tection by the addition of sufficient amounts of
inhibitor. Chlorination of Butadiene. The reaction of
chlorine with butadiene can be carried out in an
adiabatically operating reactor (see Fig. 30) at
6.4.3. Production
temperatures not exceeding 250 ◦ C and at pres-
6.4.3.1. Chloroprene from Butadiene sures of 0.1 – 0.7 MPa (1 – 7 bar). Intensive and
rapid mixing of the reactants is of decisive im-
The production of chloroprene (2-chloro-1,3- portance in preventing soot formation. In addi-
butadiene) from butadiene comprises three tion, temperature control is ensured by conduct-
steps: ing the reaction in such a way that there is always
90 Chlorinated Hydrocarbons

an excess of butadiene present (the molar ratio permitting recovery of chlorine and sodium hy-
of Cl2 to butadiene should be 1 : 5 – 1 : 50). The droxide solution (thereby decreasing the con-
hot gaseous reaction mixture, consisting mainly sumption of these raw materials) [623].
of dichlorobutenes, butadiene, and highly chlo- Processes have also been described for the de-
rinated C4 – C12 products, is condensed with liq- hydrochlorination of 3,4-dichloro-1-butene us-
uid dichlorobutene in a scrubber-cooler. The ex- ing an aqueous mixture of alcohols and NaOH
cess butadiene is removed at the top of the cooler [624 – 627]. These processes have the advantage
and returned to the chlorinator together with that the resulting sodium chloride is obtained as
fresh butadiene. The HCl gas which is formed a solid, permitting its direct use in a chlor – alkali
must be removed in a scrubber. The liquid reac- electrolysis plant.
tion products are removed at the bottom of the Chloroprene can be dried by the freezing
cooler and purified by distillation. The propor- method: moist chloroprene is cooled to <0 ◦ C
tion of dichlorobutenes in the reaction mixture and passed through a refrigerator, on the walls
is about 92 % [578]. of which ice crystals form. These ice crystals
Chlorination processes which utilize high re- are separated from the liquid chloroprene in a
actor temperatures (280 – 400 ◦ C) and very short recrystallizer, the water content of the resulting
residence times but avoid the need for an excess chloroprene being < 150 ppm [628].
of butadiene are known [571, 572]. Purification. The crude chloroprene ob-
Isomerization of the Dichlorobutenes. The tained at the end of the dehydrochlorination step
distillate from the preceding chlorination step is purified by distillation. Chloroprene should
consists of a mixture of 1,4-dichloro-2-butene be made prior to polymerization, as free from
and 3,4-dichloro-1-butene. This mixture is sub- 1-chloroprene as possible. Accomplishing this
sequently isomerized to pure 3,4-dichloro-1- requires a column with a large number of plates.
butene by heating to temperatures of 60 – 120 ◦ C Sieve plate or packed columns are generally
in the presence of a catalyst [590 – 592]. A mix- used.
ture which is enriched in 3,4-dichloro-1-butene To prevent polymerization in the column, in-
can be removed continuously from the reactor. hibitors are added and the crude chloroprene is
The desired 3,4-dichloro-1-butene, whose boil- distilled under reduced pressure.
ing point is lower than that of 1,4-dichloro-2- Inhibited chloroprene can be stored at a tem-
butene, is separated from the latter in a subse- perature of − 10 to − 20 ◦ C under nitrogen for
quent distillation step. Unreacted 1,4-dichloro- fairly long periods without risk.
2-butene is then returned to the isomerization The purity of chloroprene (target value
reactor. 99.9 %) is checked by gas chromatography. Im-
Dehydrochlorination of 3,4-Dichloro-1- purities can be identified by IR spectroscopy.
butene to Chloroprene. The dehydrochlorina- The Fischer method can be used to determine
tion of 3,4-dichloro-1-butene with dilute NaOH water.
in the presence of inhibitors gives 2-chloro-
1,3-butadiene. 1-Chloro-1,3-butadiene is also
formed as a byproduct [618]. 6.4.3.2. Chloroprene from Acetylene
The reaction is carried out at a temperature of Production of Monovinylacetylene. Acety-
40 – 80 ◦ C. Addition of phase transfer catalysts, lene dimerizes to monovinylacetylene in the
such as quaternary phosphonium or ammonium presence of aqueous or anhydrous copper(I)
compounds, accelerates the reaction consider- chloride and a catalyst solution containing ei-
ably and gives higher yields per unit time, e.g., ther an alkali metal salt or an ammonium salt.
99 % in 30 min [619 – 621].
The chloroprene and sodium chloride solu-
tion leaving the dehydrochlorination reactor is
separated in a distillation column or by decanta- The acetylene is led in under conditions that
tion [622]. The salt in the wastewater is either assure a short contact time, and the products
recovered by evaporation, or else the wastewater are rapidly removed from the catalyst solution.
is recycled to a chlor – alkali electrolysis plant Byproducts of the reaction are divinylacetylene,
 Chlorinated Hydrocarbons 91

acetaldehyde, and vinyl chloride [629]. Yields To date, however, none of these processes has
of monovinylacetylene range from 75 to 95 % become commercially important.
depending on the catalyst system. After con-
centration and purification, monovinylacetylene
is obtained as a colorless liquid boiling at 5.5 6.4.4. Economic Importance
◦
C and 101.3 kPa. Because of its tendency to
decompose, monovinylacetylene is diluted for Chloroprene is the starting monomer for the spe-
handling, hydrocarbons commonly being used cialized rubber known as polychloroprene.
as the diluent. The vulcanizates of polychloroprene have fa-
Production of Chloroprene. The first step vorable physical properties and excellent resis-
in the reaction of hydrogen chloride with tance to weathering and ozone. Articles made
monovinylacetylene is a 1,4-addition to give 4- with this rubber include electrical insulating and
chloro-1,2-butadiene [630]. sheathing materials, hoses, conveyor belts, flex-
ible bellows, transmission belts, sealing materi-
CH2 = CH−C≡CH+HCl→ClCH2 −CH = C = CH2
als, diving suits, and other protective suits.
The chlorine in this compound is very reac- Adhesive grades of polychloroprene are used
tive and the substance rearranges in the pres- mainly in the footwear industry. Polychloro-
ence of the Cu2 Cl2 -containing catalyst solution prene latexes have found application for dipped
to give 2-chloro-1,3-butadiene: goods (balloons, gloves), latex foam, fiber
binders, adhesives, and rug backing.
Chloroprene and polychloroprene are pro-
duced:
Under conditions where yields of 95 % are
achieved the principal byproduct is 1,3-di- – in the United States: by Du Pont and Petrotex
chloro-2-butene, resulting from further HCl ad- – in Western Europe: by Bayer in the Federal
dition: Republic of Germany, Distugil S.A. in France,
and Du Pont in Northern Ireland
– in Japan: by Showa-Denko, Denki Kagaku,
and Toyo Soda
The latter can be used as a starting material for – and in the Soviet Union
2,3-dichlorobutadiene, a comonomer of chloro-
prene. World polychloroprene capacity, 1983, in
Chlorides of mercury, magnesium, calcium, 1000 t [641]:
gold, and copper are all used in the produc-
United States 213
tion of chloroprene, as are ammonium chlo- Federal Republic of Germany 60
ride, ammonium bromide, pyridinium chloride, France 40
and methylammonium chloride. The most com- United Kingdom 30
monly used material, however, is the system Japan 85
Central planned economy countries 220
Cu2 Cl2 / NH4 Cl/HCl. Two reactors for chloro-
prene production have been described [631].

6.4.3.3. Other Processes 6.5. Dichlorobutadiene

Other processes described in the literature for 6.5.1. 2,3-Dichloro-1,3-butadiene

the production of chloroprene include oxychlo-
rination of butenes [583 – 588], chlorination of CH2 = CCl – CCl = CH2 ; M r 122.95[1653-19-
butadiene in organic solvents [632 – 636] and 6]
electrochemical chlorination of butadiene [637, Physical Properties.
638].
bp at 101.3 kPa 98 ◦ C
The direct chlorination of butadiene to d20 1.1829
4
chloroprene has been described in patents [639, n20
D 1.4890
640].
92 Chlorinated Hydrocarbons

Chemical Properties. 2,3-Dichlorobutadiene group which gave methallyl chloride its com-
is more reactive than chloroprene. Therefore, it mon name on the basis of the analogy of meth-
is not known to have been produced industrially acrylic acid. The IG Farben chemical works at
in the pure form. Inhibition with an inert gas Leuna in Germany prepared methallyl chloride
containing 0.1 vol% of NO has been reported on a semi-works scale a short time later (from
[642]. 1939 to 1942) in order to carry out investigations
Production. 2,3-Dichlorobutadiene is pro- in the polyamide field. Methallyl chloride pro-
duced by reacting butyne-1,4-diol with phos- duction by chlorination of isobutylene resumed
gene, followed by isomerization of the in- in Germany after World War II (about 1960) at
termediate 1,4-dichloro-1-butyne [62519-07-7] Chemische Werke Hüls AG.
in the presence of copper(I) chloride and
amines [643 – 645]. The dehydrochlorination of 6.6.1. Physical Properties
both 2,3,4-trichlorobutene (see Section 6.3) and
Mr 90.5
1,2,3,4-tetrachlorobutane with sodium hydrox-
mp <− 80 ◦ C
ide solution [598, 605 – 608, 646 – 648] has ac- bp at 101.3 kPa 72.0 ◦ C
quired industrial importance. Density at 20 ◦ C 0.9251 g/cm3
2,3-Dichlorobutadiene is an important mono- n20
D 1.4274
mer for special grades of polychloroprene in
Vapor pressure vs. temperature:
which the tendency to crystallize has been re- ◦
C − 13 18.8 36 53
duced. kPa 2.66 13.3 26.6 53.2

Heat of formation ∆H 0298 (liquid) − 105.1 kJ/mol

6.5.2. Other Dichlorobutadienes Heat of vaporization (calculated 31.8 kJ/mol
from the vapor pressure curve)
1,1-Dichloro-1,3-butadiene [6061-06-9] and Viscosity at 20 ◦ C 4.2 × 10−4 Pa s
Dielectric constant 7.0
1,3-dichloro-1,3-butadiene [41601-60-9] are Flash point − 16 ◦ C
obtained by chlorination of 1-chloro-1,3- (Pensky-Martens)
butadiene, followed by dehydrochlorination Autoignition temperature 540 ◦ C
Limits of inflammability in air 2.2 and 10.4 vol%
[649, 650]. at 20 ◦ C
1,1-Dichloro-1,3-butadiene is also obtained
by reduction of 4,4-dichloro-3-buten-2-one with Methallyl chloride is a colorless liquid of low
NaBH4 , followed by dehydrogenation with viscosity, irritating to the mucous membranes,
Al2 O3 [651]. This compound is used as a and with a pungent odor. It is miscible with all
comonomer for rubber and as an insecticide. of the common organic solvents.
1,4-Dichloro-1,3-butadiene (trans, trans: Solubility in water at 20 ◦ C is ca. 0.05 wt %;
[3588-12-3]; trans, cis: [3588-13-4]; cis, cis: water solubility in methallyl chloride is 0.04
[3588-11-2]) is manufactured by dehydrochlo- wt %
rination of tetrachlorobutane with zinc powder Methallyl chloride forms an azeotrope with
(yield: 60 %) [652]. water (5.8 wt %), which boils at 64.6 ◦ C.

6.6. 3-Chloro-2-methyl-1-propene 6.6.2. Chemical Properties

Methallyl chloride shows chemical behavior
3-Chloro-2-methyl-1-propene, [563-47-3] CH2 very similar to that of allyl chloride and un-
= C(CH3 ) – CH2 Cl, methallyl chloride, was first dergoes essentially the same reactions as the
prepared in 1884 by M. Sheshukov by the chlo- latter. The presence of a β-methyl group in-
rination of isobutylene at room temperature. In- creases its reactivity considerably, however. Un-
vestigation of the compound was taken up again der the influence of light and/or heat, the forma-
in the late 1930s by the research group of A. P. A. tion of low concentrations of dimeric methal-
Groll at the Shell Development Co. leading to lyl chloride (2-methyl-4,4-bis(chloromethyl)-1-
its production at the pilot plant scale. It was this pentene) occurs. Moisture causes samples of
 Chlorinated Hydrocarbons 93

methallyl chloride to become markedly acidic as double bond, thereby producing a tertiary car-
a result of hydrolysis. A similar phenomenon is bonium ion. This tertiary carbonium ion can re-
induced by either iron or iron chloride through act in one of three ways: either it can eliminate
dehydrochlorination of dimeric and polymeric a proton from C1 or C3 , both of which possi-
material. bilities lead to restoration of a double bond, or
The chlorine atom of methallyl chloride is else it can react further by addition of the chlo-
readily exchanged, as occurs, for example, in ride anion. All three possible products are ob-
its conversion to alcohols, ethers, amines, and tained in the chlorination of isobutylene: methal-
esters. Furthermore, the presence of the methyl lyl chloride (the favored product), the isomeric
group activates the double bond with respect to 1-chloro-2-methyl-1-propylene (isocrotyl chlo-
reactions such as hydration, addition of halo- ride), and 1,2-dichloroisobutane.
gen or halogen halides, sulfonation, dimeriza-
tion, and polymerization. Of greatest commer- Table 30. Critical temperature ranges for selected olefins for the
cial significance are its reaction with sodium sul- transition from chlorine addition to chlorine substitution, based on
fite to give sodium methallyl sulfonate and the [658]
production of 2-methylepichlorohydrin. For fur- Olefin Critical tempera-
ther chemical reactions of methallyl chloride, ture range, ◦ C
see [653 – 657]. Isobutylene (and other olefins
branched at the double bond) <– 40
2-Pentene 125 – 200
6.6.3. Production 2-Butene 150 – 225
Propylene 200 – 350
Ethylene 250 – 350
Methallyl chloride is produced exclusively by
chlorination of pure isobutylene in the gas phase.
Yields of 80 – 85 % are achieved at atmospheric Process Description. In carrying out the re-
pressure and a relatively low temperature (not action on the industrial scale, gaseous isobut-
exceeding 100 ◦ C). ylene (99 % pure) and chlorine are mixed at
Chlorination Mechanism. The chlorina- room temperature by using a dual-component
tion of isobutylene is somewhat unusual as jet, and the mixture is allowed to react in a cooled
compared to most olefin chlorinations. Treat- tube reactor at atmospheric pressure. The reac-
ment of olefins with elemental chlorine at a low tion rate is exceedingly high for such a low reac-
temperature normally leads to addition as the tion temperature, all of the chlorine being con-
dominant reaction. The competing substitution verted within ca. 0.5 s. Proper mixing of the com-
reaction, in which the double bond remains in- ponents by the inlet jet is a prerequisite to obtain-
tact, increases in importance as the temperature ing a high yield of methallyl chloride; reaction
is raised until a critical temperature is reached, is so rapid that high local concentrations of chlo-
above which one obtains almost exclusively the rine cannot be dissipated, leading instead to the
substitution product. The temperature range of production of more highly chlorinated products.
this transition from addition to substitution lies In order to minimize further chlorination of
highest for simple straight-chain olefins. Com- methallyl chloride, an excess of isobutylene
pounds with branching at the double bond, on the must be used, the amount necessary being de-
other hand, including isobutylene or 3-methyl- pendent on the extent of reverse mixing of the
2-butene, react principally by substitution even reaction products in the reactor. An excess of
at a very low temperature (−40 ◦ C), as shown isobutylene greater than ca. 25 % leads to no fur-
in Table 30. ther significant increase in the yield of methallyl
Presumably, chlorination of isobutylene fol- chloride with reactors in which minimal axial
lows an ionic mechanism, and solid metallic and mixing occurs; greater excesses would simply
liquid surfaces catalyze the reaction [659]. Ac- increase the effort required to recover unreacted
cording to [660 – 662], the following mecha- isobutylene. Low reaction temperatures are ad-
nism is likely: isobutylene reacts with a chlo- vantageous in respect to the product distribution:
rine molecule such that the equivalent of a pos- 100 ◦ C is generally regarded as the limit below
itive chlorine adds to the terminal carbon of the which the reaction should be kept.
94 Chlorinated Hydrocarbons

The use of liquid isobutylene as starting ma- In contrast to other hydrocarbon chlorina-
terial would seem a logical alternative, since one tion procedures (those employed with methane
could then take advantage of the cooling effect or propylene, for example), an aqueous workup
resulting from the compound’s heat of vaporiza- cannot in this case be avoided if isobutylene is to
tion. It has been shown, however, that this ap- be recycled. This is because isobutylene reacts
proach increases the yield of high boiling prod- with hydrogen chloride to form tert-butyl chlo-
ucts, presumably due to the decrease in effec- ride at the low temperature required for the sepa-
tiveness of mixing of the components relative to ration of the chlorinated hydrocarbons. If one is
the gas phase reaction. willing to accept the presence of tert-butyl chlo-
A typical analysis of a methallyl chloride pro- ride as a byproduct, however, one could, perhaps
duction run is shown in Table 31. with the aid of catalysts, avoid the complications
The tert-butyl chloride which is reported as of isobutylene recycling.
being formed is a secondary product from ad- Other Production Methods. A thorough
dition of hydrogen chloride to isobutylene. For investigation has been made of the use in place
information on the influence of other variables of pure isobutylene in the methallyl chloride
on the chlorination, see [663]. synthesis of a butane – butene (B – B) mixture
The work-up of the crude reaction product remaining after extraction of butadiene from
is, in principle, quite simple. The only difficulty the C4 fraction of petroleum cracking gases
would be removal by distillation of isocrotyl [664]. The C4 fraction can also be chlorinated
chloride, given its very similar boiling point (see directly by using the liquid products as a reac-
Table 31). The vinylic placement of its chlorine, tion medium, in which case any straight-chain
however, makes this substance very unreactive alkenes that are present react only to an insignif-
relative to methallyl chloride, so that its pres- icant extent [665]. As far as can be determined,
ence is not detrimental in many applications. For however, these interesting possibilities have not
this reason, it is normally separated only incom- yet seen useful commercial application.
pletely, if at all. Oxychlorination of isobutene is possible by
The effluent gas stream is led out of the reac- using tellurium compounds as catalysts [666].
tor into a water scrubber-cooler which absorbs High yields of methallyl chloride are achieved
the hydrogen chloride and causes the majority of on a small scale. Solution chlorination of
the chlorinated hydrocarbons to condense. Re- isobutene in the presence of TeCl4 or SeCl4 is
maining isobutylene exits from the top of the also known [667].
scrubber column. It is then collected, dried, com-
pressed, and returned to the reactor. The crude
methallyl chloride is separated from hydrochlo- 6.6.4. Quality Specifications and Chemical
ric acid in separatory flasks, dried by azeotropic Analysis
distillation, and freed by a preliminary distilla-
tion from more volatile byproducts (largely tert- The commercial product usually has a purity
butyl chloride and part of the isocrotyl chloride). of 96 – 98 % and contains isocrotyl chloride as
Methallyl chloride and residual isocrotyl chlo- its chief impurity, along with traces of 1,2-di-
ride are finally taken off at the head of a second chloroisobutane. It is stabilized with substituted
column. The more highly chlorinated distillation phenols or marketed without a stabilizer. The de-
residue is either worked up in a chlorinolysis unit gree of purity is established by gas chromatog-
or else it is burned under conditions permitting raphy. In many of its applications — such as co-
recovery of hydrogen chloride. polymerizations to produce synthetic fibers —
The use of glass apparatus is recommended even traces of iron are detrimental. The presence
both because of the fact that it is necessary to of iron is best determined spectroscopically, us-
work to some extent with the crude product ing o-phenanthroline, for example. Additional
while it is still moist, and also because even the information which should accompany any ship-
anhydrous crude product can evolve hydrogen ment would include the material’s color, water
chloride at elevated temperatures and in the pres- content, pH value, residue on evaporation, and
ence of ferrous materials. boiling range.
 Chlorinated Hydrocarbons 95
Table 31. Product distribution from isobutene chlorination, with physical properties of the substances

Compound Concentration Mr bp at 101.3 kPa, d20

4 n20
D
◦
range, wt % C

tert-Butyl chloride 2–4 92.5 50.8 0.8410 1.3860

Isocrotyl chloride 4–5 90.5 68.1 0.9186 1.4221
Methallyl chloride 83 – 86 90.5 72.0 0.9250 1.4274
1,2-Dichloroisobutane 6–8 127.0 108.0 1.089 1.436
3-Chloro-2-chloromethyl-1-propene 125 138.1 1.1782
1-Chloro-2-chloromethyl-1-propene 2–3 125 132.0 (cis) 1.1659 1.4702 (25 ◦ C)
130.0 (trans)
1,2,3-Trichloroisobutane 161.5 163.9
2-Methyl-4,4-bis(chloromethyl)-1-pentene 181 84.4 1.0711 1.4773
(1.3 kPa) (d20
20 )

6.6.5. Storage and Shipment Physical Properties.

mp − 18 ◦ C
Methallyl chloride is best stored under cool con- bp at 101.3 kPa 212 ◦ C
ditions in porcelain enameled vessels. Provided Density at 20 ◦ C 1.680 g/cm3
n20
D 1.5663
the material is kept very dry, it can also be
stored in tightly-sealed stainless steel storage Vapor pressure vs. temperature:
tanks. Porcelain enameled or baked enameled ◦
C 20 34 60 64 111
tankers are suitable for its transport, as are, for kPa 0.036 0.097 0.497 0.623 5.87
small shipments, special types of baked enam-
eled drums. Specific heat at 22 ◦ C 0.85 kJ kg−1 K−1
Heat of vaporization 48 kJ/mol
Coefficient of thermal conductivity 0.101 W K−1 m−1
Viscosity at 15 ◦ C 9.22 × 10−3 Pa s
6.6.6. Uses at 21 ◦ C 3.68 × 10−3 Pa s
at 50 ◦ C 2.40 × 10−3 Pa s
The potential uses for methallyl chloride as a Surface tension at 20 ◦ C 3.14 × 10−2 N/m
starting material in syntheses are, just as in Dielectric constant at 12 ◦ C 2.56
Dielectric strength when freshly ca. 200 kV/cm
the case of allyl chloride, extremely numer- prepared
ous [653]. Its use in pure form as a fumi-
gant and disinfectant has been suggested, as
has its application as a fumigating agent for Hexachlorobutadiene is a colorless, oily liq-
seed grains [668, 669]. Methallyl chloride and uid with a faint terpene-like odor. Its solubility
other methallyl derivatives prepared from it are in water at 20 ◦ C is 4 mg/kg, that of water in
exceptionally well suited to copolymerization hexachlorobutadiene at 20 ◦ C 10 mg/kg.
[670, 671]. The copolymerization of methallyl Chemical Properties. Chemically, hex-
sulfonate with acrylonitrile has gained particu- achlorobutadiene is very stable to acids and
lar industrial significance [672]. Since 1970, 2- alkali and has no tendency to polymerize even
methylepichlorohydrin for use in the production under high pressure (10 MPa). Hexachlorobu-
of special epoxy resins has been manufactured tadiene reacts with chlorine only under severe
from methallyl chloride at a production facil- reaction conditions (e.g., under pressure in an
ity in Japan with an annual capacity of 6000 t. autoclave at 230 – 250 ◦ C), and then generally
Methallyl chloride is used, together with allyl with cleavage of the carbon skeleton and forma-
chloride, in the manufacture of Allethrin, a syn- tion of hexachloroethane and perchloroethylene
thetic pyrethrum with applications as a pesticide. [673]. Octachlorobutene and decachlorobutane
are also produced in the temperature range 60
– 150 ◦ C [674, 675]. For further information
6.7. Hexachlorobutadiene about the properties, reactions, and application
possibilities of hexachlorobutadiene, see also
CCl2 = CCl – CCl = CCl2 ; M r 260.8 [87-68-3]. the compilations [676].
96 Chlorinated Hydrocarbons

Production. Hexachlorobutadiene occurs as nation of straight-chain paraffins or wax frac-

a byproduct in all chlorinolysis processes for the tions. The carbon chain length of commeri-
production of perchloroethylene or carbon tetra- cal products is usually between C10 – C30 and
chloride. Depending on the method employed, the chlorine content between 20–70 wt%. Four
the crude product contains ca. 5 % or even more main types of chlorinated paraffins are in regular
of hexachlorobutadiene, and this material can be use today (see Table 32).
recovered in pure form rather than being recy-
cled into the reactor. Since chlorolysis plants are Table 32. Types of chlorinated paraffins
of large capacity, the demand for hexachlorobu- Chlorinated paraffin type Common CAS registry
tadiene is generally met without the need for abbreviation number*
separate production facilities.
C10 – C13 (short-chain) SCCP [085535-84-8]
If hexachlorobutadiene is to be prepared di- chlorinated paraffins
rectly, the preferred starting materials are chlo- C14 – C17 (medium-chain) MCCP [085535-85-9]
rinated derivatives of butane. These are chlori- chlorinated paraffins
nated at 400 – 500 ◦ C and atmospheric pressure C18 – C20 (long-chain)
chlorinated paraffins
LCCP [063449-39-8]

with a 4-fold excess of chlorine, giving a 75 % C20 – C30 chlorinated paraffin [063449-39-8]
yield of hexachlorobutadiene [677]. waxes (liquid and solid
products)
The compound can also be prepared by chlo-
rination of butadiene in a fluidized-bed reactor * These CAS numbers are appropriate for Europe and denote
using a large excess of chlorine at 400 – 500 ◦ C
existing chemicals within the European EINECS inventory.
However they do not necessarily appear on the inventories of other
[678]. countries and it may be necessary to use alternative numbers in
territories outside of Europe. For example [085535-84-8] and
According to a method of the Consortium [085535-85-9] do not exist in the USA’s TSCA inventory, so
für Elektrochemische Industrie, hexachloro- [61788-76-9] “alkanes, chloro; alkanes chlorinated” is often used
1,3-butadiene can be made from 1,1,2,3,4,4- to describe these types of product.
hexachlorobutane, which comprises about 60 %
of the residue from the production of tetrachloro-
Compounds of this sort were first detected
ethane. The material is chlorinated repeatedly at
in the middle of the 19th century by J. B. A.
70 – 80 ◦ C in the presence of iron(III) chloride
Dumsa. It was he who showed that long-chain
and subsequently dehydrochlorinated at 170 ◦ C.
paraffins, known up to this date only as rela-
Uses. As a consequence of its low vapor pres- tively inert substances, are in fact subject to cer-
sure at room temperature, hexachlorobutadiene tain chemical reactions, and that the influence of
is suitable as an absorbent for the removal of artificial light promotes the processes. The first
impurities in gases, e.g., removing carbon tetra- systematic study on chlorinated paraffins was
chloride and other volatile compounds from hy- conducted some years later, between 1856 and
drogen chloride [679]. A mixture composed of 1858, by P. A. Bolley [683].
hexachlorobutadiene (50 – 70 %) and trichloro- Chlorinated paraffins acquired industrial im-
ethylene has found use as a coolant in transform- portance in the early 1930s and consumption
ers [680]. The production of electrically con- grew rapidly, particularly during World War
ductive polymers with hexachlorobutadiene has II, with increasing use of the substances as
been patented [681]. The compound’s herbicidal flameproofing and rot-preventing agents. Fur-
properties have led to its use in the prevention of ther rapid expansion subsequently took place
algal buildup in industrial water reservoirs, cool- during the 1960s when low-cost normal paraf-
ing towers, and cooling water systems [682]. Fi- fin became freely available as feedstocks and
nally, it has been repeatedly suggested as a hy- chlorinated paraffins were recognized as effec-
draulic fluid, as a synthetic lubricant, and as a tive plasticizers for PVC. Recent developments
nonflammable insulating oil. in this area have seen the introduction of a range
of chlorinated α-olefins and aqueous based pro-
cesses for producing solid chlorinated paraffin
7. Chlorinated Paraffins waxes [684, 685].
“Chlorinated paraffins” is the collective name The total world production of chlorinated
given to industrial products prepared by chlori- paraffins is estimated to be 500 000 t per year,
 Chlorinated Hydrocarbons 97

and they are regarded as important substances The resulting polyalkenes once becoming con-
with a wide range of applications. The major jugated cause a deepening of color.
markets for chlorinated paraffins are the USA,
Europe, and Asia. The vast majority of the mar-
ket comprises of liquid chlorinated paraffins
with only limited quantities of solid chlorinated
paraffin produced.

7.1. Physical Properties

Chlorinated paraffins are homogeneous, neutral,

colorless to pale yellow liquids. Their viscosi-
ties, densities and refractive indices rise with
increasing chlorine content for a given carbon
chain length and also with chain length at con- Figure 32. Densities of chlorinated paraffins
stant chlorine content (see Fig. 31). Volatili-
ties, on the other hand, decrease with an in- Accumulated hydrogen chloride operates as
crease in chain length and degree of chlorina- a catalyst for further dehydrochlorination.
tion (see Fig. 32). Physical properties of selected Elimination of hydrogen chloride becomes
commercially available chlorinated paraffins are significant at temperatures above 220 ◦ C and
given in Table 33. for most applications this marks the upper limit
of chlorinated paraffin use. For most commer-
cially available grades volatility also becomes
unacceptably high above this temperature.
The thermal stability of a chlorinated paraf-
fin is defined by the extent to which it undergoes
degradation at 175 ◦ C over a 4 h period. The
determination of the thermal stability requires
use of a standardized piece of apparatus. There
are a number of efficient stabilization systems,
which increase the thermal stability of chlori-
nated paraffins, facilitating their use at the upper
end of the temperature range noted above. Typi-
cally these involve the addition of small amounts
of epoxide-containing compounds, antioxidants
and organic phosphites. Likewise, stabilizers are
Figure 31. Viscosities of chlorinated paraffins known which prevent darkening of chlorinated
paraffins caused by the adverse effects of ultra-
Chlorinated paraffins are practically insolu- violet light.
ble in water and lower alcohols. They are sol- Apart from chlorine content and chain length,
uble, however, in chlorinated aliphatic and aro- no convenient physical or physicochemical
matic hydrocarbons, esters, ethers, ketones, and properties are available for the characterization
mineral or vegetable oils. Their solubility in of individual types of chlorinated paraffins.
unchlorinated aliphatic and aromatic hydrocar-
bons is only moderate. Different types of chlori-
nated paraffins are completely miscible with one 7.2. Chemical Properties and Structure
another.
At temperatures above 120 ◦ C, some decom- Commercially available chlorinated paraffins
position of chlorinated paraffins may occur ac- are not simple well defined chemical com-
companied by elimination of hydrogen chloride. pounds. Instead they are complex mixtures of
many molecular species differing in the lengths
98 Chlorinated Hydrocarbons

Table 33. Physical properties of selected commercial chlorinated paraffins

Trade name Paraffin carbonNominal Color hazen, Viscositya , Densitya , Thermal Volatilityc , Refractive
chain length chlorine APHA mPas g/mL stabilityb , wt % index
content, wt % wt % HCl

CERECLORTMC10 – C13 50 100 80 1.19 0.15 16.0 1.493

50LV
CERECLORTMC10 – C13 56 100 800 1.30 0.15 7.0 1.508
56L
CERECLORTMC10 – C13 60 135 3 500 1.36 0.15 4.4 1.516
60L
CERECLORTMC10 – C13 63 125 11 000 1.41 0.15 4.3 1.522
63L
CERECLORTMC10 – C13 65 150 30 000 1.44 0.20 2.5 1.525
65L
CERECLORTMC10 – C13 70 200 800d 1.50d 0.20 0.5 1.537
70L
CERECLORTMC14 – C17 40 80 70 1.10 0.20 4.2 1.488
S40
CERECLORTMC14 – C17 45 80 200 1.16 0.20 2.8 1.498
S45
CERECLORTMC14 – C17 52 100 1 600 1.25 0.20 1.4 1.508
S52
CERECLORTMC14 – C17 58 150 40 000 1.36 0.20 0.7 1.522
S58
CERECLORTMC18 – C20 40 150 300 1.13 0.20 1.2 1.491
M40
CERECLORTMC18 – C20 47 150 1 700 1.21 0.20 0.8 1.506
M47
CERECLORTMC18 – C20 50 250 18 000 1.27 0.20 0.7 1.512
M50
CERECLORTMC>20 42 250 2 500 1.16 0.20 0.4 1.506
42
CERECLORTMC>20 48 300 28 000 1.26 0.20 0.3 1.516
48
Solid 70 100e 1.63 0.20 0.2
chlorinated
paraffin wax
a
At 25 ◦ C unless otherwise stated.
b
Measured in a standard test for 4 h at 175 ◦ C.
c
Measured in a standard test for 4 h at 180 ◦ C.
d
At 50 ◦ C.
e
10 g in 100 mL toluene.
f
Solid, softening point 95 – 100 ◦ C.
CERECLOR is a trade mark, the property of INEOS Chlor Limited.

of their carbon chains and in the number and During paraffin chlorination, which is es-
relative positions of chlorine atoms present on sentially a free radical process, tertiary carbon
each carbon chain. Their chemical formula can atoms react faster than those which are sec-
be stated as follows: ondary; secondary carbon atoms in turn react
faster than primary ones. The stability of chlori-
Cn H2n+2−m Clm
nated paraffins toward dehydrochlorination fol-
where n usually lies between 10 and 30 and lows the reverse pattern, with chlorines attached
m between 1 and 22. In the less chlorinated to a tertiary carbon atom being the least stable
products, unchlorinated paraffin molecules may and those linked to a primary one the most stable.
also be present. Studies have been conducted Therefore, it can be concluded that most of the
on the distribution of chlorine atoms within the chlorine atoms present in the commercial prod-
molecule [686]. The results show that it is rare uct are attached to a secondary carbon atom with
to find two chlorine atoms bound to one and the no more than about one in twelve primary-linked
same carbon atom.
 Chlorinated Hydrocarbons 99

hydrogens substituted by chlorine atoms. Any The reaction between chlorine and paraffin is
methyl side-chains are usually unchlorinated. exothermic with an enthalpy of reaction of ca.
Because of their very limited reactivity, chlo- −150 kJ/mol; therefore, the reaction once ini-
rinated paraffins are of little significance as tiated must be carefully controlled by cooling.
chemical intermediates, although their conver- Other important considerations are the need for
sion to alcohols [687] and the substitution of var- efficient mixing to prevent localized overheat-
ious chlorine atoms by sulfuric acid have been ing and control of the chlorine flow rate in order
studied [688]. to minimize the amount of unreacted chlorine in
the off gas. These requirements become increas-
ingly important as the reaction proceeds and the
7.3. Production viscosity of the product increases. For these rea-
sons it is nearly impossible to prepare chlori-
Raw Materials. Because of the known insta-
nated paraffins containing more than 71 wt %
bility of compounds containing tertiary-linked
chlorine by this method.
chlorine atoms, only straight-chain paraffins
The reaction is terminated by stopping the
with a minimum content of branched isomers
chlorine flow once the required degree of chlo-
can be used as raw materials for the industrial
rination is reached. The end point is assessed by
production of useful chlorinated paraffins. The
a variety of methods including refractive index
quality of the technical products underwent a
and viscosity. The product is then blown with
significant increase when the petrochemical in-
nitrogen gas to remove any unreacted chlorine
dustry succeeded in producing paraffin fractions
and residual HCl. In most case a small amount of
enriched in straight-chain components through
a storage stabilizer, usually an epoxidized veg-
urea adduction and later by treatment with mo-
etable oil, is then added prior to sending the fin-
lecular sieves.
ished product for storage or drumming.
The paraffin fractions used most frequently
Other important considerations when pro-
by producers of chlorinated paraffins are the
ducing chlorinated paraffins are the ability to
three straight-chain mixtures C10 – C13 , C14 –
deal effectively with HCl which is co-produced
C17 , C18 – C20 , which make short-chain chlo-
in large amounts.
rinated paraffins (SCCPs), medium-chain chlo-
Both batch and continuous processes are
rinated paraffins (MCCPs), and long-chain chlo-
known for the preparation of chlorinated paraf-
rinated paraffins (LCCPs) respectively, together
fins on an industrial scale. Batch processes are
with waxes in the range of C20 – C28 . The feed-
preferred, because of the large variety of special
stocks used most frequently to make chlorinated
products synthesized. Figure 33 gives a general
olefins are C14 or C16 linear α-olefins or mix-
outline of the process employed in the commer-
tures of the two. The ranges employed can vary,
cial production of chlorinated paraffins.
depending on the regional availability of suitable
The same basic principle is used in continu-
raw materials.
ous processes. In this case, however, groups of
Preparation. Chlorinated paraffins are pre- three or four reactors are arranged in series.
pared by reacting pure gaseous chlorine with the The production of solid chlorinated paraf-
starting paraffins in the absence of any solvents fin wax generally employs a two-stage pro-
at temperatures between 80 ◦ C and 100 ◦ C. cess, the first of which involves production of
an intermediate liquid chlorinated paraffin wax
C1n H2n+2 +mCl2 →Cn H2n+2−m Clm +mHCl with between 40–50 wt % chlorine. Tradition-
Small amounts of oxygen are frequently used ally, this was then dissolved in carbon tetrachlo-
to catalyze the chlorination process. Tempera- ride solvent and further chlorinated to around
tures above 120 ◦ C must be avoided as these 70 wt %, at which point the carbon tetrachloride
may cause dark or black products. Ultraviolet was stripped off and the resulting cake ground
light is used by some manufacturers for initiat- to a fine powder. Since the beginning of the
ing the reaction at relatively low temperatures. 1990s producers of the solid chlorinated paraf-
Once the reaction has started, the light source fin wax have developed aqueous reaction sys-
may be reduced in intensity or eliminated. tems to replace carbon tetrachloride [684] due to
the restrictions on the use and emissions of car-
100 Chlorinated Hydrocarbons

Figure 33. Commercial production of chlorinated paraffins

a) Reactor; b) Agitator; c) Heating/cooling coils; d) Jackets; e) Addition of special stabilizers; f) Batch tanks; g) Absorption
of hydrogen chloride

bon tetrachloride, an ozone depleting substance, ation by use of appropriate separators. Thus, the
arising from the Montreal Protocol. only wastes are those to be expected from clean-
Construction Materials. Older reactors are ing procedures in the plant, in addition to acti-
generally lead-, ceramic- or occasionally silver- vated charcoal. Such wastes and other byprod-
lined, whereas more modern reactors are nor- ucts should be burned in approved incinerators
mally constructed of glass-lined steel. Ferrous at a temperature above 1200 ◦ C to prevent for-
metal surfaces must be avoided to prevent dis- mation of cyclic or polycyclic chlorinated com-
coloring or blackening of the finished prod- pounds.
uct. Other equipment such as pumps, stirrers, Contamination of water caused by spillages
pipework and valves should be constructed of must also be avoided. Asphalt surfaces of roads
corrosion-resistant materials and be resistant to may be damaged by chlorinated paraffins, par-
hydrochloric acid. ticularly when the product is at elevated temper-
atures.
Environmental Protection. The production
process of chlorinated paraffin has minimal en- Producers and Trade Names. Commercial
vironmental impact because little contaminated grades of chlorinated paraffins are always mix-
water or other wastes are formed in the course of tures of different alkanes chlorinated to varying
the reaction. Either after absorption or while it degrees. Producers normally supply a range of
is still in the gaseous phase, the hydrogen chlo- materials intended to meet the differing needs
ride leaving the reactors as a byproduct must be of their customers.
cleaned in accordance with its future use. Hy- In order to provide sufficient definition for in-
drochloric acid is usually separated from any dividual products, numbers are often appended
organic liquids and subsequently treated with to the trade names. These typically indicate the
activated charcoal. Purification of gaseous hy- approximate chlorine content of a given material
drogen chloride can be carried out after refriger- and in some cases provide additional informa-
 Chlorinated Hydrocarbons 101

tion regarding the alkanes used as starting ma- GC-MS [690]. Resolution of groups of isomers
terial (see Table 33). and homologues has been obtained by a GC-MS
Table 34 gives the major producers of chlori- method [691].
nated paraffins together with the corresponding For routine quality control of chlorinated
trade names. There are also a number of smaller paraffins, usually the density, the viscosity,
plants producing products to meet local market color, thermal stability and the chlorine content
demands in China, India, and Russia. The largest of specific products are determined. Approved
single producer of chlorinated paraffins is IN- standard methods are available for determina-
EOS, who operate three plants worldwide. tion of densities, viscosities, and color. In order
to determine their chlorine content, chlorinated
Table 34. Producers of chlorinated paraffins and trade names paraffin samples are combusted under well-
Producer Country Trade name
defined conditions, after which chloride is deter-
mined argentometrically, microcoulometrically,
INEOS UK (Thailand, CERECLOR or by use of ion-selective electrodes. Good re-
France)
Caffaro Italy CLOPARIN, CLOPAROL sults have been obtained by the Wurtzschmitt
Leuna Tenside Germany HORDALUB, method, in which a small sample of chlorinated
HORDAFLAM,
HORDAFLEX
paraffin is oxidized in a nickel bomb in the pres-
Dover North America PAROIL, CHLOROWAX ence of an excess of sodium peroxide. Routine
Navácke Chemické Slovakia Chlorparaffin chlorine content determinations of production
Závody
batches are usually carried out by direct correla-
Handy Taiwan PLASTOIL
NCP South Africa PLASTICLOR tion with other physical properties such as den-
Tosoh Japan TOYOPARAX sity or refractive index where well-established
Asahi Denka Japan ADKciser relationships exist for each feedstock.

7.4. Analysis and Quality Control 7.5. Storage and Transportation

The properties of chlorinated paraffins may be Chlorinated paraffins are non-corrosive sub-
influenced by the process used for their prepara- stances at ordinary temperatures. Therefore,
tion. Products prepared in a continuous process their storage for many months without deteriora-
sometimes have a lower thermal stability and tion of either products or containers is possible in
a higher volatility than products prepared in a mild steels drums. Nevertheless, temperatures of
batch process [689]. A less homogeneous dis- storage should not exceed 40 ◦ C and prolonged
tribution of the introduced chlorine seems to be storage should not be in direct sunlight, since this
responsible for this difference. Moreover, batch may cause discoloration. Reconditioned drums
products are said to be more compatible with should be internally lacquered before use. In the
poly(vinyl chloride). case of bulk storage, stainless or mild steel tanks
Even though chlorinated paraffins are well- are recommended. If mild steel is used as the
known and very important substances with many construction material, the tanks must be inter-
applications, analysis for determining their com- nally lined with epoxy or phenol – formaldehyde
position or their presence in environmental resins. Appropriate producers of resins should
samples is particularly problematic. Techniques be contacted with respect to the suitability of
employing gas chromatographic investigations their coatings. Many of the chlorinated paraffin
(GC) are very difficult, both because chlorinated types are very difficult to handle at low tempera-
paraffins are complex mixtures and because de- ture because of their high viscosities. Installation
hydrochlorination may occur during separation of storage tanks in heated rooms is, therefore,
in a GC column. Furthermore, the sensitivity of advantageous in order to keep the products in
the usual GC detection systems is often insuffi- a usable state. Outdoor tanks must be equipped
cient. Capillary GC combined with negative ion with some sort of moderate warming system.
chemical ionization mass spectrometry (MS) re- Circulated warm water is recommended as the
presents a suitable approach as does on-column preferred heating agent, since it does not pro-
reduction followed by either GC or combined
102 Chlorinated Hydrocarbons

duce local hot spots where deterioration of the as a result of studies of lifetime exposure to
stored product might occur. a C12 chlorinated paraffin with 58% chlorine
If steam is used for warming, its pressure [694]. This information has led some authorities
must be reduced to ensure that the temperature to classify SCCPs (C10 – C13 ) as carcinogens
will not exceed 105 ◦ C at the inlet. It is also (e.g., IARC Group 2B: “possibly carcinogenic
recommended that external pipe work is elec- to humans”; European Union Category 3: “lim-
trically trace-heated to prevent the formation ited evidence of a carcinogenic effect”). Toxico-
of cold plugs of product. Chlorinated paraffins logical studies have elucidated the mechanism
swell most types of rubber, therefore, any gas- of the carcinogenic effect observed in rats and
kets, etc. should be made of poly(tetrafluoroeth- mice and have suggested that these effects are
ylene). not relevant for humans [695, 696]. In general,
Positive displacement type pumps, prefer- the highest exposure levels under industrial con-
ably ones equipped with an automatically op- ditions of use are likely to be far less than those
erated security device, are preferred for material that would elicit toxicological effects.
transfer at end use locations. It is particularly im- The water solubilities of chlorinated paraf-
portant that adequate flow rates be maintained on fins are low and decrease with increasing chain
the suction side of such pumps. length. SCCPs are significantly more soluble (up
Storage of both drums and bulk liquid in tanks to 150 µg/L) than the higher chain length ma-
should incorporate secondary containment such terials. Laboratory studies have demonstrated
as bunding to prevent uncontrolled loss of prod- that SCCPs exhibit toxicity effects towards
uct to the environment. fish and other varieties of aquatic life. Conse-
quently these products are classified as “Dan-
gerous For the Environment” by the European
7.6. Toxicology, Environmental Impact Union and as “Severe Marine Pollutants” un-
and Regulation der the UN International Maritime Organization
regulations. MCCPs (C14 – C17 ) show signifi-
The unreactive nature of chlorinated paraffins cantly lower toxicity to most aquatic species
has led to them being generally regarded as low than the short-chain products, however, their
toxicity products. Studies have shown that they recently confirmed toxicity towards Daphnia
exhibit very low acute oral toxicity following a magna, an aquatic invertebrate species, has led
single exposure, with no signs of toxicity indi- some European producers to provisionally clas-
cated in laboratory animals at doses of between 4 sify products based on MCCPs as “Danger-
and 10 g per kilogram body weight [692]. Based ous For the Environment” in anticipation of a
on more limited data, chlorinated paraffins show harmonized European Union classification ex-
similarly low acute toxicity for single exposures pected to be implemented in the next adaptation
through dermal and inhalation routes. These re- of the EU’s Dangerous Substances Directive.
sults for acute toxicity are in accordance with The very low solubilities and high molecular
the poor skin absorption and extremely low va- masses of the longer chain chlorinated paraf-
por pressures that characterize these substances. fins means they show little or no toxicity to-
Studies of longer-term exposure in a number wards aquatic species at or above their limits of
of mammalian species have found target organ solubility. In Germany chlorinated paraffins are
toxicity primarily in the liver, kidney, and thy- given appropriate WGK classes under the cri-
roid gland [690]. An effect on postnatal survival teria laid down by the Kommission zur Bewer-
in newborn rats, which is associated with an ef- tung Wassergefährdender Stoffe. The classifica-
fect on Vitamin K levels, has also been described tions recommended by Eurochlor, representing
[693]. the European producers of chlorinated paraffins,
Chlorinated paraffins are considered to be are as follows:
nongenotoxic, supported by negative muta-
genicity findings in bacterial [692] and animal C10−13 Chlorinated paraffins WGK class 3
bone marrow studies [690]. In 1985, however, C14−17 Chlorinated paraffins WGK class 2
the USA’s National Toxicity Program (NTP) C18−20 Chlorinated paraffins WGK class 2
(liquid)
reported evidence of tumors in rats and mice
 Chlorinated Hydrocarbons 103
C18+ Chlorinated paraffins WGK class 1
(solid)
wall covering and general extrusion and injec-
C20+ Chlorinated paraffins WGK class 1 tion molding. Examples of the typical products
(liquid) most frequently used in these applications are
CERECLOR S45 and S52 chlorinated paraffins
Chlorinated paraffins biodegrade only (Table 33).
slowly, the rate of biodegradation being higher Chlorinated paraffins also act as plasticizers
for products with lower chlorine content and in polyurethane and liquid polysulfide sealants
chain length. Bioconcentration factors (BCF) where they also replace phthalates. Again cost
of 5300 for short-chain chlorinated paraffins, reduction is an important feature as is their
1000 for medium chains and 50 for long-chain very low solubility in water and stability to-
products have been measured [690, 697]. By wards biodegradation, hence their use in sealants
comparison, the BCF for chlorinated paraffins for aggressive biological environments such as
are considerably lower than those for polychlori- sewage treatment works. Very low volatility also
nated biphenyls (PCBs) and chlorine-containing makes them useful as plasticizers for insulating
pesticides, and there is no evidence of biomag- glass sealants. Typical grades used in these ap-
nification of chlorinated paraffins by fish. plications are CERECLOR 56L, 63L, S52 and
Recent regulatory activity has focussed on M50 chlorinated paraffins (Table 33). Adhesive
short-chain chlorinated paraffins in particular. systems such as certain types of hot melt, pres-
The European Union undertook a Risk Assess- sure sensitive and poly(vinyl acetate) emulsion
ment for SCCPs (under the EU Existing Sub- adhesives are also effectively plasticized and
stances Regulation 793/93), that was completed tackified by chlorinated paraffins.
in 1999 and updated in 2005. The Risk Assess- Finally their very low volatility, inert nature
ment has led to the implementation of a mar- and low water solubility makes them effective
keting and use restriction in Europe for SCCPs, plasticizers for a range of paint systems. In gen-
prohibiting their use in metal-working fluids and eral use is focused in heavy duty industrial ap-
leather treatment from January 2004. An EU plications with typical host paint resins being
Risk Assessment for medium-chain chlorinated chlorinated rubbers, chlorosulfonyl polyethyl-
paraffins is underway and nearing completion. ene, styrene – butadiene rubbers, and modified
acrylics. Typical grades used for paint applica-
tions are those based on wax feedstocks such as
7.7. Uses CERECLOR 42 chlorinated paraffin (Table 33).
Solid 70 wt % chlorinated paraffin waxes also
Chlorinated paraffins find widespread industrial
find use in this application where their low plas-
use as plasticizers, flame-retardants, solvents,
ticizing action allows them to act as a paint resin
extreme-pressure additives and to lesser extent,
extender as well as conferring additional fire re-
as resin extenders. Choice of grade is frequently
tardancy.
a compromise between the physical properties
outlined above, in particular chlorine content, Fire Retardants. Chlorinated paraffins are
viscosity and volatility, together with a consid- excellent cost effective flame-retardants [698],
eration of compatibility with the host polymer however their plasticizing action and limit on
or base oil. upper processing temperature can restrict their
Plasticizers. This represents by far the use in this application area. An important area
largest use of chlorinated paraffins with the sin- of use is PVC where chlorinated paraffins act as
gle largest application being the partial replace- a fire retardant plasticizer and are used to par-
ment of phthalate plasticizers in flexible PVC. tially replace more expensive phosphate plasti-
The main reason for their use is reduction in cizers in applications such as mine belting and
formulation costs plus the additional benefits of safety flooring. Chlorinated paraffins are often
flame retardancy, improved water and chemi- used in combination with a synergist, such as an-
cal resistance and better viscosity aging stabil- timony trioxide, to enhance the fire retardancy
ity (i.e. a lesser increase in viscosity with time) of phthalate-based PVC formulations, such as
of plastisols (→ Poly(Vinyl Chloride)). Typical those found in fire retardant wire and cable.
end use applications include cables, flooring, Other fire retardant applications include their use
104 Chlorinated Hydrocarbons

in a range of rubbers including natural, nitrile, pared to competitive products such as dialkyl
styrene – butadiene and chlorosulfonyl polyeth- naphthalenes.
ylene rubbers. Also of importance is their use
in polyurethanes, in particular rigid foams and
one-component foams (OCF) and unsaturated 7.8. Summary
polyesters. The actual grades used vary consid-
erably depending on the host polymer. Solid 70 Chlorinated paraffins are a versatile range of
wt % chlorinated paraffin wax may be used as substances, which function as cost effective
a flame retardant and can be used in polyeth- property-enhancing additives in a wide range of
ylene, polypropylene and high-impact polysty- important end applications including secondary
rene compounds in addition to those polymers plasticizers and flame retardants in flexible PVC
already mentioned. and other resins used in paints, sealants, foams
Extreme-Pressure Additives in Metal and safety flooring, and as extreme-pressure ad-
Working. Chlorinated paraffins are used as ditives in metal-working fluids. The thorough
extreme-pressure additives to enhance lubrica- investigation of the varied toxicological profile
tion and surface finish in demanding metal work- and environmental impact of the different types
ing and forming applications where hydrody- of chlorinated paraffins allows for their contin-
namic lubrication cannot be maintained. They ued safe use through risk assessment and the im-
function by providing a convenient source of plementation of responsible working practices.
chlorine that is liberated by frictional heat to
form a chloride layer on the metal surface. This
film has a lower shear strength than the metal 8. Nucleus-Chlorinated Aromatic
itself, so the friction between the metals in slid- Hydrocarbons
ing contact is reduced. Chlorinated paraffins are
used predominantly in neat oils and to a lesser The term “nucleus-chlorinated aromatic com-
extent in soluble oil emulsions. They are fre- pound” as used here refers to a substance con-
quently used in combination with other extreme- taining a mesomeric π-electron system in a car-
pressure additives including fatty acids, phos- bocyclic framework in which at least one of the
phorus- and sulfur-containing compounds, with ring carbons bears a chlorine substituent rather
which they display a synergistic action. Typi- than hydrogen.
cal end use applications are stamping, forming, Laboratory work on the compounds making
drawing and a range of cutting operations such up this class began long ago. For example, A.
as broaching. Historically, grades used in this Laurent reported in 1833 that he had obtained
application were based on C10 – C13 paraffins, waxlike compounds in the course of chlorinat-
however, as a result of environmental concerns ing naphthalene. Nevertheless, their industrial
and the market restrictions in Europe described manufacture and use was delayed until the first
in Section 7.6, producers have developed highly third of the 20th century.
effective medium chain grades for extreme pres- Chlorinated aromatic hydrocarbons are of
sure use, e.g., the CERECLOR E grade products substantial economic significance. This is par-
of INEOS Chlor. In North America chlorinated ticularly true of the chlorinated benzenes, the
ααolefins also find widespread use as extreme most important being monochlorobenzene, and
pressure additives. the chlorinated toluenes. The compounds are
Solvents. Chlorinated paraffins have found now recognized as important starting materials
use as solvents for the color formers used in and additives in the production of high-quality
carbonless copy paper. The main benefits are insecticides, fungicides, herbicides, dyes, phar-
good solvating power for the color formers, low maceuticals, disinfectants, rubbers, plastics, tex-
volatility, stability in the encapsulation process tiles, and electrical goods.
and fast color development especially with blue In general, the environmental degradabil-
color formers and clay-coated color fronts (CF). ity of heavily chlorinated organic compounds,
Chlorinated paraffins also tolerate higher levels whether by biotic or by abiotic mechanisms, is
of the diluents widely used by the industry com- low. This persistence has led in recent years to
 Chlorinated Hydrocarbons 105

such drastic measures as prohibitions, restric- + 1.5 ◦ C. Further physical data are given in Ta-
tions on production and use, and legislation reg- ble 35.
ulating waste disposal. Some highly chlorinated Tetrachlorobenzene C6 H2 Cl4 , also occurs
aromatics have been affected as well. in three isomeric forms: 1,2,3,4-Tetrachloro-
benzene and 1,2,3,5-tetrachlorobenzene crys-
tallize as colorless needles. 1,2,4,5-Tetrachlo-
8.1. Chlorinated Benzenes robenzene forms colorless, sublimable needles
with a strong, unpleasant odor.
8.1.1. Physical Properties
All of the tetrachlorobenzenes are insoluble
Monochlorobenzene C6 H5 Cl, is a colorless in water, but they are soluble in many organic
liquid which is volatile with steam and is a good solvents, particularly at an elevated temperature.
solvent. It is miscible with all commonly used or- Further physical data are given in Table 36.
ganic solvents and forms many azeotropes [699,
700]. Monochlorobenzene is flammable and has Pentachlorobenzene C6 HCl5 , forms color-
an aromatic odor. Upon addition of 24 % ben- less needles and is insoluble in water.
zene, it forms a eutectic mixture with a solidifi- Hexachlorobenzene C6 Cl6 , forms colorless
cation point of − 60.5 ◦ C. and sublimable prismatic crystals. It is insoluble
Important physical data for monochloro- in water, but soluble at an elevated temperature
benzene are compiled in Table 35. in several organic solvents (e.g., benzene, chlo-
Dichlorobenzene C6 H4 Cl2 , occurs in three roform, and ether).
isomeric forms. 1,2-Dichlorobenzene is a col-
orless, mobile liquid which is miscible with the
commonly used organic solvents. It is difficult 8.1.2. Chemical Properties
to ignite and has an unpleasant odor. The proper-
ties of 1,3-dichlorobenzene are similar to those The chlorobenzenes are neutral, thermally sta-
of 1,2-dichlorobenzene. 1,4-Dichlorobenzene is ble compounds. Reactions may occur to replace
a white, volatile, crystalline compound soluble hydrogen at unsubstituted positions on the ring
in many organic solvents. It has a strong cam- (e.g., halogenations, sulfonations, alkylations,
phor odor. 1,4-Dichlorobenzene occurs as a sta- nitrations), by substitution of the chlorine (e.g.,
ble monoclinic α-modification, which is trans- hydrolysis), and with de-aromatization (e.g.,
formed into the triclinic β-form at 30.8 ◦ C. chlorine addition).
Eutectic mixtures of the dichlorobenzenes Monochlorobenzene. In this compound the
are: 86.0 % 1,2-dichlorobenzene, 14.0 % 1,4- chlorine is firmly bound to the aromatic ring and
dichlorobenzene, solidification point − 23.7 can only be substituted under energetic condi-
◦
C; 85.3 % 1,3-dichlorobenzene, 14.7 % 1,4-di- tions. Chlorobenzene can be hydrolyzed to phe-
chlorobenzene, solidification point − 30.8 ◦ C. nol with aqueous sodium hydroxide at 360 –
Further physical data are given in Table 35. 390 ◦ C under high pressure [701 – 703] or with
Trichlorobenzene C6 H3 Cl3 , occurs in three steam at 400 – 450 ◦ C over calcium phosphate.
isomeric forms. 1,2,3-Trichlorobenzene forms Monochlorobenzene reacts with ammonium hy-
colorless tabular crystals. 1,2,4-trichloroben- droxide at high temperature and in the presence
zene is a colorless liquid of low flammability, of copper catalysts to give aniline [704].
and 1,3,5-trichlorobenzene forms long, color- In electrophilic substitution, e.g., nitration,
less needles. the directing influence of the chlorine atom leads
The trichlorobenzenes are insoluble in water, to the formation of derivatives in which the add-
slightly soluble in alcohol, and very soluble in ed substituent is found predominantly in the or-
benzene and solvents like petroleum ether, car- tho or para position.
bon disulfide, chlorinated aliphatic and aromatic Light-induced addition of chlorine produces
hydrocarbons. heptachlorocyclohexane [715].
A combination of 34 % of 1,2,3-trichloroben-
zene and 66 % of 1,2,4-trichlorobenzene forms
a eutectic mixture with a solidification point of
106 Chlorinated Hydrocarbons
Table 35. Physical properties of mono- to trichlorobenzenes
 Chlorinated Hydrocarbons 107
Table 35. (continued)
108 Chlorinated Hydrocarbons
Table 36. Physical properties of tetra-, penta-, and hexachlorobenzenes

Dichlorobenzenes. The reactivity to further The action of alkaline solutions or alcoholic

substitution on the ring increases from 1,4- via ammonia solution on dichlorobenzene at 200
◦
1,2- to 1,3-dichlorobenzene. C under pressure gives chlorophenols and di-
The position at which a third substituent is hydroxybenzenes, or chloroanilines and phenyl-
introduced into the ring depends on the di- enediamines, respectively. The addition of chlo-
recting influence of the two chlorine atoms. rine leads to octachlorocyclohexane [715].
Thus, for example, no 1,3,5-derivatives can be Trichlorobenzenes. The reactivity of these
formed in this way. Electrophilic substitution compounds toward chlorine decreases in the or-
of 1,2-dichlorobenzene leads to 4-derivatives der 1,3,5- > 1,2,3- > 1,2,4-trichlorobenzene.
as main products and 3-derivatives as byprod- As expected, electrophilic substitution occurs
ucts. Electrophilic substitution of 1,3-dichloro- preferentially at certain positions on the aro-
benzene gives 4-derivatives as main product matic ring: With 1,2,3-trichlorobenzene an elec-
and 2-derivatives as byproduct, whereas 1,4- trophilic substituent is led into the 4-position,
dichlorobenzene as starting material yields 2- with 1,2,4-trichlorobenzene into the 5-position
derivatives.
 Chlorinated Hydrocarbons 109

(main product) and 3-position (byproduct), and extent if at all. The velocity of chlorination for
with 1,3,5-trichlorobenzene into the 2-position. an individual chlorine compound depends on the
The trichlorobenzenes can be hydrolyzed to compound’s structure and, because of this, both
dichlorophenol. the degree of chlorination and also the isomer
Tetrachlorobenzenes. Like the lower chlo- ratio change continuously during the course of a
rinated benzenes, the tetrachlorobenzenes can be reaction. Sets of data on the composition of prod-
chlorinated and nitrated. The reactivity toward ucts from different reactions are only compara-
chlorine decreases from 1,2,3,5- via 1,2,3,4- ble with one another if they refer to identical re-
to 1,2,4,5-tetrachlorobenzene. At a tempera- action conditions and materials having the same
ture above 160 – 180 ◦ C, the chlorine sub- degree of chlorination. By altering the reaction
stituents can be hydrolyzed with sodium hy- conditions and changing the catalyst, one can
droxide in methanol. In the preparation of vary the ratios of the different chlorinated prod-
trichlorophenol from tetrachlorobenzene, the ucts within certain limits. Lewis acids (FeCl3 ,
toxic polychlorinated dibenzo-p-dioxins – and AlCl3 , SbCl3 , MnCl2 , MoCl3 , SnCl4 , TiCl4 ) are
also the extremely toxic compound 2,3,7,8-tetra- used as principal catalysts (Table 37). Elevated
chlorodibenzo-p-dioxin – may be formed if the temperatures in substitution reactions favor the
very narrowly defined reaction conditions are introduction of a second chlorine atom in the
not precisely maintained. ortho and meta positions, whereas para substi-
tution is favored if cocatalysts and lower tem-
Pentachlorobenzene. Pentachlorobenzene peratures are used. As a further example of the
can be chlorinated to hexachlorobenzene and influence of catalysts on the composition of the
nitrated to pentachloronitrobenzene. Hydrolysis product, attention is drawn to the formation of
to 2,3,4,5- and 2,3,5,6-tetrachlorophenol is also 1,2,4,5-tetrachlorobenzene (Table 38). The opti-
possible. mal reaction temperature depends on the desired
Hexachlorobenzene. Hexachlorobenzene, degree of chlorination. Mono- and dichlorina-
like the other polychlorobenzenes, can be de- tion are carried out at 20 – 80 ◦ C. In the pro-
halogenated to lower chlorinated benzenes with duction of hexachlorobenzene by chlorination
hydrogen or steam at a temperature above 500 of benzene, however, temperatures of about 250
◦
◦
C in the presence of catalysts [716]. At a C are needed toward the end of the reaction.
high temperature a mixture of hexachloroben-
zene, chlorine, and ferric chloride gives car- The usual catalyst employed in large scale
bon tetrachloride in high yield [717]. Reaction production is ferric chloride, with or without the
with sodium hydroxide and methanol leads to addition of sulfur compounds. Ferric chloride
pentachlorophenol. complexed with 1 mol of water is claimed to
have the best catalytic effect [732]. Benzene and
chlorine of technical purity always contain some
8.1.3. Production water, however, thus, it may be that this hydrate
compound is always present in iron-catalyzed
Benzene Chlorination in the Liquid Phase. industrial reactions.
Chlorobenzenes are prepared industrially by re- The ratio of resulting chlorobenzenes to one
action of liquid benzene with gaseous chlorine another is also influenced by the benzene : chlo-
in the presence of a catalyst at moderate temper- rine ratio. For this reason, the highest selectiv-
ature and atmospheric pressure. Hydrogen chlo- ity is achieved in batch processes. If the same
ride is formed as a byproduct. Generally, mix- monochlorobenzene : dichlorobenzene ratio ex-
tures of isomers and compounds with varying pected from a batch reactor is to result from con-
degrees of chlorination are obtained, because tinuous operation in a single-stage reactor, then
any given chlorobenzene can be further chlo- a far lower degree of benzene conversion must
rinated up to the stage of hexachlorobenzene. be accepted (as a consequence of a low benzene :
Because of the directing influence exerted by chlorine starting ratio). The selectivity of a con-
chlorine, the unfavored products 1,3-dichloro- tinuous reactor approaches that of a discontinu-
benzene, 1,3,5-trichlorobenzene, and 1,2,3,5- ous reactor as the number of reaction stages is
tetrachlorobenzene are formed to only a small
110 Chlorinated Hydrocarbons

Table 37. Influence of catalysts on the ratio 1,4-:1,2-dichlorobenzene

Catalyst Proportion of 1,4-dichlorobenzene Ratio References

(in %) in the 1,4- : 1,2-
dichlorobenzene fraction dichlorobenzene

MnCl2 + H2 O ca. 50 1.03 [718]

SbCl5 1.5 [719]
FeCl3 or Fe ca. 59 1.49 – 1.55 [720, 724,
727]
Metallosilicon organic
compounds 61 – 74 1.56 – 2.8 [721]
AlCl3 – SnCl4 2.21 [722]
AlCl3 – TiCl4 2.25 [722]
Fe – S – PbO ca. 70 [723]
FeCl3 – diethyl ether 2.38 [724]
Aluminum silicate –
hexamethylene-
diamine 2.7 [725]
FeCl3 – S2 Cl2 ca. 76 [726]
FeCl3 – divalent
organic sulfur
compounds ca. 77 3.3 [727]
L-type zeolite ca. 88 8.0 [728]
TiCl4 (chlorinating
agent is FeCl3 ) 20 – 30 [729]

Table 38. Influence of catalysts on the ratio 1,2,4,5-:1,2,3,4-tetrachlorobenzene

Catalyst Substrate Ratio Ref.

1,2,4,5- : 1,2,3,4-tetrachlorobenzene

FeCl3 1,2,4-trichlo- 2.3 – 2.4 [720],

robenzene [727]
Lewis acids – di- 1,2,4-trichlo- 3 [727]
valent organic robenzene
sulfur compounds
FeCl3 – aromatic 1,2,4-trichlo- 2.7 – 4.6 [730]
iodine compounds robenzene
SbCl3 – I2 benzene 10 – 17 [731]

C6 H6 + Cl2 → C6 H5 Cl + HCl ∆H = − 131.5 kJ/mol

increased [733]. Mathematical models analyz- C6 H5 Cl + Cl2 → C6 H4 Cl2 + HCl ∆H = − 124.4 kJ/mol
ing and interpreting benzene chlorination will C6 H4 Cl2 + Cl2 → C6 H3 Cl3 + HCl ∆H = − 122.7 kJ/mol
be found in [733 – 736] and elsewhere. C6 H3 Cl3 + Cl2 → C6 H2 Cl4 + HCl ∆H = − 115.1 kJ/mol
Solvents can also influence the chlorination
rate as well as the selectivity of the reaction, al- Unwanted heat of reaction can be dissipated
though solvents are not used in industrial chlo- either by circulating some of the reactor liquid
rination. through an external heat exchanger or by permit-
Continuous Chlorination. Benzene or a ting evaporative cooling to occur at the boiling
chlorobenzene derivative is treated with chlo- temperature. Circulation cooling has the advan-
rine gas in a suitable reactor in the presence of tage of enabling the reaction temperature to be
dissolved ferric chloride. The reactants must be varied in accordance with the requirements of
mixed as intensively as possible. The catalyst a given situation. Evaporative cooling is more
can be introduced along with the substrate or economical, however.
it can be allowed to form during the reaction The reactor must be designed to ensure that
on the surface of iron rings in the reactor. The the liquid within it has a suitable residence spec-
reaction is highly exothermic. trum, since this favors high chlorination selectiv-
ity. As noted above, the quantity ratio of the chlo-
robenzenes to one another is determined by the
benzene : chlorine starting ratio.
 Chlorinated Hydrocarbons 111

Almost quantitative conversion of chlorine is tion, insofar as this is economically justifi-

achieved in continuously operated plants for the able, would consist of combined crystalliza-
manufacture of mono- and dichlorobenzenes un- tion/distillation processes.
der normal operating conditions. Discontinuous Chlorination. Batch chlori-
Cast iron, steel, nickel, and glass-lined steel nation of liquid, molten, or dissolved aromat-
can be used as construction materials. How- ics is carried out industrially in agitator ves-
ever, all starting materials must be substantially sels equipped with external or internal cooling.
free from water; otherwise, severe corrosion is The agitator must provide maximum exchange
caused by the hydrochloric acid formed. Intru- between the liquid and gas phases. Gaseous
sion of water is dangerous for another reason: chlorine is introduced through a valve at the
water causes the ferric chloride catalyst to be in- bottom of the vessel or through an ascension
activated. If this occurs, chlorine collects in the pipe beneath the agitator. The vessel may be
reactor and exhaust system, and local overheat- constructed of glass-lined steel, cast iron, steel,
ing may ensue, causing spontaneous combustion or nickel. Absence of water must be ensured
of the aromatic hydrocarbon with chlorine in a as a precaution against corrosion. The degree
highly exothermic reaction to form carbon and of chlorination can be ascertained from density
hydrogen chloride (2 mol of HCl/mol of Cl2 ). determinations. The amount of chlorine which
Furthermore, above 280 ◦ C metallic iron begins can be introduced in unit time depends on the
to burn in the chlorine stream. It is, therefore, heat output of the vessel and on the chlorine
advisable to monitor the reaction continuously conversion rate. It is obviously desirable to keep
by observing the heat production rate and the the chlorine content of the off-gas as low as pos-
chlorine content of the waste gas. sible. It is also important that the reaction begins
On leaving the reactor, the liquid and gas por- as soon as chlorine is introduced (the beginning
tions of the reaction mixture are separated. The of the reaction is indicated by a temperature
waste gas contains hydrogen chloride and — in increase and by the formation of hydrogen chlo-
proportions corresponding to their vapor pres- ride). Chlorine is soluble in many hydrocarbons
sures at the temperature of the waste gas — ben- (see Table 39); therefore, if the onset of reaction
zene and chlorobenzenes. If the chlorine conver- is delayed, hydrogen chloride may be formed
sion is incomplete, chlorine may be present as very rapidly, resulting in a substantial increase
well. Concerning the treatment of the waste gas, in the temperature of the reactants in the vessel.
see Section 8.5. Other Benzene Chlorination Processes.
The liquid phase contains benzene, chlo- The following additional benzene chlorination
robenzenes, hydrogen chloride, and iron cata- processes are known:
lyst. Production processes exist in which the 1) Chlorination in the vapor phase with chlorine
product mixture is neutralized with sodium hy- 2) Chlorination in the vapor or liquid phase with
droxide solution or soda before it is subjected hydrogen chloride and air (oxychlorination)
to fractional distillation. In modern continu- 3) Chlorination with chlorine-containing com-
ous distillation trains, the mixture of prod- pounds
ucts can be distilled without preliminary treat- 4) Electrolysis of benzene and hydrochloric acid
ment, however. The separated fractions consist
Apart from oxychlorination these processes
of benzene, monochlorobenzene, dichloroben-
are not industrially important. In oxychlorina-
zenes, trichlorobenzenes, and higher chloroben-
tion, benzene vapor and a mixture of hydro-
zenes. Iron catalyst is removed along with the
gen chloride and air are reacted at about 240
distillation residue, disposal of which is dis- ◦
C in the presence of catalysts (e.g., CuCl2 –
cussed in Section 8.5. Dissolved hydrogen chlo-
FeCl3 /Al2 O3 or CuO – CoO/Al2 O3 ). The main
ride is removed during the benzene distillation
product is monochlorobenzene accompanied by
and combined with the waste gas. Unreacted
6 – 10 % dichlorobenzene [738 – 746].
benzene is recycled to the reactor.
Whereas chlorobenzene and 1,2-dichloro- C6 H6 +HCl+0.5O2 →C6 H5 Cl+H2 O
benzene are obtainable as pure distillates, the This process was developed in connection
other fractions are mixtures of close-boiling with the production of phenol from chloroben-
polychlorobenzene isomers. A further separa- zene (Raschig-Hooker process; → Phenol). The
112 Chlorinated Hydrocarbons
Table 39. Solubility (in wt %) of chlorine in benzene and chlorobenzenes [737]

Solvent Temperature
20 ◦ C 50 ◦ C 75 ◦ C 100 ◦ C

Benzene 27 6 0.8
Monochlorobenzene 15 5 1.2
1,2-Dichlorobenzene 9 4 1.1
1,2,4-Trichlorobenzene 6 3.5 1.0

benzene conversion must be limited to 10 – 15 % ity in favor of 1,4-dichlorobenzene (1,4 : 1,2-di-

in order to control the heat in the catalyst solid chlorobenzene ratio till 25) is achieved [729,
bed (222 kJ/mol). An excessively high reaction 759].
temperature favors the formation of dichloro- Chlorobenzenes can also be produced by
benzene and a side reaction, the highly exother- electrolysis [767, 768], resulting in high selec-
mic oxidation of benzene to carbon dioxide and tivity for monochlorobenzene (98 %) and in the
water (330 kJ/mol). exceptional yield of 94 % [769].
Concerning material balance and heat, see Other Processes. The conversion of substi-
[747]. The high cost of energy and for a tuted aromatics to chlorobenzenes is of par-
corrosion-resistant plant, as well as an insuffi- ticular interest in connection with the prepa-
cient shift of the ratio of monochlorobenzene to ration of not easily accessible isomers, such
dichlorobenzene, makes the process uneconom- as 1,3-dichlorobenzene and 1,3,5-trichloroben-
ical. zene. The replacement of amino [770, 771], ni-
Gulf has developed a process for the oxychlo- tro [772 – 774], sulfonic acid or sulfonyl chlo-
rination of benzene in the liquid phase under ride [775 – 779], or acyl chloride groups [780]
pressure with aqueous hydrochloric acid, cat- by chlorine leads to appropriate specialty chlo-
alytic quantities of nitric acid, and air or oxy- robenzenes.
gen. The process leads to a high rate of ben-
zene conversion and good selectivity for mono-
chlorobenzene [748], but it has not been reported 8.1.3.1. Monochlorobenzene
whether commercial operation has commenced.
The reaction of benzene and chlorine at 400 to Most monochlorobenzene is now produced from
500 ◦ C in the vapor phase [749, 750] is likewise benzene and chlorine in continuously operated
uneconomical. One interesting feature is asso- plants. Depending on the ratio of benzene to
ciated with vapor phase chlorination catalyzed chlorine chosen, one can achieve either a low
by non-metals, however: the isomer ratio at the rate of benzene conversion and little dichloro-
dichlorobenzene stage is shifted in the direction benzene formation, or almost complete conver-
of m-dichlorobenzene (10 % ortho, 66 % meta, sion of the benzene with a higher degree of di-
24 % para isomer). This effect is a consequence chlorobenzene formation. Which of the two al-
of the radical chain mechanism that is followed ternatives is favored depends on a profitability
[751, 752]. calculation, in which the distillation costs occa-
Chlorine compounds are more selective for sioned by the dichlorobenzenes need to be taken
chlorination than chlorine itself, and they are into account. The composition of a chlorination
thus used in the manufacture of special chlo- mixture containing the highest possible propor-
robenzenes. The range of suitable chlorinat- tion of monochlorobenzene has been given as
ing agents includes metal chlorides (e.g., of 4 – 5 % unreacted benzene, 73 % monochloro-
iron, antimony, titanium, and copper) of differ- benzene, and 22 – 23 % dichlorobenzene [727].
ent valence stages [753 – 760], sulfuryl chlo- The production of monochlorobenzene from
ride [761 – 764], chlorine monoxide [765], and benzene, hydrogen chloride, and air has been de-
chlorosulfuric acid [766]. The latter three com- scribed briefly in “Other Benzene Chlorination
pounds are particularly suitable for the perchlo- Processes”, Section 8.1.3.
rination of aromatics. In the chlorination of chlo- Only if special chlorinating agents are used
robenzene with ferric chloride, high selectiv- benzene can be chlorinated to monochloro-
 Chlorinated Hydrocarbons 113

benzene without dichlorobenzene being formed dichlorobenzene can be removed chemically by

simultaneously [757]. exploiting the fact that they are considerably
more reactive than 1,4-dichlorobenzene. In sul-
fonation [783, 784], bromination [785], chlori-
8.1.3.2. Dichlorobenzenes nation [786], and other reactions first the 1,3- and
then the 1,2-dichlorobenzene are consumed; this
Dichlorobenzenes are formed unavoidably in the leaves pure 1,4-dichlorobenzene, which can be
production of monochlorobenzene. They arise separated by some suitable means.
as isomeric mixtures with a low content of the Pure 1,3-dichlorobenzene can be obtained
1,3-isomer. A maximum dichlorobenzene con- by working up the unavoidable 1,3-dichloro-
centration of 98 % is obtainable in a batch pro- benzene-containing mother liquor that results
cess in which 2 mol of chlorine is used per mole from p-dichlorobenzene crystallization. Com-
of benzene in the presence of ferric chloride and bined crystallization/distillation processes, ex-
sulfur monochloride at mild reaction tempera- tractive distillation [787], or separation on zeo-
tures. The remainder of the product consists of lites [788] are feasible. However, there also exist
mono- and trichlorobenzene. About 75 % 1,4-di- synthetic processes which lead directly to 1,3-di-
chlorobenzene, 25 % 1,2-dichlorobenzene, and chlorobenzene:
only 0.2 % 1,3-dichlorobenzene are obtained
[781]. If the reaction is carried out with only Chlorination of benzene in the gas phase at
ferric chloride as catalyst the maximum yield of 200 – 500 ◦ C in a tube or in molten salt [749,
dichlorobenzene is ca. 85 %. For further infor- 750, 789].
mation about the effects of catalysts on isomer Sandmeyer reaction of 3-chloroaniline [770,
distribution, see Table 37. 790] or direct replacement of the amino group
If discontinuous separation of dichloro- by chlorine [791].
benzene isomer mixtures is to be carried out, Reaction of 1,3,5-trialkylbenzene with chlo-
a distillation column with at least 60 practi- rine in the presence of I2 or ferric chloride to
cal plates is needed. At a reflux ratio of about give 2,6-dichloro-1,3,5-trialkylbenzene, the
35 : 1, monochlorobenzene (if present), 1,3-di- alkyl groups then being cleaved in the pres-
chlorobenzene – 1,4-dichlorobenzene mixture, ence of aluminum chloride [792, 793].
and 1,2-dichlorobenzene are removed succes- Chlorination of 1,3-dinitrobenzene or
sively at the top of the column. chloronitrobenzene at a temperature above
The intermediate fractions are recycled, their 200 ◦ C [772 – 774].
amounts being dependent on the separation ca- Two-step chlorination of benzenesulfonyl
pability of the column. chloride or diphenyl sulfone, with sulfur diox-
The 1,4-dichlorobenzene fraction is concen- ide being eliminated [778, 779].
trated from the melt by crystallization – in one Cleavage of sulfur dioxide or carbon dioxide
or more steps, depending on the impurities from the corresponding disulfonyl chlorides
present. It can then be separated into pure 1,4-di- or dicarbonic acid chlorides at temperatures
chlorobenzene and the eutectic of 1,3-dichloro- above 200/300 ◦ C in the presence of catalysts
benzene and 1,4-dichlorobenzene (14.7 % 1,4- [775, 777, 780].
and 85.3 % 1,3-dichlorobenzene). In industry Catalytic dechlorination of 1,2,4-trichloro-
(for economic reasons), the fraction is not cooled benzene with hydrogen in the vapor phase
until the eutectic is obtained. Several different [794, 795].
techniques are employed for the melt crystal- Isomerization of 1,2- and 1,4-dichloro-
lization [782], e.g., the batch tube bundle crys- benzene at a temperature of 150 – 200 ◦ C
tallizer (a new development of this type is the in the presence of catalysts containing alu-
Proabd-Raffineur), the semi-continuous falling minum chloride [796 – 798]. The conversion
film crystallizer from Sulzer-MWB, or the con- to 1,3-dichlorobenzene is said to be quantita-
tinuous purifiers from Brodie or Kureha Chem. tive if the isomerization is carried out in an an-
Ind. timony pentafluoride – hydrogen fluoride sys-
Small amounts of 1,2- and 1,3-dichloro- tem at 20 ◦ C [799].
benzene that are present as contaminants in 1,4-
114 Chlorinated Hydrocarbons

Except in the case of the chlorinolysis of 1,3- It should be pointed out that polychlorinated
dinitrobenzene, no details are available on the dibenzofurans and dibenzodioxins are formed
extent to which these processes are employed during the reaction.
on an industrial scale. References to further literature on the decom-
position of benzene hexachloride will be found
in [812].
8.1.3.3. Trichlorobenzenes 1,3,5-Trichlorobenzene is not formed in the
course of liquid phase chlorination of ben-
1,2,3-Trichlorobenzene and 1,2,4-tri- zene (see Section 8.1.3). It can be produced,
chlorobenzene are formed in minor quantities in however, by Sandmeyer reaction on 3,5-di-
the production of monochlorobenzene and di- chloroaniline, by reaction of benzene-1,3,5-tri-
chlorobenzene. Trichlorobenzenes become the sulfonic acid derivatives with phosgene [777],
main product if the chlorine input is increased by vapor phase chlorination of 1,3-dichloro-
to about 3 mol of chlorine per mole of benzene. benzene [813], and by chlorination of 3,5-di-
The batch reaction of benzene with a 2.8- chloronitrobenzene [814] or 1-bromo-3,5-di-
fold molar quantity of chlorine in the pres- chlorobenzene at 300 – 400 ◦ C [815]. The pro-
ence of fer-ric chloride at temperatures increas- portion of the 1,3,5-isomer in a mixture can be
ing to 100 ◦ C gives a chlorination mixture raised by isomerization of the other trichloro-
consisting of 26 % 1,4-dichlorobenzene, 4.5 % benzenes with aluminum chloride [816, 817]
1,2-dichlorobenzene, 48 % 1,2,4-trichloroben- or by reacting tetrachlorobenzenes and higher
zene, 8 % 1,2,3-trichlorobenzene, 8 % 1,2,3,4- chlorobenzenes with alkali metal amides [818].
tetrachlorobenzene, 5.5 % 1,2,4,5-tetrachloro- Total isomerization is reported to occur when
benzene, and less than 1 % pentachlorobenzene. SbF5 – HF is used as a catalyst system [799].
The proportion of 1,4-dichlorobenzene, and thus The three trichlorobenzenes can be separated by
also of 1,2,4-trichlorobenzene, can be raised by distillation and crystallization.
adding sulfur compounds as cocatalysts. After
the chlorination mixture has been neutralized it
can be separated by fractional distillation pro- 8.1.3.4. Tetrachlorobenzenes
vided a column with more than 60 practical
plates is used. 1,2,3,4-Tetrachlorobenzene and 1,2,4,5-
1,2,4-Trichlorobenzene can be obtained more tetrachlorobenzene are obtained by chlorination
directly by starting with pure 1,4-dichloro- of benzene or of intermediate fractions obtained
benzene. Because of the directing influence of in the production of di- and trichlorobenzene.
the chlorine substituents present (see Section Antimony trichloride – iodine [819] is a catalyst
8.1.2), only 1,2,4-trichlorobenzene and (to an combination that is particularly effective in giv-
extent depending on the degree of conversion) ing 1,2,4,5-tetrachlorobenzene, the industrially
higher chlorobenzenes are formed. preferred isomer (cf. Table 37). It is advisable to
Another production method applicable to discontinue the chlorination before an apprecia-
1,2,4- and 1,2,3-trichlorobenzenes is based ble amount of hexachlorobenzene has formed,
on the dehydrohalogenation of 1,2,3,4,5,6- since the low solubility of this compound makes
hexachlorocyclohexane (stereoisomeric mix- separation of the chlorination mixture difficult.
ture), a byproduct of γ-hexachlorocyclohexane After the lower chlorinated benzenes have been
production (→ Insect Control). In the pres- removed by distillation, the tetrachlorobenzenes
ence of aqueous alkali or alkaline earth so- are separated from one another by crystallization
lutions [800 – 803] or of ammonia [804], or with or without a solvent (the eutectic mixture
directly through use of catalysts [805 – 811], consists of 12 % 1,2,4,5- and 88 % 1,2,3,4-tetra-
hexachlorocyclohexane is converted at a temper- chlorobenzene and has a freezing point of 35
◦
ature of 90 – 250 ◦ C mainly to trichlorobenzene. C).
The yield lies between 80 and 99 %, with the The 1,2,4,5-tetrachlorobenzene crystals
product mixture consisting of 70 – 85 % 1,2,4- which result are of high purity. The fraction
trichlorobenzene and 13 – 30 % 1,2,3-trichloro- containing 1,2,3,4-tetrachlorobenzene must be
benzene. purified by distillation, however.
 Chlorinated Hydrocarbons 115

1,2,3,5-Tetrachlorobenzene which is not an approach which is both rapid and reliable.

available by direct chlorination of benzene, can Glass capillary and specially packed columns
be obtained by chlorination of 1,3,5-trichloro- are used. For those chlorobenzenes with solid-
benzene. ification points above 0 ◦ C, the temperature of
solidification can serve as a criterion of purity of
the main component. Typical analyses of several
8.1.3.5. Pentachlorobenzene commercial chlorobenzenes are as follows:
Pentachlorobenzene is of no economic signifi- Monochlorobenzene > 99.9 %, < 0.02 %
cance. Chlorination of benzene gives a mixture benzene, < 0.05 % dichlorobenzenes.
of tetra-, penta-, and hexachlorobenzenes, from 1,2-Dichlorobenzene. Technical grade: 70 –
which pentachlorobenzene can be isolated by 85 % 1,2-dichlorobenzene, < 0.05 % chloroben-
combined distillation and crystallization steps. zene, < 0.5 % trichlorobenzene, remainder 1,4-
and 1,3-dichlorobenzene
Pure grade: > 99.8 % 1,2-dichlorobenzene,
8.1.3.6. Hexachlorobenzene < 0.05 % chlorobenzene, < 0.1 % trichloroben-
zene, < 0.1 % 1,4-dichlorobenzene.
Hexachlorobenzene can be produced by exhaus-
tive chlorination of benzene, using chlorine in 1,3-Dichlorobenzene 85 – 99 %, < 0.01 %
the presence of such catalysts as ferric chloride. chlorobenzene, < 0.1 % 1,2-dichlorobenzene,
The reaction is conducted at a temperature above remainder 1,4-dichlorobenzene.
230 ◦ C in the liquid or vapor phase [820 – 822]. 1,4-Dichlorobenzene > 99.8 %, < 0.05 %
Because much of the chlorine remains unreacted chlorobenzene and trichlorobenzene, < 0.1 %
and because hexachlorobenzene sublimes, the 1,2- and 1,3-dichlorobenzene, bulk density
off-gas from the process is passed through fresh about 0.8 kg/L.
starting material, in the course of which the chlo- 1,2,4-Trichlorobenzene > 99 %, < 0.5 %
rine is reacted and the sublimate washed out. dichlorobenzenes, < 0.5 % 1,2,3-trichloroben-
The difficulties caused by sublimed hexachloro- zene, < 0.5 % tetrachlorobenzenes.
benzene can be eliminated by batch chlorination
with liquid chlorine in an autoclave [823]. 1,2,4,5-Tetrachlorobenzene > 98 %, <
Hexachlorobenzene can also be produced by 0.1 % trichlorobenzenes, < 2 % 1,2,3,4-tetra-
decomposition of hexachlorocyclohexane in the chlorobenzene, bulk density about 0.9 kg/L.
presence of chlorine. The resulting lower chlo-
rinated benzenes, mainly trichlorobenzenes, are
converted to hexachlorobenzene without first 8.1.5. Storage and Transportation
needing to be isolated [824 – 826].
High yields of hexachlorobenzene are obtain- The chlorobenzenes are all neutral, stable com-
able under very mild reaction conditions when pounds which can be stored in the liquid state in
chlorine-containing reagents such as chlorine steel vessels. The official regulations of various
monoxide [765] or chlorosulfuric acid/iodine countries must be adhered with respect to the
are used [766]. equipment of storage vessels, e.g., safety reser-
voir requirements, overflow prevention, and off-
gas escape systems.
8.1.4. Quality and Analysis Chlorobenzenes that are liquid at ambient
temperatures are shipped in drums, contain-
The usual separating processes employed in in- ers, or road/rail tankers. Solid compounds, such
dustry give chlorobenzenes of high purity. Those as 1,4-dichlorobenzene and 1,2,4,5-tetrachloro-
impurities which remain, as well as their concen- benzene, can be transported in the molten state in
trations, depend on the nature of the production heatable road/rail tankers or as granules or flakes
process and the separating technique applied. in paper sacks and fiber drums. Steel containers
The method now used almost exclusively to are suitable. Any paper or fiber materials that
determine the quantitative compositions of com- are used must be impermeable to vapors arising
mercial chlorobenzenes is gas chromatography, from the product.
116 Chlorinated Hydrocarbons

Liquid transfer must incorporate provisions recently, of polyphenylene-sulfide-based plas-

for gas compensation, as well as protection tics, materials with excellent thermal stability
against static charge. Chlorobenzene vapors [827, 828].
form flammable mixtures with air. The com- 1,2,4-Trichlorobenzene is used as a dye car-
pounds are regarded as potential water pollutants rier and (via 2,4,5-trichloronitrobenzene) in the
and must not be allowed to enter groundwater. production of dyes. Other uses are associated
Spills must be collected (proper precautions with textile auxiliaries and pesticide production
being taken to safeguard the health of the work- (where 2,5-dichlorophenol serves as an interme-
ers involved) and burned in a suitable incinera- diate). In the field of electrical engineering, it
tor. finds use as an additive for insulating and cool-
It should be noted that chlorobenzenes may ing fluids.
decompose with the release of hydrogen chlo- The hydrolysis of 1,2,4,5-tetra-
ride if they are exposed to severe heat. chlorobenzene to 2,4,5-trichlorophenol, an
Freight classifications are given in Table 40. intermediate for pesticides, has been almost
entirely discontinued throughout the world
8.1.6. Uses due to the risk of formation of 2,3,7,8-tetra-
chlorodibenzo-p-dioxin (TCDD).
The chlorobenzenes, particularly mono-, 1,2- Pentachlorothiophenol, a mastication agent
di-, and 1,2,4-trichlorobenzene, are widely used used in the rubber industry, is obtained from
as solvents in chemical reactions and to dissolve hexachlorobenzene. In the Federal Republic of
such special materials as oils, waxes, resins, Germany, the use of hexachlorobenzene as an
greases, and rubber. They are also employed in active ingredient for pesticides has been prohib-
pesticide formulations (the highest consumption ited since 1981.
of monochlorobenzene in the United States). Producers of chlorinated benzenes are: Anic
Monochlorobenzene is nitrated in large SpA (Italy); Bayer AG (FRG); Hodogaya Chem-
quantities, the product subsequently being con- ical Co., Ltd. (Japan); Hoechst AG (FRG);
verted via such intermediates as nitrophenol, Kureha Chemical Ind. Co., Ltd. (Japan); Mit-
nitroanisole, nitrophenetole, chloroaniline, and sui Toatsu Chemicals, Inc. (Japan); Mon-
phenylenediamine into dyes, crop protection santo Chemical Corp. (USA); Nippon Kayaku
products, pharmaceuticals, rubber chemicals, Co., Ltd. (Japan); Produits Chimiques Ugine
etc. The production of phenol, aniline, and DDT Kuhlmann SA (France); Rhône-Poulenc Chimie
from monochlorobenzene, formerly carried out de Base (France); Standard Chlorine Chemical
on a large scale, has been almost entirely discon- Co., Inc. (USA); Sumitomo Chemical Co., Ltd.
tinued due to the introduction of new processes (Japan).
and legislation forbidding the use of DDT.
1,2-Dichlorobenzene after conversion to
1,2-dichloro-4-nitrobenzene, is used mainly in 8.2. Chlorinated Toluenes
the production of dyes and pesticides. It is also
used to produce disinfectants and deodorants 8.2.1. Physical Properties
and on a small scale as a heat transfer fluid.
The chlorotoluenes occur in five chlorination
1,3-Dichlorobenzene is used in the produc- stages, four of which have several isomers:
tion of various herbicides and insecticides. It is
also important in the production of pharmaceu- Formula Num- Table in
ticals and dyes. ber of which phys-
isomers ical data
1,4-Dichlorobenzene is used mainly in the are given
production of disinfectant blocks and room de- Monochlorotoluenes C7 H7 Cl 3 41
odorants and as a moth control agent. After con- Dichlorotoluenes C7 H6 Cl2 6 42
version into 2,5-dichloronitrobenzene, it finds Trichlorotoluenes C7 H5 Cl3 6 43
application in the production of dyes. It is also Tetrachlorotoluenes C7 H4 Cl4 3 44
Pentachlorotoluene C7 H3 Cl5 44
used in the production of insecticides and, more
 Chlorinated Hydrocarbons 117

Table 40. Freight classification

GGVE/GGVS and IMDG Code and IATA-DGR US-DOT

RID/ADR
class number class UN No. pack. group

Monochlorobenzene 3 3 3.3 1134 II UN 1134 Flamm. liquid

1,2-Dichlorobenzene 3 4 6.1 1591 III ORM. A UN 1591
1,4-Dichlorobenzene – 6.1 1592 III ORM. A UN 1592
1,3-Dichlorobenzene 3 4 6.1 1591 III ORM. A UN 1591
Trichlorobenzene 6.1 62 6.1 2321 III Poison B UN 2810
Tetrachlorobenzene – 6.1 2811 III Poison B UN 2811
Hexachlorobenzene 6.1 62 6.1 2729 III Poison B UN 2811

All of the monochlorotoluenes are colorless, hydrolysis of monochlorotoluene with sodium

mobile, flammable liquids with a faint odor, hydroxide solution is possible at 350 – 400 ◦ C
similar to that of benzene; they form binary and pressures up to 30 MPa (300 bar), the result
azeotropes with many organic compounds [699, being isomeric cresol mixtures.
700]. Hydrogenation of chlorotoluenes over noble
The dichlorotoluenes, apart from 3,5-di- metal catalysts leads to dechlorination, just as in
chlorotoluene, are liquid at room temperature, the case of chlorobenzenes.
and they are likewise colorless and flammable. Chlorine substituents can be exchanged for
The tri, tetra-, and pentachlorotoluenes are col- amino groups [829], but this reaction has no in-
orless crystalline compounds. dustrial application.
The liquid chlorotoluenes are good solvents Under free-radical conditions at elevated
and are miscible with most organic solvents. All temperatures, it is possible to replace sequential-
chlorotoluenes are insoluble in water. The poly- ly the three hydrogen atoms of the methyl group
chlorotoluenes can be dissolved in many organic by halogen, leading to ring-chlorinated benzyl-,
solvents, particularly at elevated temperatures. benzal-, and benzotrihalides (see Chap. 9).
Oxidation of the methyl group leads to chlo-
rinated benzaldehydes and benzoic acids [830,
8.2.2. Chemical Properties 831].
Catalytic ammonoxidation with oxygen and
The chlorotoluenes are neutral and stable com- ammonia at 350 – 550 ◦ C converts the methyl
pounds. group into a nitrile group [832].
Chemical reactions may occur at unsubsti- The polychlorinated toluenes are similar to
tuted positions on the aromatic ring (e.g. halo- one another in their chemical behavior. Their
genation, nitration, or sulfonation), by replace- principal industrial use is in the manufacture of
ment of the chlorine substituent (e.g, hydroly- side-chain-halogenated products.
sis), and on the methyl group (e.g., side-chain
chlorination or oxidation).
The influence of the methyl group of toluene 8.2.3. Production
leads to electrophilic substitution at positions 2 Toluene Chlorination in the Liquid Phase.
and 4, whereas in chlorotoluenes the directing Monochlorotoluenes are produced on a large
influences of the methyl and chlorine groups scale by reacting liquid toluene with gaseous
overlap unpredictably. Introduction of a third chlorine at a moderate temperature and nor-
substituent (e.g., – Cl, – NO2 , – SO3 H) into 2- mal pressure in the presence of catalysts. Mix-
chlorotoluene can lead to all four possible iso- tures of isomers reflecting various chlorination
mers being formed, though position 5 is occu- stages are obtained. The chlorination conditions
pied preferentially. In 4-chlorotoluene, position should be such as to give the highest possible
2 is the most preferred position. The chlorine yield of monochlorotoluene, because the di-
atoms in these compounds are bound very firmly chlorotoluenes, all isomeric forms of which
to the aromatic ring and cannot be displaced ex- (with the exception of 3,5-dichlorotoluene)
cept under forcing conditions. Nevertheless, the
118 Chlorinated Hydrocarbons
Table 41. Physical properties of the monochlorotoluenes
result, cannot be separated economically. The
relative proportions of the various chloro-
toluenes obtained can be varied within wide lim-
its by altering the reaction conditions and cata-
lyst. With most catalyst systems, a high reac-
tion temperature favors ortho and meta substitu-
tion as well as further chlorination. Reducing the
temperature favors substitution in the para posi-
tion and increases the total yield of monochloro-
toluene. Because of the directing influence of
the methyl group, the 3-chlorotoluene fraction of
crude monochlorotoluene is limited to between
0.2 and 2 % depending on the catalyst. The influ-
ence of catalysts on the ratio of 2-chlorotoluene
to 4-chlorotoluene is apparent from the data in
Table 45. Selectivity is seen to be inversely pro-
portional to the activity of the catalyst [833].
Solvents also, influence the isomer distribu-
tion. This fact is of little significance, however,
because the toluene reactant in industrial chlo-
rinations is not diluted with solvents.
The reaction is usually conducted at a tem-
perature between 20 and 70 ◦ C. Chlorination at
temperatures below 20 ◦ C is uneconomical be-
cause the rate of reaction is too low.
Toluene has a higher π-basicity than benzene,
however, and it therefore, shows a substantially
higher rate of chlorination than the latter. As a
result, it can be chlorinated at relatively low tem-
peratures (Table 46).
This fact permits efficient conversion of
toluene to monochlorotoluenes without a sub-
stantial quantity of dichlorotoluenes also being
formed (see Table 45).
At a moderate reaction temperature (below
100 ◦ C), only traces of side-chain-chlorinated
products are formed, provided activation by light
is prevented and effective catalysts are used
(ones for which amounts of no more than several
tenths of a percent are required).
Both batch and continuous processes are used
commercially, with the former being more selec-
tive with respect to particular stages of chlorina-
tion. For continuous processes, it is necessary to
choose a toluene : chlorine starting ratio which
gives a lower degree of toluene conversion to
maximize the formation of monochlorotoluene.
 Chlorinated Hydrocarbons 119
Table 42. Physical properties of the dichlorotoluenes

Table 43. Physical properties of the trichlorotoluenes

Table 44. Physical properties of tetra- and pentachlorotoluenes

120 Chlorinated Hydrocarbons
Table 45. Influences of catalysts on the 2- : 4-chlorotoluene ratio

Catalyst 2- : 4-Chlorotoluene Dichlorotoluene Toluene Ref.

ratio in the chlorination conversion, %
mixture, %

TiCl4 , SnCl4 , WCl6 or ZrCl4 3.3 1.5 ∼99 [834]

[C6 H5 Si(OH)2 O]4 Sn 2.2 [835]
FeCl3 1.9 4.5 ∼75 [836]
SbCl3 – diethylselenide 1.9 ∼50 [837]
SbCl3 1.6 [727]
AlCl3 – KCl 1.5 <1 ∼16 [838]
SbCl3 – thioglycolic acid 1.2 [727]
FeCl3 – S2 Cl2 1.1 1.0 ∼99 [836]
Ferrocene – S2 Cl2 1.06 0.2 ∼67 [839]
Lewis acids – thianthrene 0.91 – 1.1 [840]
FeCl3 – diphenylselenide 0.93 ∼91 [837]
PtO2 0.89 2 ∼96 [841]
SbCl3 – phenoxathiin derivative 0.66 – 0.88 0.2 – 0.4 96 – 99 [842]
SbCl3 – tetrachlorophenoxathiin 0.85 – 0.87 [843]
SbCl3 – di- or tetrachlorothianthrene 0.7 – 0.9 0.1 – 0.2 [844]
Fe – polychlorothianthrene 0.76 1.2 ∼95 [845]

Table 46. Comparison of catalytic chlorination of benzene and

toluene
chlorine, then this chlorine should be removed in
order to prevent corrosion (e.g., pressure wash-
Catalyst system Ratio of the chlo- Ref. ing with aqueous alkaline solution may be car-
rination rates of
toluene to benzene ried out before the mixture enters the still).
FeCl3 16 [836]
Other Toluene Chlorination Processes.
FeCl3 – S 200 [836] The following toluene chlorination processes are
Glacial acetic acid 345 [846] known in addition to liquid phase chlorination:
Chlorination in the vapor phase with chlorine
The remarks in Section 8.1.3 on the contin- [849]
uous and batch chlorination of benzene apply Chlorination in the vapor or liquid phase with
correspondingly to the chlorination of toluene. hydrogen chloride and air (oxychlorination)
Problems related to reactor design, materials, Chlorination with chlorine-containing com-
and dissipation of heat – 139 kJ is set free pounds
per mole of monochlorotoluene [847] – are also Electrolysis of toluene and hydrochloric acid
comparable. The ignition temperature of toluene The oxidative chlorination of toluene with
in gaseous chlorine lies at 185 ◦ C. The explosive hydrogen chloride – air at a temperature of 150
limits of toluene in chlorine lie between 4 and –500 ◦ C in the presence of cupric chloride
50 vol %. Conventional refinery toluene is suf- as both catalyst and chlorinating agent gives
ficiently pure to serve as the starting material. mono- and dichlorotoluenes along with vary-
Traces of water that are entrained with techni- ing amounts of side-chain-chlorinated products
cal chlorine and toluene have no influence on the [745, 850 – 852]. In the Gulf process, the toluene
composition of the product. They must not be so is chlorinated with hydrochloric acid – oxygen
large as to reduce the efficiency of the catalyst, in the liquid phase in the presence of nitric acid
however. and an additional strong acid at a temperature
One process for reducing the water content of 60 – 150 ◦ C and pressures of 350 – 1000 kPa.
of the toluene below 30 ppm involves strip- By adding alkanes, e.g., n-octanes, the extent
ping with hydrogen chloride, and is described of side-chain attack can be reduced to 0.7 %.
in a patent on the continuous production of The addition of trialkylphenols is claimed to im-
monochlorotoluene [848]. prove the selectivity so that only one chlorine
As with the chlorobenzenes, the crude chloro- atom reacts with a given aromatic nucleus [853].
toluene mixture may be worked up by neutraliza- Good monochlorotoluene yields are obtained at
tion followed by separation in a distillation train. 50 ◦ C if ferric chloride is used as a chlorinat-
If the side-chain contains a detectable amount of ing agent in the presence of Lewis acids, such
 Chlorinated Hydrocarbons 121

as titanium chloride and aluminum chloride (o- 2-chlorotoluene distillate and a bottom prod-
chlorotoluene : p-chlorotoluene ratio 0.1 – 0.15) uct containing about 98 % 4-chlorotoluene. The
[729, 758, 854, 855]. Polymeric byproducts are boiling points of 3- and 4-chlorotoluene are
also formed but the side-chains are said to be so nearly alike that these two isomers can-
unattacked. not be separated by distillation. As in the pro-
Sulfuryl chloride [761, 856] and chlorine duction of pure 1,4-dichlorobenzene (see Sec-
monoxide [761] are other possible chlorinating tion 8.1.3.2) the latter separation must be ac-
agents. complished by crystallization from the melt.
Monochlorotoluene can also be manufac- The eutectic mixture contains 77.5 % m-di-
tured electrochemically. Thus, toluene can chlorotoluene and 22.5 % p-dichlorotoluene and
be chlorinated electrochemically in metha- has a solidification point of − 63.5 ◦ C. Conse-
nol to which water and sodium, ammoni- quently, crystallization from the melt must be
um, or lithium chloride has been added. High conducted at low temperatures.
yields of monochlorotoluene result without di- 4-Chlorotoluene can also be separated from
chlorotoluene being formed [857]. mixtures containing 2- and 3-chlorotoluene by
Other Processes. Only a few of the isomeric adsorption on zeolites at 200 ◦ C and 500 kPa
chlorotoluenes can be produced economically [860].
by direct chlorination and separation of the reac- 3-Chlorotoluene can be produced from m-
tion mixture. The other chlorotoluenes must be toluidine by a conventional Sandmeyer reaction
produced by indirect syntheses involving such [861] or by isomerization of 2-chlorotoluene on
steps as the replacement of amino substituents acid zeolites at 200 – 400 ◦ C and 2000 – 4000
by chlorine [770, 791] or introduction of meta- kPa, separation of the resulting mixture of 2-
directing sulfonic acid groups, which are then re- and 3-chlorotoluene being effected by distilla-
moved after chlorination on the ring [858, 859]. tion [860, 862].
See the following Sections for additional infor-
mation.
8.2.3.2. Dichlorotoluenes

The isomers of dichlorotoluene have very sim-

8.2.3.1. Monochlorotoluenes ilar chemical and physical properties, making
it difficult to separate individual components
Both 2- and 4-chlorotoluene are produced by from mixtures. Only 2,4-, 2,5-, and 3,4-di-
chlorination of toluene, as described in Sec- chlorotoluene can be produced economically
tion 8.2.3. The economic importance of 4- by direct chlorination of the appropriate pure
chlorotoluene is presently greater than that of monochlorotoluene isomers.
2-chlorotoluene, a circumstance which has led 2,3-Dichlorotoluene. In the chlorination of
to the development of new catalyst systems (see 2-chlorotoluene with ferric chloride, approx-
Table 45), which increase the output of the para imately 15 % of the product is 2,3-di-
isomer. The batch chlorination of toluene at 50 chlorotoluene, accompanied by 2,4-, 2,5-, and
◦
C in the presence of ferric chloride (or of ferric 2,6-dichlorotoluene; the former can be separated
chloride – sulfur monochloride at 40 ◦ C the val- by distillation. Its production by a Sandmeyer re-
ues for which are given in parentheses for com- action on 3-amino-2-chlorotoluene is more eco-
parison) gives at most 83 % (98 %) monochloro- nomical, however.
toluene, with 52 % (52 %) of the product being 2,4-Dichlorotoluene. Chlorination of 4-
o-chlorotoluene, 2 % (0.3 %) m-chlorotoluene, chlorotoluene in the presence of ring chlorina-
and 28 % (46 %) p-chlorotoluene, in addition to tion catalysts (e.g. chlorides of iron, antimony, or
7 % (1 %) unreacted toluene and 11 % (1 %) di- zirconium) leads to 2,4- and 3,4-dichlorotoluene
chlorotoluene [836]. in a ratio of ca. 4 : 1; the two can be sepa-
2-Chlorotoluene and 4-chlorotoluene are rated by fractional distillation. Only traces of
separated by fractional distillation. Continuous other dichlorotoluenes are formed [863, 864].
separation is possible with columns having more A low reaction temperature reduces the forma-
than 200 theoretical plates, leading to a pure tion of trichlorotoluene. According to [856],
122 Chlorinated Hydrocarbons

2-chlorotoluene is converted primarily into 2,4- ride leads to a product in which 2,3,4-tri-
dichlorotoluene when sulfuryl chloride is used chlorotoluene accounts for 22 % of the tri-
as the chlorinating agent. chlorotoluene fraction. The compound can be
2,5-Dichlorotoluene. The proportion of 2,5- separated from this mixture by distillation. It
dichlorotoluene in the dichlorotoluene fraction can also be produced from 3-amino-2,4-di-
can be raised to 60 % by chlorination of 2- chlorotoluene by using the Sandmeyer reaction
chlorotoluene with sulfur compounds as cata- [875].
lysts or cocatalysts. The product is separated 2,3,6-Trichlorotoluene. The chlorination of
from the reaction mixture by crystallization 2-chlorotoluene with an iron powder cata-
[865, 866]. Chlorination with iodine cataly- lyst gives a trichlorotoluene fraction containing
sis is also possible [867]. In addition, 2,5-di- 63 % 2,3,6-trichlorotoluene [876]. As 2,3,6-
chlorotoluene can be produced by a Sandmeyer and 2,4,5-trichlorotoluene have similar boil-
reaction on either 2-amino-5-chlorotoluene or ing points, their separation by distillation is
2,5-diaminotoluene. impractical. The concentration of 2,3,6-tri-
2,6-Dichlorotoluene. This isomer can be pro- chlorotoluene can be raised to 71 % by fractional
duced by chlorination of p-toluenesulfonyl crystallization in the absence of a solvent. This
chloride in the presence of antimonous chlo- procedure gives a eutectic mixture containing
ride, followed by desulfonation [858]. Alter- 29 % 2,4,5-trichlorotoluene and having a solid-
natively it can be made by chlorination of ification point of 21.5 ◦ C.
4-tert-butyltoluene or 3,5-di-tert-butyltoluene Higher yields of 2,3,6-trichlorotoluene
with subsequent dealkylation [868, 869] or by are possible from chlorination of 2,3-di-
means of a Sandmeyer reaction on 2-amino-6- chlorotoluene (75 %, in addition to 25 % 2,3,4-
chlorotoluene [870]. Distillatory separation of trichlorotoluene) or 2,6-dichlorotoluene (∼
the 2,6-dichlorotoluene from a chlorination mix- 99 %) [773]. 2,3,6-Trichlorotoluene can also be
ture (in which it constitutes about 30 % of the obtained by chlorination of p-toluenesulfonyl
dichlorotoluene fraction) is prohibitively expen- chloride or from 3-amino-2,6-dichlorotoluene
sive. It is impossible at this time to assess the eco- by a Sandmeyer reaction [875].
nomics of its continuous separation by means of 2,4,5-Trichlorotoluene. Chlorination of 4-
adsorption on faujasite-type zeolite [871]. chlorotoluene at 20 – 50 ◦ C gives > 80 % 2,4,5-
3,4-Dichlorotoluene. The proportion of 3,4- trichlorotoluene if ferrous sulfide is used as a
dichlorotoluene in the product mixture from catalyst. The product is separated from the chlo-
chlorination of 4-chlorotoluene can be raised to rination mixture by distillation [877].
about 40 % if sulfur compounds are used as cat- 2,4,6-Trichlorotoluene. The chlorination of
alysts or cocatalysts. This increase is at the ex- 2,4-dichlorotoluene in the presence of ferric
pense of the 2,4-dichlorotoluene [872]. chloride gives a trichlorotoluene fraction con-
3,5-Dichlorotoluene. This isomer is not taining 22 % of the 2,4,6-isomer, which can be
formed in the direct chlorination of toluene. Its isolated by fractional distillation.
indirect synthesis is possible via 2-amino-3,5-
dichlorotoluene [873]. 3,5-Dichlorotoluene can
also be produced to an extent corresponding to 8.2.3.4. Tetrachlorotoluenes
its equilibrium ratio by isomerization of other
dichlorotoluenes. The three tetrachlorotoluene isomers are all
formed when toluene is chlorinated (Table 48)
[874].
8.2.3.3. Trichlorotoluenes
2,3,4,5-Tetrachlorotoluene. The proportion
When toluene is chlorinated with 3 mol chlo- of the 2,3,4,5-isomer in the tetrachlorotoluene
rine per mole of toluene, four of the six possi- fraction can be raised to 49 % by starting with
ble trichlorotoluenes are formed in the following 2,4,5-trichlorotoluene. Its separation by distilla-
catalyst-dependent ratios (Table 47) [874]. tion is possible.
2,3,4-Trichlorotoluene. Chlorination of 4-
chlorotoluene in the presence of iron trichlo-
 Chlorinated Hydrocarbons 123
Table 47. Distribution of the isomeric trichlorotoluenes in the chlorination of toluene

Catalyst 2,3,4- 2,3,6- 2,4,5- 2,4,6-

Trichlorotoluene, % Trichlorotoluene, % Trichlorotoluene, % Trichlorotoluene, %

Ferric chloride 15 46 35 4
Ferric chloride – sulfur
monochloride 11 20 67 2

Table 48. Distribution of the isomeric tetrachlorotoluenes

Catalyst 2,3,4,5- 2,3,4,6- 2,3,5,6-

Tetrachlorotoluene, % Tetrachlorotoluene, % Tetrachlorotoluene, %

Ferric chloride 20 44 36
Ferric chloride – sulfur 25 45 30

2,3,4,6-Tetrachlorotoluene. Yields of 51 % 8.2.4. Quality and Analysis

and 66 % of this isomer are obtainable by
chlorination of 2,4,5-trichlorotoluene and 2,3,4- The industrially important chlorotoluenes can be
trichlorotoluene, respectively. 2,3,4,6-Tetra- produced such that they have a high degree of
chlorotoluene is the exclusive product of chlori- purity. No general agreement exists as to appro-
nation of 2,4,6-trichlorotoluene [874]. priate specifications. The following are typical
2,3,5,6-Tetrachlorotoluene. This isomer is analyses found for several chlorotoluenes:
obtained by exhaustive chlorination of p-
toluenesulfonyl chloride, followed by desul- 2-Chlorotoluene
Content >99 %
fonation [859]. toluene < 0.1 %
The various tetrachlorotoluenes are also ob- 4-chlorotoluene < 0.9 %
tainable from the corresponding amino com- 3-chlorotoluene < 0.01 %
4-Chlorotoluene
pounds by the Sandmeyer reaction.
Technical grade with >98 %
3-chlorotoluene < 1%
2-chlorotoluene < 0.5 %
8.2.3.5. Pentachlorotoluene dichlorotoluenes < 0.5 %
Pure grade with >99.5 %
3-chlorotoluene < 0.2 %
Exhaustive chlorination of toluene gives pen- 2-chlorotoluene < 0.2 %
tachlorotoluene. The reaction can be carried out dichlorotoluenes < 0.1 %
with chlorine in either carbon tetrachloride or 2,4-Dichlorotoluene
Content >99 %
hexachlorobutadiene as solvent in the presence 4-chlorotoluene < 0.2 %
of iron powder and ferric chloride as catalysts 2,5-dichlorotoluene < 0.3 %
[878], or with chlorine monoxide in carbon tetra- 2,6-dichlorotoluene < 0.1 %
3,4-dichlorotoluene < 0.4 %
chloride as solvent in the presence of an acid, 3,4-Dichlorotoluene
e.g., sulfuric acid [765]. Sulfuryl chloride, used Content >95 %
in the presence of sulfur monochloride and alu- 2,4-dichlorotoluene < 5%
minum chloride catalysts, is also a suitable chlo- trichlorotoluenes < 0.5 %
rinating agent, the method being that of O. Sil-
Chlorotoluenes are preferably analyzed by
berrad [761].
gas chromatography. Packed columns are used
Further chlorination of pentachlorotoluene in
to separate 2-, 3-, and 4-chlorotoluene. The more
the presence of a chlorination catalyst at a tem-
highly chlorinated toluenes can be separated by
perature above 350 ◦ C leads to the formation
means of glass capillary columns.
of hexachlorobenzene and carbon tetrachloride
[879].
8.2.5. Storage and Transportation
The mono- and dichlorotoluenes are stable, neu-
tral liquids. They are shipped in drums, contain-
124 Chlorinated Hydrocarbons

ers, and road or rail tankers. Steel is a suitable duction of 3,4-dichlorobenzyl chlo-
material for construction of containers. ride, 3,4-dichlorobenzaldehyde, 3,4-di-
For information on storage and handling, see chlorobenzotrichloride, and 3,4-dichloroben-
Section 8.1.5. zoic acid, from which disinfectants, crop pro-
Freight classifications are given in Table 49. tection products, and dyes are produced.
2,3,6-Trichlorotoluene. 2,3,6-Trichloro-
toluene is used on a small scale, together
8.2.6. Uses
with 2,4,5-trichlorotoluene, to produce 2,3,6-
trichlorobenzoic acid, a herbicide precursor.
Isomeric mixtures of the monochlorotoluenes
Producers of chlorinated toluenes are: Bayer
are hydrolyzed to cresol on a considerable scale.
AG (FRG); Enichem (Italy); Hodogaya Chemi-
Chlorotoluenes are also used as solvents in reac-
cals Co. Ltd. (Japan); Hoechst AG (FRG); Ihara
tions and to dissolve special products, e.g., dyes.
Chemical Ind., Ltd. (Japan); Occidental Chem-
2-Chlorotoluene. 2-Chlorotoluene is a start- ical Co., Ltd. (USA).
ing material in the production of 2-chloro-
benzyl chloride, 2-chlorobenzaldehyde, 2-
chlorobenzotrichloride, 2-chlorobenzoyl chlo- 8.3. Chlorinated Biphenyls
ride and 2-chlorobenzoic acid, which are
precursors for dyes, pharmaceuticals, opti- Industrial use of the polychlorinated biphenyls
cal brighteners, fungicides, and products of first began in 1929 in the USA [880, 881]. The
other types. 2-Chlorotoluene is also used in outstanding properties of these compounds, such
the production of dichlorotoluenes (chlorina- as their high chemical and thermal stability, high
tion), 3-chlorotoluene (isomerization), and o- dielectric constant, and the fact that they form
chlorobenzonitrile (ammonoxidation). only incombustible gases in an electric arc, made
4-Chlorotoluene. 4-Chlorotoluene is used them appear ideally suited for use as insulating
mainly to produce p-chlorobenzotrichloride, and cooling fluids for transformers and as di-
from which is obtained p-chlorobenzotrifluoride, electric impregnants for capacitors.
an important precursor of herbicides (e.g., In subsequent years many other applications
trifluralin:α,α,α,-trifluoro-2,6-dinitro-N,N- were found as well (see Section 8.3.5), particu-
dipropyl-p-toluidine). Other side-chain-chlo- larly for isomeric mixtures containing two to six
rinated products or their derivatives are 4- atoms of chlorine per mole of biphenyl.
chlorobenzyl chloride (for pharmaceuticals, In the mid-1960s, improved analytical meth-
rice herbicides, and pyrethrin insecticides), 4- ods revealed that polychlorinated biphenyls
chlorobenzaldehyde (for dyes and pharmaceuti- were accumulating in nature as a consequence of
cals), 4-chlorobenzoyl chloride (for pharmaceu- their extremely low rates of biological degrada-
ticals and peroxides), and 4-chlorobenzoic acid tion (rates which decrease as the chlorine content
(for dyes). 4-Chlorotoluene is also a starting rises). The compounds were detected in fresh
material in the synthesis of 2,4- and 3,4-di- water in all parts of the world, but also in many
chlorotoluene and of 4-chlorobenzonitrile. animals (e.g., birds, fish, and plankton). In the
late 1970s, it was further discovered that at tem-
2,4-Dichlorotoluene. 2,4-Dichlorotoluene
peratures of 500 to 800 ◦ C in the presence of
is used via its side-chain-chlorinated intermedi-
oxygen, polychlorinated biphenyls can give rise
ates to produce fungicides, dyes, pharmaceuti-
to polychlorinated dibenzofurans and dibenzo-
cals, preservatives, and peroxides (curing agents
dioxins, including (although to a much smaller
for silicones and polyesters).
extent) the particularly toxic compound 2,3,7,8-
2,6-Dichlorotoluene. 2,6-Dichlorotoluene tetrachlorodibenzodioxin [882 – 887].
is used to produce 2,6-dichlorobenzaldehyde, a In the meantime, all but a few of the well-
dye precursor, and 2,6-dichlorobenzonitrile, a known producers (see Section 8.3.5) discon-
herbicide. tinued the production of chlorinated biphenyls.
3,4-Dichlorotoluene. 3,4-Dichlorotoluene Moreover, in many countries the production,
is used in small amounts in the pro- sale, and use of polychlorinated biphenyls have
 Chlorinated Hydrocarbons 125
Table 49. Freight classification

GGVE/GGVS and IMDG Code and IATA-DGR US-DOT

RID/ADR
class number class UN No. pack. group

2- and 4-Chlorotoluene3 3 3.3 2238 III UN 1993

Flammable liquid
2,3-Dichlorotoluene 3 4 not restricted
2,4-Dichlorotoluene 3 4 not restricted
2,6-Dichlorotoluene 3 4 not restricted
3,4-Dichlorotoluene 3 4 not restricted

been restricted or entirely prohibited by legisla- hexachlorobiphenyl [26601-64-9]. Such mix-

tion. tures are liquid to viscous (pour points increase
For many years, o-, m- and p-terphenyl mix- with chlorine content from − 22 to + 18 ◦ C), and
tures were chlorinated and then used as plasticiz- they are fire-resistant. Further chlorination gives
ers, flame retardants, and fillers in thermoplastic soft to brittle thermoplastic waxes.
pattern and holding waxes. This application like- Chlorinated biphenyls are soluble in many
wise has been substantially discontinued [888], organic solvents, particularly when heated, but
particularly in view of the persistent nature of are soluble in water only in the ppm range. Al-
the compounds in question and their accumula- though they are chemically very stable, includ-
tion in the environment. Possible toxicological ing to oxygen of the air, they can be hydrolyzed
hazards are either unknown or have not been ad- to oxybiphenyls under extreme conditions, e.g.,
equately investigated (Table 50). with sodium hydroxide solution at 300 – 400 ◦ C
and under high pressure. Toxic polychlorodiben-
Table 50. MAK and TLV values of chlorinated biphenyls zofurans may be formed under these conditions.
The fact that the compounds may eliminate
MAK TLV
(FRG) (USA)
hydrogen chloride to a small extent at a high tem-
mg/m3 mg/m3 perature explains why hydrogen chloride accep-
tors are often added to transformer fluids based
Chlorinated biphenyls (42 % Cl) 1 III B 1
Chlorinated biphenyls (54 % Cl) 0.5 III B 0.5 on polychlorinated biphenyls.
The excellent electrical property data of
polychlorinated biphenyls, such as high dielec-
In view of the above, this article is devoted tric constant, low power factor, high resistivity,
primarily to a review of recent patents covering favorable dielectric loss factor, and high dielec-
methods for the disposal of polychlorinated bi- tric strength, have already been mentioned.
phenyls. For information regarding the produc-
tion of these compounds and their specific physi-
cal and chemical properties, attention is directed 8.3.2. Disposal
to earlier surveys [882, 889, 890].
Many products containing chlorinated biphenyls
are still in use throughout the world, particu-
8.3.1. Physical and Chemical Properties
larly in transformers, rectifiers, and capacitors
There are 209 possible chlorinated biphenyls. with long service lives. Industry and national
The mono- and dichlorobiphenyls [27323-18- governments are now faced with the need to
8], [25512-42-9] are colorless crystalline com- dispose of these products without causing addi-
pounds (the melting points of the pure isomers tional pollution of the environment. Appropriate
lie between 18 and 149 ◦ C). When burned in air, official regulations exist in many countries [888,
they give rise to soot and hydrogen chloride. 891 – 902].
The most important products are mixtures Attention is drawn in the following survey to
whose principal components are trichlorobiphe- patents concerned with the removal of polychlo-
nyl [25323-68-6], tetrachlorobiphenyl [26914- rinated biphenyls from electrical devices and
33-0], pentachlorobiphenyl [25429-29-2], or
126 Chlorinated Hydrocarbons

with the disposal of these compounds. It is im- 8.3.3. Analysis

possible to say which of the processes have ac-
tually reached maturity and which are already The analytical methods most frequently used
being used. for detecting chlorinated biphenyls are capil-
According to the present state of knowl- lary column gas chromatography coupled with
edge, polychlorinated biphenyls can be de- mass spectrometry in the MID (Multiple Ion De-
stroyed harmlessly by combustion at tempera- tection) mode and capillary column gas chro-
tures above 1000 ◦ C and a residence time of 2 s, matography with ECD (Electron Capture Detec-
e.g., in a rotary burner equipped with a scrubbing tor). These methods are suitable for solution of
tower for hydrogen chloride [888, 902 – 904]. even the most difficult problems. Clean-up steps
Regulations in the Federal Republic of Germany are necessary when complex matrices are con-
specify a temperature of 1200 ◦ C, a residence cerned, such as preliminary separation by col-
time of 0.2 s, and a residual oxygen content in umn chromatography.
the combustion gas of 6 % [897]. HPLC (High Pressure Liquid Chromatogra-
Removal of polychlorinated biphenyls from phy) and infrared spectroscopy are applicable to
silicone- and hydrocarbon-based transformer a limited extent.
fluids and heat transfer media is accomplished Summary polychlorinated biphenyl determi-
through the formation of a separable fraction nations are also possible, though not usual.
rich in polychlorinated biphenyls [905], treat- These require either exhaustive chlorination and
ment with polyalkylene glycol and alkali metal measurement of the decachlorobiphenyl content
hydroxide [906, 907], treatment with sodium or else dechlorination and subsequent measure-
naphthalenide [908], or heating with a sodium ment of the biphenyl content.
dispersion to 75 ◦ C [909]. For literature references on the subject of
Polychlorinated biphenyls are removed from analysis, see [902, 921 – 927].
impregnated electrical parts by irradiation with
microwaves, which causes gasification of the
compounds [910], or by dry distillation at 500 – 8.3.4. Storage and Transportation
1000 ◦ C followed by addition of oxygen [911].
Destruction of polychlorinated biphenyls has At a normal temperature the commercially used
been reported to be possible by the following polychlorinated biphenyls are liquid to viscous
methods: treatment with sodium naphthalenide mixtures with a comparatively low vapor pres-
in the presence of metallic sodium [912]; treat- sure (trichlorobiphenyl 6.5×10−5 kPa at 20 ◦ C).
ment at 145 ◦ C with a dehalogenating reagent Steel and aluminum are suitable as container ma-
prepared from an alkali metal, polyethylene gly- terials. The storage and shipping of these com-
col, and oxygen [913];reaction with sulfur in the pounds are subject to a variety of national reg-
vapor phase [914];adsorption on paramagnetic ulations. Since these compounds accumulate in
or ferromagnetic material and subsequent irra- the environment they must be handled so that
diation with microwaves in the presence of oxy- release cannot occur.
gen [915]; and irradiation with light in aqueous Exposure of polychlorinated biphenyls to fire
solution in the presence of a catalyst [916]. may result in the formation of toxic chlorinated
Thermal decomposition of polychlorinated dibenzofurans and dibenzodioxins [882 – 887]
biphenyls occurs by pyrolysis under oxidative and in the evolution of hydrogen chloride.
conditions (oxygen-enriched air) on molten al- Classification of polychlorinated biphenyls
kali carbonates at 900 – 980 ◦ C [917]; by use are:
of a plasma burner at 3000 – 4000 ◦ C [918]; by
GGVE/GGVS and RID/ADR: Class 6.1, Num-
dissolution in kerosene, followed by combustion
ber 23
in air and introduction of the combustion gases
IMDG-Code and IATA-DGR: Class 9, UN
into a special decomposition furnace [919]; or
Number 2315, Packaging group II
by evaporation with hydrogen as a carrier gas,
US D.O.T.: ORM.E, UN Number 2315
followed by combustion in oxygen [920].
 Chlorinated Hydrocarbons 127

8.3.5. Uses 8.4. Chlorinated Naphthalenes

Use of these compounds has fallen drastically The first industrial applications of chlorinated
[928] as a result of the extensive discontinua- naphthalenes took place at the beginning of
tion of their production, voluntary renunciation the 20th century [929]. The compounds were
of their application, and national restrictions. No used most extensively in the 1930s to 1950s,
details were available concerning products in especially in cable and capacitor production,
which polychlorinated biphenyls are still used, prompted by their dielectric, water-repellent,
nor concerning the scale of such use. The follow- and flame-retardant properties.
ing list of important fields of application should More recently, most producers of polychlo-
be regarded as retrospective: rinated naphthalenes have stopped their pro-
duction, and output has been reduced drasti-
Cooling and insulating fluids for transformers cally in all parts of the world. The reasons
Dielectric impregnating agents for capacitors for this follow. First, connections have been
Flame-retardant additives for resins and plas- established between highly chlorinated naph-
tics used in the electrical industry thalenes, especially pentachloronaphthalene and
Alkali- and acid-resistant plasticizers for lac- hexachloronaphthalene, and illness. Moreover,
quers, plastics, adhesives, fillers and sealing because of their high chemical and thermal sta-
compositions bility, highly chlorinated naphthalenes are able
Formulations for paints and printing inks to accumulate in the environment. Finally, new
Water-repellent additives for surface coatings materials (polyesters and polycarbonate) have
Dye carriers for pressure-sensitive copying been introduced as substitutes for chlorinated
paper naphthalenes in the capacitor and cable indus-
Additives for thermally-stable lubricants and tries.
gear oils Monochloronaphthalenes, by contrast, are
Incombustible hydraulic fluids (particularly not considered to be problematic with regard to
suitable for use in locations to which access their effects on health and accumulation in the
is difficult, e.g., in mines) environment [930].
Heat transfer fluids of high heat stability Official regulations relating to chlorinated
Inert sealing fluids for vacuum pumps naphthalenes differ considerably from country
Dust control agents for road construction to country. In Japan, for example, polychlori-
Mono- and dichlorobiphenyls have been used nated naphthalenes are prohibited entirely. In the
on a small scale as precursors for the correspond- USA they may still be used without restriction,
ing oxybiphenyls. but changes in their production, importation, or
Some registered trademarks are listed in Ta- use must be reported to the U.S. Environmental
ble 51. Most of the listed producers have discon- Protection Agency (EPA) [931], so that the ef-
tinued production. fects of these changes on the environment may
be monitored.

Table 51. Trade names of chlorinated biphenyls

8.4.1. Physical Properties
Apirolio Caffaro, Italy
Aroclor Monsanto, USA, UK Naphthalene has 75 chlorinated derivatives. To
Clophen Bayer AG, FRG date, however, only a few have been synthesized
Delor Chemco, Czechoslovakia
Fenclor Caffaro, Italy and isolated in pure form. Only isomeric mix-
Inerteen Westinghouse, USA tures characterized according to their chlorine
Kanechlor Kanegafuchi Chem. Co., Japan content are as a general rule commercially avail-
Pyralene Prodelec, France
Pyranol Monsanto, UK
able. This situation arises because of the fact that
Pyroclor Monsanto, USA the most important characteristics of the com-
Sovtol USSR pounds are a function solely of their degree of
chlorination, as a result of which there is lit-
tle demand for the pure compounds. Moreover,
precisely because the physical properties of the
128 Chlorinated Hydrocarbons

various isomers are very similar, the cost of their copper catalysts [936] to give 1-naphthol and
separation is unrealistically high. also 2-naphthol.
Except for 1-monochloronaphthalene, which In the absence of a catalyst, additive chlo-
is a liquid at room temperature, pure chlo- rination of 1-chloronaphthalene yields penta-
rinated naphthalenes are colorless, crystalline chlorotrihydronaphthalene and hexachlorodi-
compounds. Mixtures of the compounds for in- hydronaphthalene [937].
dustrial use have different degrees of chlorina-
Table 52. Physical data for monochloronaphthalenes*
tion, and their softening points lie considerably
below the melting points of the pure compo- 1-Chloronaphtha- 2-Chloronaphtha-
nents (generally between − 40 and + 190 ◦ C). As lene lene
the degree of chlorination increases, a transition [90-13-1] [91-58-7]

occurs from liquids, via waxes, to hard solids, Melting point, ◦ C −2.3 95.5 – 60
which causes the vapor pressures and water sol- Boiling point
at 101.3 kPa, ◦ C 260.2 258.6
ubilities to fall. In contrast, the melting points, Density, g/cm3
boiling points, and densities tend to rise, and any at 20 ◦ C 1.194 1.178
characteristics that are dependent on these prop- 80 ◦ C 1.144 1.130
erties become more pronounced. Mono- and di- Temperature corresponding
to vapor pressure , ◦ C
chloronaphthalenes are freely soluble in most or- 0.13 kPa 80.6
ganic solvents. Highly chlorinated naphthalenes 0.67 kPa 104.6
are most soluble in chlorinated aliphatic and aro- 1.33 kPa 118.6
2.67 kPa 134.4
matic solvents and in petroleum naphthas. 5.33 kPa 153.2
Chlorinated naphthalenes have excellent di- 8.00 kPa 165.6 161.2
electric properties. The tri- to hexachloronaph- 13.30 kPa 180.4
thalenes have dielectric constants of 4.5 – 5, a 26.70 kPa 204.2
dissipation factor of 1×10−3 at 800 Hz and 20 53.30 kPa
101.30 kPa
230.8
260.2
◦
C, and a specific resistivity (100 V, 1 min) above Refractive index n20
D 1.6326
1014 Ω cm. Viscosity at 25 ◦ C, mPa s 2.94
Chlorinated naphthalenes are compatible Flash point, ◦ C 115
Ignition temperature, ◦ C >500
with many other commercial products, e.g.,
chlorinated paraffins, petroleum waxes, bitu- * A eutectic mixture of 75 % of 1-chloronaphthalene and 25 % of
2-chloronaphthalene has a solidification point of −17.5 ◦ C.
men, various plasticizers (e.g., tricresyl phos-
phate), and polyisobutylene.
A selection of physical data obtained for pure The chemical and thermal stabilities of chlo-
monochloronaphthalenes and commercial mix- rinated naphthalenes increase with the num-
tures is given in Tables 52 and 53 . For physical ber of chlorine substituents. Highly chlorinated
data on pure polychlorinated naphthalenes, see naphthalenes withstand acids, caustic solutions,
[932]. and oxidizing agents, even at elevated tem-
peratures. An exception is concentrated ni-
tric acid, which forms nitro derivatives rela-
8.4.2. Chemical Properties
tively easily with polychlorinated naphthalenes
Reactions of the compounds may occur on the and which at 90 ◦ C oxidizes octachloronaph-
ring (electrophilic substitution), at the chlo- thalene to hexachloro-1,4-naphthoquinone and
rine substituent (e.g., hydrolysis), or with de- tetrachlorophthalic acid [938].
aromatization (chlorine addition). If naphthalene is chlorinated beyond the stage
1-Chloronaphthalene participates in elec- of octachloronaphthalene at a temperature ex-
trophilic substitution reactions such as nitration ceeding 200 ◦ C in the presence of ferric chloride
[934], sulfonation, halogenation, and chlorome- catalyst, perchloroindane and carbon tetrachlo-
thylation [935]. Reaction is especially favored ride are formed. This phenomenon is a result of
at the para position relative to chlorine. chlorine addition and subsequent ring constric-
Hydrolysis with sodium hydroxide solution tion [939], decachlorodihydronaphthalene being
takes place at about 300 ◦ C in the presence of an intermediate.
 Chlorinated Hydrocarbons 129
Table 53. Physical data for commercial chlorinated naphthalene mixtures [930, 932, 933]

CAS reg. no. Average Softening Boiling point Vapor Density atFlash MAK TLV
chlorine point pressure 25 ◦ C point (FRG) TWA
content (USA)
◦ ◦
% C C kPa g/cm3 ◦
C mg/m3 mg/m3

Monochloronaphthalene [25586-43-0] 22 −25 250 – 260 1.2 135

Mono-/dichloronaphthalene [28699-88-9] 26 −33 250 – 290 1.22 130
Tri-/tetrachloronaphthalene [1321-65-9] 50 93 304 – 354 8×10−3 1.58 200 5 5
Tetrachloronaphthalene [1335-88-2] 52 115 312 – 360 10−5 1.65 210 2
Tetra-/pentachloronaphthalene [1321-64-8] 56 120 327 – 371 1.67 230 0.5 0.5
Penta-/hexachloronaphthalene [1335-87-1] 62 137 343 – 384 1.78 250 0.2
Heptachloronaphthalene [32241-08-0]
Octachloronaphthalene [2234-13-1] 70 185 – 197 440 (101.3 kPa) 2.0 >430 0.1
246 (0.067 kPa)

8.4.3. Production Further information on the industrial chlorina-

tion of naphthalene will be found in the preced-
The chlorination of naphthalene proceeds less ing edition of this encyclopedia [942].
rapidly than that of benzene or toluene. Conse- The preparation of pure isomers representing
quently, chlorinated naphthalenes are produced the various chlorination stages is only of scien-
batchwise in agitator vessels. Molten naphtha- tific interest. A review of the procedures is given
lene, initially at 80 ◦ C, is mixed with gaseous in [932].
chlorine in the presence of ferric chloride or an- For information regarding the disposal of
timony pentachloride until the desired degree of waste gas and chlorinated naphthalene wastes,
chlorination has been reached. As the degree of see Section 8.5.
chlorination increases, the reaction temperature
must be raised to keep the mixture above its soft-
ening point. 8.4.4. Quality and Analysis
The crude chlorination mixture is neutral-
The quality of chlorinated naphthalenes is mon-
ized, e.g., with soda. The neutralizing agent is
itored by wet analysis for chlorine content, as
then separated and the crude product is fraction-
well as by gas chromatography employing glass
ated by vacuum distillation.
capillary columns. Traces are determined by the
Chlorine addition occurs if the chlorination
same analytical methods that have been devel-
is carried out in the absence of a catalyst, result-
oped for polychlorinated biphenyls. For litera-
ing in the unstable materials 1,2-dichloro-1,2-
ture on this subject, see [932, 943 – 950].
dihydro- and 1,2,3,4-tetrachloro-1,2,3,4-tetra-
One particular grade of monochloronaphtha-
hydronaphthalene.
lene is used in wood preservatives and consists
Incomplete naphthalene conversion is ac-
of
cepted in the production of monochloronaphtha-
lene in order to keep the proportion of polychlo- 90 – 94 % 1-chloronaphthalene
rinated naphthalenes small. The best possible 6 – 10 % 2-chloronaphthalene
result with ferric chloride as catalyst is 75 % < 0.1 % dichloronaphthalene
monochloronaphthalene and 13 % polychlori- < 0.01 % trichloronaphthalene and a
nated naphthalenes in an isomer ratio of 90 – chlorine content of 22 %.
94 % 1-chloro- and 6 – 10 % 2-chloronaphtha-
lene. If peroxodisulfate and chloride ions are
used as chlorinating agents, mainly monochlori- 8.4.5. Storage and Transportation
nated derivatives are obtained [940]. Because of The chloronaphthalenes are stable, neutral sub-
the large difference between their boiling points, stances. They can be stored in tanks as liquids,
the monochloronaphthalene isomer mixture is in which case adequate heating must be pro-
easily separated by distillation from the chlori- vided consistent with the melting point of the
nation mixture, and it is of high purity. The iso- material. Steel containers are suitable, although
mers can be separated by crystallization [941]. stainless steels should be used for applications
130 Chlorinated Hydrocarbons

in the electrical industry. Chlorinated naphtha- stricted their output and simultaneously reduced
lenes that are liquid at ambient temperatures are the content of highly chlorinated naphthalenes in
shipped in drums, containers, or road tankers. their products.
Solid chloronaphthalenes are supplied as pow-
Cerifal types, Caffaro, Italy
der or flakes, either in fiber drums or in pa-
Clonacire types, Prodelec, France
per sacks. Existing national regulations must be
Halowax types, Koppers Co., Inc., USA
complied with in connection with storage and
Nibren Wax types, Bayer AG, FRG
transportation.
Seekay wax types, ICI, Ltd., UK
Polychlorinated naphthalenes are not ex-
pressly mentioned in the shipping regulations of
either the EEC or the USA. Monochloronaph-
thalene has neither been allocated to a hazard 8.5. Environmental Protection
class nor given a UN number.
In the production of chlorinated aromatics, or-
ganic compounds are contained in three different
8.4.6. Use waste streams:
waste gas
The use of chlorinated naphthalenes has di- wastewater
minished considerably during the last 30 years. liquid or solid organic wastes
Thus, except in special cases, chlorinated naph-
thalenes are no longer used in capacitors or elec- The correct disposal of these wastes results
tric cable coverings. Their use as lubricants has in no harm to the environment.
also been largely discontinued. Practice in indi- Waste Gas Treatment. It is necessary to
vidual countries varies, however. In the USA, for distinguish between hydrogen chloride reaction
example, chlorinated naphthalenes are no longer gas from the chlorination process and substan-
used as wood preservatives. It is impossible to tially neutral waste gas, e.g. from distillation
generalize concerning which of the following columns or storage containers. The second of
potential applications are permissible at present. these waste gas streams can be purified in an
Monochloronaphthalenes: dye precursor; activated charcoal tower or incinerator. The hy-
dye dispersant; fungicide and insecticide wood drogen chloride reaction gas is processed in a
preservative; engine oil additive for dissolving complex manner to recover usable hydrochloric
sludges [951]; chemically and thermally sta- acid:
ble sealing fluid; ingredient in special cleaning
agents. 1) If the reaction gas contains chlorine, this is re-
Polychlorinated naphthalenes: dielectric for moved in a scrubbing tower (e.g., a bubble col-
impregnation of paper windings in automo- umn [952]) containing an easily chlorinatable
bile capacitors; insulating, waterproof, and compound, preferably a raw material used in
flameretardant dipping and encapsulating com- the chlorination process, and a chlorination
pounds for special electrical parts; binder in catalyst.
the manufacture of ceramic elements for the 2) In a second scrubbing tower, organic con-
electrical industry; paper coatings with water- stituents of the reaction gas are washed out
repellent, flame-retardant, fungicidal, and in- with a high-boiling solvent.
secticidal properties; plasticizers; electroplating 3) In addition to (or instead of) being passed
stop-off compound. through the second scrubbing tower, the hy-
Octachloronaphthalene: ingredient in the drogen chloride gas is cooled to the lowest
production of carbon elements by carbonization; possible temperature in a cooler, in which fur-
additive for lubricants used under extreme con- ther organic constituents are condensed out.
ditions and for flame-retardant plastics. 4) The hydrogen chloride is then absorbed in
Trade names for chlorinated naphthalenes. water in an adiabatic scrubber, from which
Most of the producers in the following list ei- it emerges as about 30 % hydrochloric acid
ther have entirely discontinued the production of with < 5 ppm of organically bound carbon.
chlorinated naphthalenes, or else they have re-
 Chlorinated Hydrocarbons 131

Absorption in calcium chloride solution in an excess of oxygen, the chlorinated compounds

the presence of calcium carbonate lumps has are converted into hydrogen chloride, carbon
also been described [953]. In this case, organic dioxide and water. The hydrogen chloride is re-
compounds are removed with the escaping car- moved from the flue gas by water scrubbers.
bon dioxide, and a 33 % calcium chloride so- Hydrodehalogenation is effected with hydro-
lution containing about 4 ppm of organic com- gen on palladium, platinum, or nickel catalysts
pounds remains. at elevated temperature and high pressure. The
Aqueous hydrochloric acid can be substan- nucleus-bound chlorine is substituted by hydro-
tially freed from organic substances by extrac- gen, and hydrogen chloride is thus formed. Mix-
tion with dodecylbenzene [954]. tures of different chlorination stages down to
The hydrogen chloride can also be liquefied the chlorine-free fundamental compound are ob-
in the absence of water and purified by distilla- tained [706, 957 – 959].
tion in a pressure column. Exhaustive chlorination of chlorinated hy-
The pure hydrogen chloride and its aque- drocarbons in the vapor phase at a temperature
ous solution are suitable for chemical processes. above 600 ◦ C and pressure up to 200 bar splits
There are also techniques to recover the chlorine the molecules, thus giving high yields of carbon
by electrolysis (e.g., the Hoechst-Uhde process) tetrachloride [707, 708].
or oxidation (Shell-Deacon process or Kel Chlo-
rine process).
Wastewater Treatment. The biological 8.6. Economic Facts
degradation rate of chlorinated aromatics de- Overall, it may be said that the use of chlorinated
creases as their chlorine content increases. Only aromatic hydrocarbons is stagnant or declining
chlorinated aromatics with low degrees of chlo- worldwide (see Tab. 54).
rination are degradable in biological wastewater
treatment plants, and then only if their con- Monochlorobenzene output in the USA fell
centration in the wastewater does not exceed from 275 100 t in 1960 to 115 700 t in 1982
certain levels. Therefore, wastewater streams [709] and increased in 1994 to 151 000 t. At the
containing chlorinated aromatics require pre- middle of 1984, Monsanto (at Muscatine, Iowa)
liminary purification. The following techniques discontinued the use of monochlorobenzene as
[955] are suitable: stripping, extraction, and ad- a carrier for the herbicide Lasso [710]; this is
sorption on activated carbon or polymeric resins expected to lead to a further drop in output.
[956]. As the production of monochloro-, 1,2-di-
Treatment of Wastes. These wastes may be chloro- and 1,4-dichlorobenzene is most eco-
distillation residues, useless fractions from sep- nomical in coproduction, it is becoming increas-
aration processes, or industrial products con- ingly difficult to adapt the manufacturing condi-
taining chlorinated aromatics that are no longer tions to the requirements of the market.
suitable for use. There are no output statistics for chlorinated
Normally these wastes are disposed of by in- toluenes. It is estimated that 30 000 t of 1- and 4-
cineration. In principle, it is also possible to con- chlorotoluene was produced in Western Europe
vert chlorinated hydrocarbons into usable com- in 1983 [709].
pounds by hydrodehalogenation or chlorinoly- The production of polychlorinated biphe-
sis. It is impossible to say whether these pro- nyls has been almost completely discontinued
cesses are already being used on an industrial throughout the world (cf. Section 8.3). Since the
scale. first industrial use of polychlorinated biphenyls
Chlorine-containing aromatics are burned in at the beginning of the 1930s, about 1 million
special furnaces that provide reaction temper- tons have been produced [712]; 40 % of this
atures above 1000 ◦ C and residence times of quantity is estimated to be still in use. Consump-
1 – 2 s [904]. Only then is it certain that no tion reached its highest level in the 1960s.
polychlorodibenzodioxins are formed during The production of chlorinated naphthalenes
combustion. This risk exists particularly with has also fallen greatly, with a shift toward less
polychlorinated biphenyls (see Section 8.3). In highly chlorinated naphthalenes. Output in the
132 Chlorinated Hydrocarbons

Table 54. Production of chlorobenzenes [709, 711] in 103 t/a

Monochlorobenzene 1,2-Dichlorobenzene 1,4-Dichlorobenzene Sum of all

chlorobenzenes

USA 1970 220 30 32

1981 130 23 33
1988 11 42
FRG 1970 127
1981 97 34 138
Japan 1981 34 9 16 50

USA fell from 2270 tons in 1972 [713] to 320

tons in 1978; after the manufacture of chlori-
nated naphthalenes had been discontinued, the
quantity imported into the USA settled at about
15 tons in 1980 and 1981 [714]. The output
of the USA in 1972 consisted of 25 – 28 % of
mono-/di-, 65 – 66 % of tri-/tetra-, and about 9.1. Benzyl Chloride
8 % of penta- to octanaphthalenes [713]. In the
Federal Republic of Germany with an output Benzyl chloride (chloromethylbenzene, α-
of about 1000 t of chlorinated naphthalenes chlorotoluene) [100-44-7] may be structurally
in 1972 [715], the production of polychlori- the simplest side-chain chlorinated derivative of
nated naphthalenes has likewise been discon- toluene, but economically it is the most impor-
tinued; only monochloronaphthalenes are now tant. Benzyl chloride is the starting material for
produced, output being of the order of 100 t/a. a large number of industrial syntheses. The first
preparation of it involved not the chlorination
of toluene, however, but the reaction of benzyl
9. Side-Chain Chlorinated Aromatic alcohol with hydrochloric acid (S. Cannizzaro,
1853).
Hydrocarbons
Alkyl aromatics are somewhat unique in their
9.1.1. Physical Properties
behavior with respect to chlorination reactions.
The action of elemental chlorine can lead ei-
Benzyl chloride is a colorless liquid which
ther to addition or substitution on the aromatic
fumes in moist air. It has a pungent odor and is
ring or it can cause substitution in the aliphatic
irritating to the mucous membranes and the eyes
side-chain, depending on the reaction condi-
(i.e., it has a powerful lachrymatory effect).
tions.
The side-chain chlorinated alkyl aromatics, Mr 126.58
particularly those based on toluene and xylene, bp at 101.3 kPa 179.4 ◦ C
mp − 39.2 ◦ C
have an exceptional place because of their role as
 at 0 ◦ C 1.1188 g/cm3
chemical intermediates. Indeed, they are used in 10 ◦ C 1.1081 g/cm3
the manufacture of chemical products of almost 20 ◦ C 1.1004 g/cm3
all kinds, including dyes, plastics, pharmaceuti- 30 ◦ C 1.0870 g/cm3
50 ◦ C 1.072 g/cm3
cals, flavors and perfumes, pesticides, catalysts, 87 ◦ C 1.037 g/cm3
inhibitors, and so forth. n20
D 1.5389
Those side-chain-chlorinated alkyl aromat- Dynamic viscosity η at
ics which are of greatest importance in indus- 15 ◦ C 1.501 mPa s
20 ◦ C 1.38 mPa s
trial chemistry are the toluene derivatives benzyl 25 ◦ C 1.289 mPa s
chloride, benzal chloride, and benzotrichloride. 30 ◦ C 1.175 mPa s
 Chlorinated Hydrocarbons 133
Surface tension σ at
15 ◦ C 38.43 mN/m
rine in 100 g of benzyl chloride is 8.0 g at 30 ◦ C,
20 ◦ C 37.80 mN/m 5.4 g at 50 ◦ C, and 2.1 g at 100 ◦ C [971].
30 ◦ C 36.63 mN/m
88 ◦ C 29.15 mN/m
17 ◦ C 19.5 mN/m
Specific heat at
9.1.2. Chemical Properties
0 ◦C 178 J mol−1 K−1
(1403 J kg−1 K−1 ) Benzyl chloride can serve as a starting point
20 ◦ C 181 J mol−1 K−1 for the preparation of benzal chloride and ben-
(1432 J kg−1 K−1 )
25 ◦ C 183 J mol−1 K−1
zotrichloride, both of which are accessible by
(1444 J kg−1 K−1 ) side-chain chlorination. Nuclear chlorination,
50 ◦ C 189 J mol−1 K−1 on the other hand, leads to chlorobenzyl chlo-
(1495 J kg−1 K−1 ) rides. Oxidation with sodium dichromate gives
100 ◦ C 212 J mol−1 K−1
(1675 J kg−1 K−1 )
sodium carbonate in aqueous solution benzalde-
Heat of vaporization at 25 ◦ C 50.1 kJ/mol (396 kJ/kg) hyde and benzoic acid.
Heat of combustion at 3708 kJ/mol Metals undergo a variety of reactions with
constant volume (29.29×103 kJ/kg) benzyl chloride. For example, magnesium in
Flash point 60 ◦ C
Ignition temperature 585 ◦ C ether gives benzyl magnesium chloride (Grig-
Explosive limits in air, nard), whereas copper powder or sodium gives
lower 1.1 vol% 1,2-diphenylethane as the main product (Wurtz
upper 14 vol%
Explosive limits in chlorine,
synthesis). The action of Friedel-Crafts catalysts
lower ca. 6 vol% such as FeCl3 , AlCl3 , and ZnCl2 gives conden-
upper ca. 60 vol% sation products of the (C7 H6 )n type [972], but
Specific conductivity at 20 ◦ C 1.5×10−8 S/cm despite the fact that the degree of condensation
Vapor pressure at
0 ◦C 0.025 kPa
can be controlled by changing the reaction con-
10 ◦ C 0.05 kPa ditions, these polymers have no commercial sig-
20 ◦ C 0.12 kPa nificance. If benzene or toluene is added to ben-
30 ◦ C 0.37 kPa zyl chloride in the presence of Friedel-Crafts
50 ◦ C 0.99 kPa
100 ◦ C 7.96 kPa catalysts, one obtains diphenylmethane or the
130 ◦ C 23.40 kPa isomeric benzyltoluenes, respectively.
179.4 ◦ C 101.33 kPa The action of hydrogen sulfide and sulfides
of the alkali metals leads to benzyl mercap-
Numerous binary and ternary azeotropes con- tan and dibenzyl sulfide, respectively. Reactions
taining benzyl chloride are known [970]. Exam- with sodium salts of carboxylic acids produce
ples are given in Table 55. the corresponding benzyl esters.
Hydrolysis with hot water is said to result in
Table 55. Azeotropic mixtures with benzyl chloride
the formation of benzyl alcohol; nevertheless,
Component Boiling point, Benzyl this reaction has no industrial applications be-
◦
C chloride, wt % cause the hydrochloric acid formed causes the
Benzaldehyde 177.9 50 re-formation of benzyl chloride from the product
Hexanoic acid 178.7 95 benzyl alcohol; it also catalyzes the formation of
Isovaleric acid 171.2 38 dibenzyl ether.
Valeric acid 175 25
Ethyl acetoacetate 175 35
Hydrolysis in the presence of alkali does lead
Methyl acetoacetate 167 <80 to benzyl alcohol, however.
1,3-Dichloro-2-propanol 168.9 57 Benzyl chloride reacts with sodium cyanide
2,3-Dichloro-2-propanol 171 40 to give phenylacetonitrile (benzyl cyanide).
Ethylene glycol ca. 167 ca. 30
Reaction with ammonia or amines gives pri-
mary, secondary, tertiary amines, and quaternary
The solubility of benzyl chloride in water is ammonium salts.
0.33 g/L at 4 ◦ C, 0.49 g/L at 20 ◦ C, and 0.55 g/L The reaction with hexamethylenetetramine
at 30 ◦ C. Benzyl chloride is freely soluble in produces benzaldehyde (Sommelet reaction).
chloroform, acetone, acetic acid esters, diethyl
ether, and ethyl alcohol. The solubility of chlo-
134 Chlorinated Hydrocarbons
◦
9.1.3. Production C). In both cases, the effect is a result of ex-
citation of chlorine molecules.
Substitution of chlorine for hydrogen in the Irradiation is generally carried out with mer-
aliphatic side-chain occurs by way of a radical cury vapor lamps that emit light in the wave-
chain mechanism; by contrast, chlorine substi- length range 300 – 500 nm, corresponding to
tution on the aromatic ring takes place according the region in which the absorption bands of
to an electrophilic polar mechanism. chlorine lie (hence, its yellowish-green color).
The steps in the radical chain process are as The effects of varying the wavelength have
follows: been investigated in detail [975 – 977]. A so-
lution containing 0.1 % chlorine absorbs 90 %
chain initiation Cl2 + hν → 2 Cl · (1) of the available light energy over a distance of
chain propagation Cl · + RH → R · + HCl (2) only 12 cm [978]. At a chlorine concentration
R · + Cl2 → RCl + Cl · (3)
chain termination Cl · + Cl · → Cl2 (4) of 3 – 4 mol/L, the corresponding distance is
R · + Cl · → RCl (5) reduced to 0.01 cm [973]. Consequently, thor-
R · + R · → RR (6) ough mixing of the reactor contents is ad-
vantageous, as is the use of reactors of rel-
This chlorination is highly exothermic (96 – atively small diameter. These considerations
105 kJ/mol chlorine). In view of the high rate of apply regardless of whether the sources of ra-
chlorine radical formation and of hydrogen dis- diation are inside the reactor or external to
placement, it is not surprising that, depending it [979 – 981]. In the case of bubble column
on the substrate and reaction conditions, radical reactors, the height of the reactor is also im-
chain lengths of 103 [973] to 106 [974] have been portant in view of the velocity of the rising
found. Because the mechanisms of side-chain gas bubbles, which is ca. 20 cm/s [982, 983].
chlorination and nuclear chlorination are fun- 2) Friedel-Crafts catalysts favor nuclear chlori-
damentally different, selectivity can be readily nation. For this reason, particular attention
achieved. The prerequisites for high side-chain must be paid to ensure, for example, that the
chlorination efficiency are as follows: starting toluene is free of dissolved iron salts
1) Achievement and maintenance of an optimal and that all rust particles have been filtered.
radical concentration By extension, steel, including stainless steel,
2) Elimination of components that might impart is unsuitable as a reactor material. The pre-
an electrophilic course to the reaction ferred reactor materials are glass, enamel, and
3) Elimination of components capable of termi- polytetrafluoroethylene.
nating the radical chains Extensive purification of technical-grade
4) Elimination of components conducive to starting materials is very expensive, how-
other side reactions ever. For this reason, numerous suggestions
5) In general, taking those precautions, which have been made for additives that might in-
would encourage radical reactions or suppress hibit the undesirable effects of heavy met-
electrophilic reactions als. Most such additives are assumed to
The discussion which follows considers each complex with, e.g., iron cations. Some ad-
of these points separately. ditives are reported to accelerate the side-
chain chlorination, thereby inhibiting in a rel-
1) Chlorine radical formation can be promoted ative sense nuclear chlorination. The follow-
by the addition of a radical-forming agent ing are examples of additives which have
such as 2,2 -azobis(isobutyronitrile) (AIBN), been recommended at concentrations of 0.1
benzoyl peroxide, or hexaphenylethane. Such –2 %: pyridine and phenylpyridines [984],
compounds are consumed in the reaction, alkylene polyamines [985], hexamethylene-
however, and thus have to be added repeat- tetramine [986], phosphoramides [987], acid
edly. For this reason, two other methods, amides, alkyl and dialkyl acid amides [988],
singly or in combination, are of greater impor- ureas [989], phosphorus chlorides [990], alkyl
tance, particularly in industrial chlorinations: phosphites and phosphines [991], phosphorus
irradiation (ultraviolet light, β-radiation) and trichloride and trialkyl phosphates [992],
the use of an elevated temperature (100 – 200
 Chlorinated Hydrocarbons 135

cyclic thioureas [993], lactams [994], red

phosphorus [995], and aminoethanol [996].
3) Oxygen, a well-known radical scavenger,
greatly reduces the consumption of chlorine;
its presence is therefore undesirable. Toluene The change in the composition of the mixture
can be freed of oxygen, for example, puryng as a function of the number of moles chlorine
with an inert gas. The use of distilled chlorine, that have reacted is shown in Figure 34 [1010].
likewise, is an effective means of preventing Similar results have been reported by other au-
oxygen from being present at significant con- thors [975, 977, 1001, 1011].
centrations [997 – 1001].
It has also been reported, however, that even
chlorine which contains up to 2 % oxygen
is suitable for side-chain chlorination at rel-
atively low temperatures (40 – 50 ◦ C) pro-
vided that phosphorus trichloride (1 – 3 %) is
present [1002].
4) The presence of water leads to the formation
of aqueous hydrochloric acid (indicated by
cloudiness) and possibly to the hydrolysis of
the chlorinated toluene; in addition, hydroly-
sis products which arise may be further al-
tered by chlorination. The hydrogen chloride
that is inevitably formed during chlorination
is thought to be responsible for the fact that Figure 34. Progression of toluene chlorination [975, 977,
nuclear chlorination can never be entirely sup- 1001, 1010, 1011]
pressed [1003].
5) Various authors [998, 1001, 1004] have drawn Extensive investigations [975] have shown
attention to the adverse effects caused by that for batch operations, it is practically im-
excessive chlorine concentrations (especially possible to alter the shape of these curves, nei-
nuclear chlorination, both addition and substi- ther by changing the intensity and wavelength of
tution). Besides ensuring that the level of irra- the light, by adding radical-forming agents (e.g.,
diation is adequate for rapid reaction, it may peroxides), by changing the quantity of chlorine
be useful to introduce an inert gas (N2 , HCl) introduced in unit time, by using PCl3 or PCl5
into the chlorine stream. Dividing the reactor or other catalysts, nor by other means.
into smaller units is apparently also advanta- Only the rate of the reaction and the nature
geous, particularly in the case of a continuous of the observed side reactions can be shown to
process [980, 981, 1005, 1006]. Much atten- depend significantly on the reaction conditions.
tion has also been paid to the development Little is known with certainty about the abso-
of kinetic models, to the design of reactors, lute reaction rates. One reason for the scarcity
to the effects of agitators, to the distribution of information is the fact that the actual concen-
of radiation, and to the effects of inhibitors tration of the dissolved chlorine is not accurately
[1007 – 1009]. measurable. If the chlorine concentration is as-
sumed to be constant, the reactions can be taken
In the course of radical chlorination of to be quasi first-order, leading to the following
toluene, all three hydrogen atoms of the side- calculated ratios of rate constants at 100 ◦ C:
chain are successively replaced by chlorine. As k1 : k2 6.0 [975] 7.3 [999] 9.0 [1001]
a result, mixtures of the three expected com- k2 : k3 5.7 [975] 10.7 [999] 9.0 [1001]
pounds are obtained: benzyl chloride, benzal
where k 1 , k 2 , and k 3 are defined in the equations
chloride, and benzotrichloride.
above.
The individual components of the mixture
can be isolated in pure form by fractional dis-
tillation. To prevent the decomposition of ben-
136 Chlorinated Hydrocarbons

zyl chloride during the distillation process, mea- Today, most side-chain chlorination of
sures similar to those used to effect stabilization toluene to produce benzyl chloride, together
during storage and transportation (see Section with benzal chloride (Fig. 34), is apparently car-
9.1.5) have been suggested [1012 – 1014]. ried out in a continuous fashion. The silver- or
Numerous attempts have been made to pro- lead-lined reaction columns described in the past
duce benzyl chloride that is as free as possible of [1005] represent an obsolete technology since
the secondary products benzal chloride and ben- they are subject to considerable corrosion. For
zotrichloride. One possibility is to restrict the photochlorination, it is now customary to use re-
chlorination to only 30 – 40 % of the toluene in- actors of enamel or glass, e.g., of the loop type
put and then to separate by distillation the result- [981]. The operating techniques have remained
ing mixture, which still has a very high toluene fundamentally unchanged, however.
content. Here, the principal disadvantage is the Dibenzyl ether is formed as a byproduct in the
high cost of the distillation process. alkaline hydrolysis of benzyl chloride to benzyl
According to [1015], pure benzyl chloride alcohol (see → Benzyl Alcohol). This ether can
can be produced by chlorination in the vapor be re-converted to benzyl chloride by cleavage
phase, provided the following equipment and with hydrogen chloride at a temperature below
procedure are used: The lower end of a packed 100 ◦ C. Zinc chloride, iron chloride, and anti-
column is provided with a bottom flask with mony chloride, are recommended as catalysts.
a heater and an overflow. At the upper end is Only a moderately high degree of conversion
placed a condenser and a gas outlet. The feed is achieved (60 – 70 %) [1017]. Higher yields
point for fresh toluene and for toluene return- are claimed to be obtained if the metal halo-
ing from the condenser is situated in the up- genide catalysts are replaced by pyridine, pyri-
per third of the column. The feed point for the dine derivatives, or alkylbenzylammonium chlo-
chlorine (comprised of nozzles or frits) is lo- ride [1018]. Another route to benzyl chloride
cated within the lower third. The temperature is the chloromethylation of benzene, although
of the zone in which chlorination occurs is held this approach is of no commercial significance
at 125 ◦ C during operation. This ensures that a [1019].
temperature range is maintained within which Environmental Protection. Benzyl chlo-
benzyl chloride is a liquid whereas toluene is a ride, like chlorinated hydrocarbons in general,
gas. Under these conditions, benzyl chloride is must be handled with special care. The thresh-
rapidly removed from the chlorination section, old limit value (TLV) and the Federal Republic
flowing into the bottom flask; entrained toluene of Germany’s MAK value are both 1 ppm (5
is returned from here to the chlorination sec- mg/m3 ). Benzyl chloride has been allocated to
tion by evaporation. Hydrogen chloride formed Category III B of the MAK list (the category
during the chlorination, as well as toluene va- comprising substances for which there is reason
pors, leave the column at its upper end. The to suspect carcinogenic potential). Therefore,
toluene is liquefied in the condenser and returns special requirements must be met concerning
to the chlorination section where it mixes with the sealing of production equipment and venti-
fresh toluene. The column is operated continu- lation of workrooms. Since benzyl chloride is
ously. The bottom product is claimed to consist a chlorinated hydrocarbon and homologue of
of 0.9 % toluene, 93.6 % benzyl chloride, and benzene, regular medical inspection of affected
5.5 % distillation residue. Several risks are inher- personnel is required by law.
ent in this procedure. For example, the ignition
temperature of toluene in chlorine gas is 185 ◦ C.
In addition, toluene –chlorine and benzyl chlo- 9.1.4. Quality Specifications and Analysis
ride – chlorine mixtures are explosive over wide
ranges (4 – 50 vol%, and 6 – 60 vol% respec- Benzyl chloride is sold in two quality grades,
tively). identified as “benzyl chloride, pure” and “ben-
Monochlorination in the side-chain is said to zyl chloride, pure and stabilized”. Their assay is
be possible in the presence of alkyl or aryl sul- in both cases > 99 %. Impurities include ben-
fides or red phosphorus [995, 1016]. zal chloride, toluene, chlorotoluene, chloroben-
zene, and hydrogen chloride.
 Chlorinated Hydrocarbons 137

The most reliable analysis technique is gas GGV-See/IMDG Code Class 6.1;
chromatography, performed either with capil- UN no. 1738
lary or packed columns. The usual solid support
Warning plate 6 (poison) must be displayed
in packed columns is Chromosorb AW-DMCS
when benzyl chloride is transported on land. Pri-
80 – 100 mesh; recommended liquid phases in-
mary label no. 6 (poison) and secondary label
clude 4 % Silicone Fluid DC 550 and 4 %
no. 8 (corrosive) are prescribed for marine trans-
polyphenyl ether. Silicone resins are proven
portation.
coating materials for capillary columns.
Benzyl chloride is additionally subject to the
Arbeitsstoffverordnung of the Federal Repub-
lic of Germany and to the corresponding regu-
9.1.5. Storage and Transportation
lations of the European Community (EC com-
pound no. 602–037–00–3).
As benzyl chloride is capable of reacting with
heavy metals and their salts (Friedel-Crafts con-
densation reactions with the formation of HCl
9.1.6. Uses
vapors), storage in enamel, glass, or lined ves-
sels is essential. Suitable lining materials in-
Benzyl chloride is used mainly to produce plas-
clude bricks, lead, pure nickel, and stable syn-
ticizers (e.g., benzyl butyl phthalate), benzyl al-
thetic resins. Drums with inserts of polyethylene
cohol, and phenylacetic acid via benzyl cyanide
or thick-walled polyethylene drums pigmented
(used in the production of synthetic penicillin).
with graphite are suitable for transportation. Lin-
On a smaller scale, it is used to produce qua-
ings of lead, nickel, or special synthetic resins
ternary ammonium salts (for disinfectants and
have proven to be suitable for tank cars and tank
phase-transfer catalysts), benzyl esters (benzyl
trucks. Many stabilizers have been proposed to
benzoate and benzyl acetate for the flavors and
make the storage and transportation of benzyl
perfumes industry), dyes of the triphenylmeth-
chloride safer. These act by neutralizing HCl
ane series, dibenzyl disulfide (antioxidant for lu-
and/or by forming complexes with heavy-metal
bricants), benzylphenol, and benzylamines.
ions. Examples are N,N-dimethylbenzylamine
and N,N-diethylbenzylamine [1020]; pyridine
and alkyl pyridines, quinoline, and bipyridyls
(occasionally mixed with C5 – C8 alcohols) 9.2. Benzal Chloride
[1013]; primary, secondary, and tertiary amines
[1014, 1021, 1022]; phosphines [1023]; lactams Benzal chloride (dichloromethylbenzene, α,α-
[1024]; acid amides [1025]; ureas [1026]; and dichlorotoluene, benzylidene chloride) [98-87-
nitroalkanes [1027]. Aqueous sodium carbonate 3] is produced exclusively by the side-chain
or sodium hydroxide solutions with a specific chlorination of toluene. It was first synthesized
gravity identical with that of benzyl chloride in 1848 by A. Cahours, by using the reaction of
were formerly used as stabilizers, but this prac- PCl5 with benzaldehyde. Almost the sole appli-
tice has been largely discontinued. The emulsion cation of benzal chloride is in the production of
these stabilizers produce lacks thermal stability benzaldehyde.
and their presence makes it impossible to carry
out reactions that require anhydrous benzyl chlo-
ride. 9.2.1. Physical Properties
Legal Requirements. Benzyl chloride is a Benzal chloride is a liquid which fumes in moist
toxic chlorinated hydrocarbon and as such is air and which has a pungent odor and a strong ir-
subject to numerous regulations. The following ritant effect on the mucous membranes and eyes.
regulations must be followed during its trans-
port:
GGVS/ADR Class, 6.1 no. 15 b
GGVE/RID Class, 6.1 no. 15 b
138 Chlorinated Hydrocarbons
Mr 161.03
bp at 101.3 kPa 205.2 ◦ C
Metallic sodium converts benzal chloride into
mp − 16.2 ◦ C stilbene.
 at 0 ◦ C 1.2691 g/cm3
20 ◦ C 1.2536 g/cm3
30 ◦ C 1.2417 g/cm3
57 ◦ C 1.2122 g/cm3
9.2.3. Production
79 ◦ C 1.1877 g/cm3
135 ◦ C 1.1257 g/cm3 Benzal chloride (together with benzyl chloride
Vapor pressure at and benzotrichloride) is produced exclusively by
45.5 ◦ C 0.6 kPa
75.0 ◦ C 0.8 kPa
side-chain chlorination of toluene. The preferred
82.0 ◦ C 1.3 kPa chlorination processes are those previously de-
89.5 ◦ C 1.9 kPa scribed under benzyl chloride. The pure com-
105 ◦ C 4.0 kPa
pound is isolated by fractional distillation.
118 ◦ C 8.0 kPa
205.2 ◦ C 101.3 kPa Environmental Protection. Benzal chlo-
n20
D 1.5503
Surface tension σ at 20 ◦ C 40.1 mN/m
ride is regarded as a toxic chlorinated hydro-
at 100 ◦ C 31.1 mN/m carbon. Neither a TLV nor – in the Federal Re-
Dynamic viscosity η at 20 ◦ C 2.104 mPa s public of Germany – an MAK value has been
at 50 ◦ C 1.327 mPa s established for benzal chloride. As a compound
Specific heat at 25 ◦ C 222 J mol−1 K−1
(1377 J kg−1 K−1 )
carrying a reasonable potential of being car-
Heat of vaporization at 72 ◦ C 50.4 kJ/mol cinogenic, benzal chloride has been allocated to
(313.2 kJ/kg) Category III B of the MAK list. For this rea-
Flash point 93 ◦ C
son, stringent requirements must be met in its
Ignition point 525 ◦ C
Heat of combustion at constant handling, including the sealing of production
pressure 3.852×103 kJ/mol equipment and the ventilation of workrooms.
(23.923×103 kJ/kg) Regular medical inspection is required of per-
Explosive limits in air, lower 1.1 vol%
upper 11 vol%
sonnel coming in contact with the compound
Specific conductivity at 20 ◦ C 3.4×10−9 S/cm (chlorinated hydrocarbon and benzene homo-
logues).
Benzal chloride is freely soluble in alcohol,
ether, chloroform, and carbon tetrachloride, but
only slightly soluble in water (0.05 g/L at 5 ◦ C; 9.2.4. Quality Specifications and Analysis
0.25 g/L at 39 ◦ C). The solubility of chlorine in
100 g of benzal chloride is The normal commercial form is “benzal chlo-
ride, pure,” with an assay of > 99 %. The main
6.2 g at 30 ◦ C impurities are benzyl chloride and benzotrichlo-
4.3 g at 50 ◦ C ride.
1.5 g at 100 ◦ C [971] Benzal chloride is analyzed by the same
Several azeotropic mixtures are known of methods described for benzyl chloride (see p.
which benzal chloride is a component [970]. 359).

9.2.2. Chemical Properties 9.2.5. Storage and Transportation

The action of chlorinating agents converts ben- Stabilization like that employed with benzyl
zal chloride into benzotrichloride. In the pres- chloride is not absolutely necessary. It may be
ence of Lewis acids, the aromatic ring is chlori- advisable under some conditions, however, such
nated, with isomeric chlorobenzal chlorides be- as storage or transportation in the tropics. Com-
ing formed. pounds used to stabilize benzyl chloride are also
Hydrolysis under acid or alkaline conditions effective for stabilizing benzal chloride. Enam-
gives benzaldehyde. eled steel, lead, and stainless steel are suitable
Benzal chloride polymerizes in the presence materials for the construction of storage tanks.
of AlCl3 , FeCl3 , and similar compounds. Stainless steel tanks or drums coated with baked
enamel are suitable for transportation.
 Chlorinated Hydrocarbons 139
Mr 195.48
Legal Requirements. Since benzal chloride bp at 101.3 kPa 220.7 ◦ C
is a toxic chlorinated hydrocarbon, it is subject mp − 4.5 ◦ C
to the following official regulations:  at 15 ◦ C 1.3777 g/cm3
20 ◦ C 1.3734 g/cm3
GGVS/ADR Class 6.1; 17 b 30 ◦ C 1.3624 g/cm3
GGVE/RID Class 6.1; 17 b 50 ◦ C 1.342 g/cm3
GGV-See/IMDG Code Class 6.1; Vapor pressure at
85 ◦ C 1.1 kPa
UN no. 1886 95 ◦ C 1.9 kPa
Label no. 6 (poison) must be displayed. 111 ◦ C 3.1 kPa
121.5 ◦ C 5.2 kPa
Benzal chloride is subject to the Arbeitsstoff- 147 ◦ C 13.3 kPa
Verordnung of the Federal Republic of Germany 220.7 ◦ C 101.3 kPa
and to the corresponding EC Directive (EC com- n0D 1.5677
pound no. 602–058–00–8). n20
D 1.5581
Dynamic viscosity η at 20 ◦ C 2.40 mPa s
50 ◦ C 1.517 mPa s
Surface tension σ at 20 ◦ C 39.3 mN/m
9.2.6. Uses 100 ◦ C 30.6 mN/m
Specific heat at 25 ◦ C 235 J mol−1 K−1
Benzal chloride is used almost exclusively to (1206 kJ kg−1 K−1 )
produce benzaldehyde. 52 ◦ C 248 J mol−1 K−1
(1269 kJ kg−1 K−1 )
Benzal chloride is hydrolyzed in the presence
75 ◦ C 249 J mol−1 K−1
of water at a temperature above 100 ◦ C by al- (1273 kJ kg−1 K−1 )
kaline [1028] or acidic [1029 – 1032] agents. 100 ◦ C 250 J mol−1 K−1
Friedel-Crafts catalysts or amines [1033] are (1281 kJ kg−1 K−1 )
Heat of vaporization at 80 ◦ C 52 kJ/mol (266 kJ/kg)
recommended as catalysts. The latter are even at 130 ◦ C 47.5 kJ/mol (243 kJ/kg)
recommended for mixtures of benzyl chloride Flash point 108 ◦ C
and benzal chloride, whereby it is claimed that Ignition temperature 420 ◦ C
the benzyl chloride remains unchanged and that Specific conductivity at 20 ◦ C 6×10−9 S/cm
Heat of combustion at constant
only benzaldehyde is formed. This process is pressure 3684 kJ/mol
unlikely to be of commercial interest; because (18878 kJ/kg)
benzyl chloride and benzaldehyde have almost Explosive limits in air, lower 2.1 vol%
identical boiling points their separation by frac- upper 6.5 vol%

tional distillation would be very costly.

Benzotrichloride is freely soluble in alcohol,
ether, and chloroform. It is only slightly solu-
9.3. Benzotrichloride ble in water (0.05 g/L at 5 ◦ C, 0.25 g/L at 39
◦
C). The solubility of chlorine in 100 g of ben-
Exhaustive chlorination of the side-chain of zotrichloride is
toluene leads to benzotrichloride (trichlorome-
thyl benzene, α,α,α-trichlorotoluene, phenyl 5.1 g at 30 ◦ C
chloroform) [98-07-7]. The compound was first 3.4 g at 50 ◦ C
synthesized in 1858 by L. Schischkoff and A. 1.3 g at 100 ◦ C [971]
Rosing, using the reaction of PCl5 with benzoyl
Several azeotropic mixtures are known in
chloride. Benzotrichloride is now produced on which benzotrichloride is a component [970].
a large scale, since it serves as an important in-
termediate in the preparation of acid chlorides
(benzoyl chloride), dyes, herbicides, pesticides, 9.3.2. Chemical Properties
and other products.
Acid or alkaline hydrolysis of benzotrichloride
9.3.1. Physical Properties leads to benzoic acid. Partial hydrolysis gives
benzoyl chloride.
Benzotrichloride is a colorless liquid with a pun-
gent odor and is irritating to the eyes and mucous
membranes. It fumes in moist air.
140 Chlorinated Hydrocarbons

Its reaction with carboxylic acids results in give a waste gas free of chlorine, i.e., consisting
the corresponding acid chlorides and benzoyl of pure hydrogen chloride.
chloride. Kinetic investigations of the formation of
Condensation of benzotrichloride with ben- benzotrichloride have been published on several
zene in the presence of FeCl3 , AlCl3 , or ZnCl2 occasions [975, 999]. The yield and speed of the
leads to diphenyl- and triphenylmethane. reaction are raised not only by exclusion of O2
All three chlorine atoms can be replaced by [999], but also by the use of high Reynolds num-
fluorine when benzotrichloride is treated with bers (35 000 – 160 000) [1036] or catalytic quan-
hydrofluoric acid or fluorides [1034, 1035]. tities of ammonium chloride [1037]. The chlori-
Ortho-esters of benzoic acid can be prepared nation of methylbenzenes using the correspond-
by reacting benzotrichloride with anhydrous al- ing trichlorides as solvents is claimed to give a
cohols. high yield of very pure products [1038]. Accord-
ing to [1039] the use of bromine in the produc-
tion of benzotrichlorides increases the reaction
9.3.3. Production rate and the yield. One additional manufactur-
ing process for benzotrichloride is based on the
Exhaustive chlorination of the side-chain of chlorination of dibenzyl ether [1040], which is
toluene can be carried out in a manner analogous formed as a byproduct in the conversion of ben-
to that described under benzyl chloride. Photo- zyl chloride to benzyl alcohol. This particular
chemical chlorination in particular is widely ap- chlorination leads to a mixture of benzotrichlo-
plied for benzotrichloride production. Neverthe- ride and benzoyl chloride, which can be worked
less, in order to prevent excessive chlorination in the usual way to give pure benzoyl chloride.
and the appearance of ring-chlorinated materi- Indirectly, this serves as a way to improve the
als, it is advisable, in continuous processes, to economics of benzyl alcohol production.
distribute the reaction over a cascade of six to ten Environmental Protection. Benzotrichlo-
reactors. Doing so makes it possible to introduce ride is regarded as toxic. Neither a TLV nor –
the chlorine at precisely the level appropriate to in the Federal Republic of Germany – an MAK
the progress of the reaction and results in ben- value has been established for it. Benzotrichlo-
zotrichloride containing only a small amount of ride has been allocated to Category III B of the
benzal chloride [980, 981]. MAK list (this category comprises substances
A continuously operated plant for the produc- reasonably suspected of having carcinogenic po-
tion of benzotrichloride is illustrated in Figure tential). Therefore, special requirements must be
35 [981]. Fresh toluene flows into the first of a met concerning the sealing of production equip-
cascade of ten reactors. For reasons related to the ment and the ventilation of workrooms. As with
removal of waste gases, the reactors can be re- other chlorinated hydrocarbons and homologues
garded as being divided into three groups. Reac- of benzene, regular medical inspection of per-
tors 2 – 10 receive carefully metered amounts of sonnel is necessary.
chlorine. The off-gas from reactors 5 – 10 is rich
in chlorine because the material in these reactors
has already reached a high degree of chlorina- 9.3.4. Quality Specifications and Analysis
tion; therefore, this gas is recycled to reactors 2
and 3. Benzotrichloride is sold in two quality grades,
Similarly, the off-gas from reactors 2 to 4 is known as “benzotrichloride, technical” and
introduced into reactor 1, which contains the “benzotrichloride, pure”. The corresponding as-
highest proportion of toluene, so that the final says are > 95 % and > 98 % respectively. Im-
traces of chlorine are removed. The off-gas from purities include chlorotoluenes, benzyl chlo-
reactor 1 is thus free of chlorine. ride, chlorobenzyl chlorides, benzal chloride,
With the condition that the chlorine and chlorobenzal chlorides, and chlorobenzotrichlo-
toluene are accurately metered, this technique rides.
is claimed to give practically complete conver- Gas chromatography is the preferred method
sion of toluene to benzotrichloride, and also to of analysis. The procedure is analogous to that
used for benzyl chloride (see Section 9.1.4).
 Chlorinated Hydrocarbons 141

Figure 35. Continuous process for the manufacture of benzotrichloride [981] a1 – a10 ) Reactor cascade; b) Off-gas group 2,
chlorine-containing; c) Off-gas group 3, high chlorine content; d) Off-gas group 1, chlorine-free

9.3.5. Storage and Transportation the production of pesticides (through transfor-

mation into benzotrifluoride), ultraviolet stabi-
Stabilization is unnecessary for storage pur- lizers, and dyes.
poses. Enameled, lead-lined, and stainless steel
vessels are suitable for storage. Stainless steel
tanks and drums coated with baked enamel are 9.4. Side-Chain Chlorinated Xylenes
suitable for transportation.
Legal Requirements. Being a corrosive The side-chain-chlorinated xylenes play a less
chlorinated hydrocarbon, benzotrichloride is important role in the chemical industry than
subject to various regulations: the corresponding toluene derivatives. In ad-
dition, substantial interest has been shown
ADR/GGVS: Class 8, no. 66 b in only a few of the altogether 27 theoreti-
RID/GGVE: Class 8, no. 66 b cally possible chloroxylenes, particularly the α-
GGV-See/IMDG Code: Class 6.1, monochloro, α,α -dichloro, and most notably,
UN no. 2226 the α,α,α,α ,α ,α -hexachloro derivatives.
Label 8 (corrosive) must be displayed. Ben-
zotrichloride is additionally subject to the
Verordnung über gefährliche Arbeitsstoffe of the 9.4.1. Physical and Chemical Properties
Federal Republic of Germany and to the corre-
sponding directive of the European Community A selection of chlorinated xylenes is listed in Ta-
(EC compound no. 602–038–00–9). ble 56, together with certain physical data. The
side-chain chlorinated xylenes are very similar
in their chemical properties to the corresponding
9.3.6. Uses toluenes. They can therefore be made to undergo
the same kinds of reactions as the latter. Thus,
Benzotrichloride is used mainly to produce ben- the hexachloroxylenes (m-, p-) are important in
zoyl chloride, for which purpose it is either par- the production of carboxylic acid chlorides, and
tially hydrolyzed with water or else reacted with the α,α -dichloroxylenes serve as sources of var-
benzoic acid. It is also of some significance in ious bifunctional xylenes.
142 Chlorinated Hydrocarbons

Table 56. Physical data of chlorinated xylenes

9.4.2. Production 1042] and a combination of boron trifluoride

and ammonium chloride [1043]. Removal of air,
The proven methods for the chlorination of moisture, and traces of metals by thorough pu-
toluene are basically suitable for the chlori- rification of the chlorine and xylene feedstocks
nation of xylene as well. Additives similar to is also recommended [1044].
those used in the chlorination of toluene are Chlorination in solvents, e.g., in carbon tetra-
recommended to prevent nuclear chlorination chloride [988, 992, 1000, 1045] or hexachlorox-
[985 – 996]. Specialized additives include phos- ylene [1038, 1046], has been described as partic-
phoric acid esters together with sorbitol [1041, ularly advantageous. Since in theory, there are up
 Chlorinated Hydrocarbons 143

to nine chlorinated derivatives of each of the xy- cial significance, and it is these whose manu-
lene isomers, the course of the chlorination pro- facture has been investigated most thoroughly
cess is understandably very complex (Fig. 36) [992 – 994, 1002, 1006, 1038, 1044, 1046, 1049,
[1047]. 1061].
It is worth noting that in the case of o-xylene,
the exhaustive chlorination of the side-chains
leads only as far as α,α,α,α ,α -pentachloro-
o-xylene. Steric hindrance evidently makes the
hexachloro stage inaccessible. The correspond-
ing hexafluoro derivative is known, however.

9.4.3. Storage and Transportation

Individual chloroxylenes are not subject to spe-
cial regulations. The relevant regulations con-
cerning the handling of chlorinated hydrocar-
bons should be appropriately applied, however.
The same is true for transportation, where, de-
Figure 36. Progression of p-xylene chlorination [1047] pending on the properties of the compound con-
a) p-Xylene; b) α-Chloro-p-xylene; c) α,α -Dichloro-
p-xylene; d) α,α-Dichloro-p-xylene; e) α,α,α -Tri- cerned, allocation to existing hazard categories
chloro-p-xylene; f) α,α,α ,α -Tetrachloro-p-xylene; (assimilation) is necessary.
g) α,α,α,α ,α -Pentachloro-p-xylene; h) α,α,α,α ,α ,α -
Hexachloro-p-xylene
9.4.4. Uses
The corresponding kinetics have been inves-
In terms of output quantity the m- and p-
tigated in detail [1047 – 1052].
hexachloroxylenes are the most important side-
Thus, in the manufacture of α-chloroxylene,
chain chlorinated xylenes. These find applica-
the chlorination must be discontinued suffi-
tion particularly in the production of isoph-
ciently early to ensure that only a small amount
thaloyl chloride and terephthaloyl chloride, im-
of dichloride is formed. The product is purified
portant starting materials for polyester synthesis.
by distillation [1053].
The α,α -dichloroxylenes have been used to-
p-α,α -Dichloroxylene can be produced
gether with diamines or glycols, bisphenols, or
analogously, whereby any xylene and α-
even amino alcohols in the production of poly-
chloroxylene recovered at the distillation stage
mers.
can be returned to the chlorination reactor
[1054].
An alternative route to chloroxylenes in- 9.5. Ring-Chlorinated Derivatives
volves the chloromethylation of toluene or ben-
zyl chloride [1055, 1056]. This approach has the In comparison with the toluene and xylene
disadvantage, however, that it gives an isomer derivatives that are chlorinated exclusively in the
mixture, similar to that presumably formed by side-chain, those that are also chlorinated on the
a double chloromethylation of benzene [1057]. ring have achieved considerably less industrial
This fact, together with the complexity entailed importance.
in a separation, makes its large-scale use less Normally, such products are made from
attractive. Isolation of various pure chlorox- toluenes or xylenes whose rings already bear
ylenes is also possible (in some cases with high chlorine. These are then subjected to further
yields), not only by distillation, but also by di- chlorination under the conditions described
rect crystallization from the reaction mixture above, thereby being converted into the desired
[1058 – 1060]. derivatives. If products are desired in which all
The bis(trichloromethyl)benzenes are the ring positions are chlorinated, it is often possi-
chlorinated xylenes with the most commer- ble to chlorinate both the ring and the side-chains
without purification of intermediates [1062].
144 Chlorinated Hydrocarbons
Table 57. Physical data of chlorinated toluenes
 Chlorinated Hydrocarbons 145

The uses of the ring-chlorinated compounds monomers have been incorrectly grouped with
correspond to those of the parent series. A selec- persistent chlorinated pesticides and other non-
tion of such ring-chlorinated derivatives is com- volatile chlorinated materials.
piled in Table 57. While the substances discussed in this sec-
tion show some common toxicological, chem-
ical, and physical properties, exceptions are so
9.6. Economic Aspects common that categorization must be avoided. It
is, therefore, imperative to examine the toxicity
Production capacities for the toluene derivatives of each specific substance. Fortunately, the most
discussed above were estimated to have been as common chlorinated solvents have been exhaus-
follows in 1984 (Table 58): tively studied. However, new toxicological data
are being generated and the current literature and
Table 58. Capacities for chlorinated toluenes, in t/a regulations should always be consulted.
Reviews may quickly become incomplete,
Europe World but a few are listed in the references
Benzyl chloride 80 000 160 000 [1063 – 1065]. They will be most valuable for
Benzal chloride 15 000 30 000 information about effects on the skin or eyes, as
Benzotrichloride 30 000 60 000
well as effects of single or short, repeated ex-
posures by ingestion or inhalation. Information
It is not really possible to determine the ex- on carcinogenesis, mutagenesis, and birth ef-
tent of utilization of these capacities, since many fects are presented, but these are active research
companies produce the products for their further areas and current literature must be consulted.
own use. It is likely, however, that ca. 60 % of The manufacturer or supplier of a substance is
the estimated capacity was utilized in 1984. responsible for acquiring and distributing such
The 1984 price of benzyl chloride was ca. information, and most manufacturers excercise
0.90 $/kg; that of benzotrichloride was ca. 1.30 that responsibility. Table 59 shows some data
$/kg. on the acute toxicity of the aliphatic chlorinated
hydrocarbons.
Abbreviations and Definitions.Certain terms,
10. Toxicology and Occupational names, and organizations appear in this section.
Most of the abbreviations are explained in the
Health front matter, others are defined in the text. For
detailed information on general toxicology, see
10.1. Aliphatic Chlorinated the corresponding articles in the B series.
Hydrocarbons Carcinogenesis, Mutagenesis, and Teratoge-
nesis.In the current regulatory climate, muta-
In this Section, chlorinated methanes, ethanes, genic changes, reproductive effects, and partic-
ethylenes, propanes, and propenes of major ularly cancer are of prime concern. This is ap-
commercial importance are discussed. A few propriate, but excessive concern about cancer
other substances found as minor products, re- has distracted attention from other concerns that
search chemicals, contaminants, or unwanted may be of equal or more importance.
products are included when data are extensive Many, if not most, chlorinated substances can
or if they present an unusual or high toxicity. be made to produce an increase of tumors in cer-
The diversity of the toxic properties of chlori- tain laboratory animals, particularly in organs in
nated hydrocarbons is often inadequately appre- which toxicity is exhibited and high tumor rates
ciated, despite decades of use and studies prov- exist normally, e.g., in the livers of mice. How-
ing great differences. They have all been mistak- ever, no chlorinated hydrocarbon except vinyl
enly categorized generically as hepatotoxic, al- chloride has yet been shown to have increased
though large differences in their ability to injure cancer in human populations. Many epidemio-
the liver exist. Most of the compounds discussed logical studies lack power due to small popula-
are rather volatile and have a low potential for tions and short duration. However, a number of
bioconcentration; nevertheless, the solvents and studies are of adequate size, duration, and power
146 Chlorinated Hydrocarbons

to demonstrate that cancer has not increased in vent cancer. This nongenotoxic mechanism of
the degree predicted from the studies in mice. induction is consistent with current human ex-
Because of this inconsistency and a variety of perience and other data related to most of the
other data, there has been considerable scientific chlorinated hydrocarbons discussed herein ex-
discussion about interpreting animal studies in cept vinyl chloride.
regard to human risk; see also [1066]. Vinyl chloride appears to operate by a genetic
mechanism and, although humans are much less
Table 59. Single-dose oral toxicity of common chlorinated C1 , C2 ,
responsive than rodents, the difference is quan-
C3 , and C4 aliphatic hydrocarbons [1063] titative and appears related to a lower rate of
metabolism in humans. This indicates that ex-
LD50 (oral, rats; Probably
unless other nature posure to all of these materials must be care-
species specified), mg/kg of deatha fully controlled to avoid exposures that result
Chloromethane (methyl chloride) gas – in stress or injury. Close adherence to the oc-
Dichloromethane (methylene 2 000 A cupational exposure limits (MAK or TLV) is
chloride) recommended. Furthermore, good industrial hy-
Trichloromethane (chloroform) 2 000 A, LK
Tetrachloromethane (carbon 3 000 A, LK
giene practice requires that exposures to any sub-
tetrachloride) stance be kept as low as reasonable and that care-
Monochloroethane (ethyl chloride) gas – less operation should be prohibited regardless of
1,1-Dichloroethane (ethylidene >2 000b –
dichloride)
whether the TLV or MAK is exceeded.
1,2-Dichloroethane (ethylene 700 LK Reproductive effects do not appear to be of
dichloride) concern with any of the substances discussed in
1,1,1-Trichloroethane (methyl 10 000 – 12 000 A
chloroform)
this Section, provided exposures are controlled
1,1,2-Trichloroethane (vinyl 100 – 200 LK to prevent injury to other organ systems of the
trichloride) mother during gestation. In other words, the re-
1,1,2,2-Tetrachloroethane (acetylene ca. 300 (dogs) –
tetrachloride)
productive system appears less sensitive than
Pentachloroethane 1 750 (dogs) – other systems [1067]. Likewise, mutagenic ef-
Hexachloroethane 6 000 – fects appear unlikely, based on the weight of the
Monochloroethylene (vinyl chloride) gas – evidence from in vivo and in vitro studies.
1,1-Dichloroethylene (vinylidene 1 500 LK
chloride) Occupational Exposure Limits. Table 60 lists
1,2-Dichloroethylene (cis and trans) 1 000 – 2000 A the 1985 TLV’s and MAK’s published by the
Trichloroethylene 4 900 A American Conference of Governmental Indus-
Tetrachloroethylene 2 000 A
(perchloroethylene) trial Hygienists (ACGIH) and the Deutsche
Dichloroacetylene – – Forschungsgemeinschaft (DFG), respectively
2-Propyl chloride (isopropyl >3 000 (guinea pigs) A [1068, 1069]. The definitions applied by these
chloride)
1,2-Dichloropropane (propylene 2 000 A
organizations must be understood in order to ap-
dichloride) ply the values properly. For example, both orga-
3-Chloropropene (allyl chloride) 450 – 700 LK nizations recommend that skin contact be lim-
1,3-Dichloropropene 500 – 700 LK
2-Chloro-1,3-butadiene 250 LK
ited if skin absorption is thought to influence the
(chloroprene) TLV or the significantly MAK. The reader must
Hexachlorobutadiene 200 – 350 LK always consult the latest values published an-
a
A = Anesthesia, LK = Liver and kidney injury; nually by these organizations and, further, must
b
Unpublished data, The Dow Chemical Company, Midland, not assume that they are the legal standard. It
Michigan, USA. is strongly recommended that supporting docu-
mentations be consulted when using the TLV’s
and MAK’s.
According to current scientific thought, cer-
tain substances, including the chlorinated hydro-
carbons, increase cancer in certain organs (e.g., 10.1.1. Chloromethanes
livers of mice) as a result of repeated stress Monochloromethane. Chloromethane [74-
and injury with subsequent increased cellular 87-3], methyl chloride, is an odorless gas and,
regeneration. Thus, preventing exposures that except for freezing the skin or eyes due to evap-
cause cellular changes (injury) should also pre- oration, inhalation is the only significant route
 Chlorinated Hydrocarbons 147
Table 60. Summary of TLV’s and MAK’s for common chlorinated C1 , C2 , C3 , and C4 aliphatic hydrocarbons

1985 ACGIH TLV 2001 DFG MAK

ppm mg/m3 ppm mg/m3

Chloromethane [74–87–3] 50 105 50 (3B) 100

Dichloromethane [75–09–2] 100 350 -(3A) –(3A)
Trichloromethane [67–66–3] 10 (A2) 50 (A2) 0,5 (4) 2,5
Tetrachloromethane (skin) [56–23–5] 5 (A2) 30 (A2) 0,5 (4) 3,2

Monochloroethane [75–00–3] 1000 2600 – (3B) – (3B)

1,1-Dichloroethane [75–34–3] 200 810 100 410
1,2-Dichloroethane [107–06–2] 10 40 – (2) –
1,1,1-Trichloroethane [71–55–6] 350 1900 200 1100
1,1,2-Trichloroethane (skin) [79–00–5] 10 45 10 (3B) 55 (3B)
1,1,2,2-Tetrachloroethane (skin) [79–34–5] 1 7 1 (3 B) 7 (3 B)
Pentachloroethane [76–01–7] – – 5 42
Hexachloroethane [67–72–1] 10 100 1 9,8

Monochloroethylene (vinyl chloride) 5 (A1a) 10 (A1a) 3 (2) (TRK) 8 (5) (TRK)

[75–01–4]
(1) (1)
1,1-Dichloroethylene [75–35–4] 5 20 2 (3 B) 8 (3 B)
1,2-Dichloroethylene (cis and trans) 200 790 200 800
[540–59–0]
Trichloroethylene [79–01–6] 50 270 – (1) – (1)
Tetrachloroethylene [127–18–4] 50 335 – (3B) – (3B)

Dichloroacetylene [7572–29–4] C 0.1 C 0.4 – (2) – (2)

1,2-Dichloropropane [78–87–5] 75 350 – (3B) – (3B)

3-Chloropropene (allyl chloride) [107–05–1] 1 3 – (3B) – (3B)

1,3-Dichloropropene (skin) (cis and trans, 1 5 – (2) – (2)
[542–75–6] and [126–99–8])

2-Chloro-1,3-butadiene (chloroprene) (skin) 10 36 – (2) –

Hexachlorobutadiene (skin) [87–68–3] 0.02 (A2) 0.24 (A2) – (3B) – (3B)

A2 = 3 B = Suspected carcinogen; 2 = Carcinogen in animal experiments; A1 = Human carcinogen without gentoxic effects; C = Ceiling;
TRK = Technical Guiding Concentration 3 ppm in existing facilities, 2 ppm in new facilities; skin = This designation is intended to suggest
appropriate measures for the prevention of cutaneous absorption so that the threshold limit is not invalidated.

of exposure. It acts mainly on the central ner- Dichloromethane. Dichloromethane [75-

vous system with well documented cases of ex- 09-2], methylene chloride, is the least toxic of
cessive human exposure, leading to injury and the chlorinated methanes. It is moderate in tox-
even death [1063]. The symptoms of overex- icity by ingestion, but the liquid is quite painful
posure are similar to inebriation with alcohol to the eyes and skin, particularly if confined
(a shuffling gait, incoordination, disorientation, on the skin [1063 – 1065]. Absorption through
and change in personality), but last much longer, the skin is probably of minor consequence if
possibly permanent in severe exposures. Ac- exposure is controlled to avoid irritation.
cording to experimental results, excessive ex- Inhalation is the major route of toxic expo-
posure to methyl chloride was carcinogenic in sure. The principal effects of exposure to high
mice and also affected the testes of male rats and concentrations (greater than 1000 ppm) are anes-
fetuses of pregnant female rats [1070]. It is mu- thesia and incoordination. Exposure to methy-
tagenic in certain in vitro test systems. Available lene chloride results in the formation of carboxy-
references indicate that methyl chloride may in- hemoglobin (COHb) caused by its metabolism
crease the rate of kidney tumors in mice in con- to carbon monoxide. This COHb is as toxic as
junction with repeated injury to this organ. The that derived from carbon monoxide itself. How-
TLV and the MAK (1985) are both 50 ppm (105 ever, at acceptable levels of exposure to methy-
mg/m3 ).
148 Chlorinated Hydrocarbons

lene chloride, any probable adverse effects of Tetrachloromethane. Tetrachloromethane

COHb will be limited to persons with pro- [56-23-5], carbon tetrachloride, was once rec-
nounced cardiovascular or respiratory problems. ommended as a “safety solvent.” Misuse and its
Other possible toxic effects of carbon monoxide rather high liver toxicity, as well as the ready
itself would not be expected. availability of alternate safe solvents, have elim-
Methylene chloride is not teratogenic in ani- inated its application as a solvent. Single expo-
mals [1067] and has only limited mutagenic ac- sures are not markedly injurious to the eyes and
tivity in Salmonella bacteria. It does not appear skin or toxic when small quantities are ingested.
to be genotoxic in other species. Available re- However, repeated exposure must be carefully
ports of lifetime studies at high concentrations controlled to avoid systemic toxicity, particu-
have produced inconsistent results in hamsters, larly to the liver and kidneys [1063 – 1065]. In
rats, and mice. No tumors, benign or malig- humans, injury to the kidney appears to be the
nant, were increased in hamsters; rats developed principal cause of death.
only a dose related increase in commonly oc- Inhalation can produce anesthesia at high
curring nonmalignant mammary tumors; white concentrations, but transient liver as well as
mice, both sexes, had a large increase in cancers kidney injury result at much lower concentra-
of the livers and lungs. Available epidemiolog- tions than those required to cause incoordina-
ical data do not indicate an increase in cancer tion. There appears to be individual susceptibil-
in humans; they do indicate that the current oc- ity to carbon tetrachloride, with some humans
cupational standards are protective of employee becoming nauseated at concentrations that oth-
health [1068, 1069]. ers willingly tolerate. Ingestion of alcohol is re-
Trichloromethane. Trichloromethane [67- ported to enhance the toxicity of carbon tetra-
66-3], chloroform, is only moderately toxic from chloride. Such responses should not occur, how-
single exposure, but repeated exposure can result ever, if exposures are properly controlled to the
in rather severe effects [1063 – 1065]. Its use as recommended occupational standards.
a surgical anesthetic has become obsolete, pri- Carbon tetrachloride is not teratogenic in an-
marily because of delayed liver toxicity and the imals [1067] nor mutagenic in common test sys-
development of anesthetics with a greater mar- tems, but does increase liver tumors in mice,
gin of safety. probably as a result of repeated injury to that
Ingestion is not likely to be a problem un- organ. Therefore, it is very important that hu-
less large quantities are swallowed accidentally man exposure be carefully controlled to prevent
or deliberately. Chloroform has a definite solvent liver injury.
action on the skin and eyes and may be absorbed
if exposure is excessive or repeated. Its recog-
nized high chronic toxicity requires procedures 10.1.2. Chlorinated C2 Hydrocarbons
and practices to control ingestion, skin, and eye Monochloroethane. Chloroethane [75-00-
contact, as well as inhalation exposure if liver 3], ethyl chloride, has limited use as an industrial
and kidney injury, the most likely consequence chemical and is most commonly recognized by
of excessive exposure, is to be prevented. its use as a local anesthetic that is sprayed on the
In animals, chloroform is fetotoxic (toxic to skin for minor medical procedures. There are
the fetus of a pregnant animal) but only weakly remarkably few published data on its toxicity,
teratogenic if at all [1067]. It does not appear to since there are very few people exposed in the
be mutagenic by common test procedures, but few uses in industry. It appears to be low in tox-
increases the tumor incidence in certain rats and icity by inhalation, the only likely route of toxic
mice. There is considerable evidence that the tu- exposure. Evaporation of large quantities could
mors in rat kidneys and mice livers are the result freeze the skin or eyes [1063 – 1065]. The Na-
of repeated injury to these organs and that lim- tional Toxicology Program (NTP) has a cancer
iting exposure to levels that do not cause organ bioassay underway, and while it appears to be
injury will also prevent cancer. It is, therefore, negative, complete results are not yet available.
very important that human exposure be carefully 1,1-Dichloroethane [75-34-3]. This flam-
controlled to prevent injury. mable substance has limited use and only limited
 Chlorinated Hydrocarbons 149

toxicological data are available. It appears to be der such conditions may attain 10 000 – 30 000
low in toxicity by all routes including oral, der- ppm or more. Death is due to anesthesia or pos-
mal, and inhalation. Animals tolerated repeated sible sensitization of the heart to endogenous
exposures 7 h/d for 9 months to either 500 or adrenalin. Recovery generally has been com-
1000 ppm with no adverse effect. plete and uneventful if the victim is removed
It was not teratogenic when inhaled by preg- from the exposure before death occurs.
nant rats. The doses fed by gavage in a carcino- Injury to the liver or other internal organs
genesis study of the National Cancer Institute is unlikely unless severe anesthetic effects have
(NCI) were so high that mortality was increased. been observed. It has been found to cause no
Although no tumor increases were reported, no teratogenic or reproductive effects in animals,
conclusions could be drawn concerning the in- and extensive study indicates that the vapors are
duction of cancer [1063 – 1065]. not carcinogenic in rats and mice. It is metabo-
1,2-Dichloroethane. 1,2-Dichloroethane lized only to a very slight degree in animals and
[107-06-2], ethylene dichloride, EDC, is one humans. It is probably not mutagenic. Human
of the more toxic common chlorinated sub- experience has been favorable, as have epidemi-
stances [1063 – 1065]. It can cause depression ological studies on exposed workers. Exposure
of the central nervous system, mental confu- to high concentrations, particularly in confined
sion, dizziness, nausea, and vomiting. Liver, spaces, must not be permitted.
kidney, and adrenal injury may result from both 1,1,2-Trichloroethane [79-00-5]. This sub-
acute overexposure and repeated overexposure stance is relatively toxic and must not be con-
at levels significantly above the recommended fused with the 1,1,1-isomer discussed previously
occupational standards. It has moderate toxicity [1063 – 1065]. It has little use and human ex-
when swallowed and is often vomited. Skin and perience is limited. According to data from ani-
eye irritation generally occur only if the liquid mals, it can cause liver injury as a result of single
is confined. Absorption through the skin is not or repeated exposure. It has a typical solvent ef-
likely a problem from single contact, but re- fect on the skin and eyes; hence, exposure should
peated exposure should be avoided. Studies to be minimized. It apparently has not been studied
determine the carcinogenic properties have used for its teratogenic effects on animals; it is not mu-
excessive doses and produced mixed results. Ac- tagenic in common test systems, but it increases
cording to the available data, cancer in rodents the number of liver tumors in mice, probably as
is caused by repeated injury of the organs and a result of organ injury and repeated regenera-
is not likely to occur below occupational limits tion. Therefore, it is very important that human
[1071]. Particular precautions should be taken exposure be carefully controlled to prevent liver
to assure that skin and inhalation exposures are injury.
carefully and appropriately controlled. Other Chloroethanes. 1,1,2,2-tetrachloro-
1,1,1-Trichloroethane. 1,1,1-Trichloroethane ethane [79-34-5], pentachloroethane [76-01-7],
[71-55-6], methyl chloroform, has consistently and hexachloroethane [67-72-1] have limited
been shown to be among the least toxic chlo- industrial use, partially because of their rec-
rinated or nonchlorinated solvents from both ognized high toxicity on repeated exposure
acute and repeated exposure [1063 – 1065]. It [1063 – 1065]. Symmetrical tetrachloroethane,
has been shown repeatedly to have little effect CHCl2 CHCl2 , at one time was used as a solvent,
on the liver. It is low in oral toxicity, and has but liver injury was reported among overexposed
a typical solvent (defatting) action on the skin workers. It is fetotoxic in rats and increased the
and eyes; hence, liquid exposure should be min- tumor rate in the livers of mice. The results of
imized. Exposure to more than 1000 ppm of the study of the National Cancer Institute (NCI)
the vapors (significantly above the occupational on rats was inconclusive. There is limited evi-
standards) may cause incoordination with re- dence that it is mutagenic. Much less data are
sulting lack of judgment and possible accidents. available on the toxicity of pentachloroethane,
Misuse and carelessness have resulted in un- but it is assumed to be highly toxic.
necessary deaths, primarily while working in Older data on hexachloroethane indicate a
confined spaces. Exposure concentrations un- much higher toxicity than more recent data
150 Chlorinated Hydrocarbons

[1063]. This may be due to better purity of the roderma has been associated with cleaning auto-
new sample. The recent report indicates a low claves used for polymerization. Whether the dis-
to moderate oral toxicity, only slight skin and ease, called kettle cleaner’s disease, is related to
eye irritation, but a moderate to high toxicity vinyl chloride itself or to some other substance
from repeated inhalation. It was not markedly is not known. Likewise, other cancers alleged
hepatotoxic and, at 15 ppm, caused no injury in to be caused by vinyl chloride may or may not
dogs, rats, guinea pigs, and quail exposed 6 h/d, 5 be the result of vinyl chloride itself, since they
d/week for 6 weeks. Exposure to 48 ppm caused are not consistent throughout the industry and
minimal injury, primarily in the eyes and respi- appear to be found only in certain populations.
ratory tract of the animals. It was not teratogenic Careful controls to minimize exposures and
in rats or mutagenic in bacteria, but it increased adherence to regulatory requirements are essen-
the rate of liver tumors in mice. It caused no tial.
cancer in rats, but both rats and mice had evi- Vinylidene Chloride. Vinylidene chloride
dence of kidney injury. The purity of the sample [75-35-4], 1,1-dichloroethylene, is an anesthetic
needs to be verified, however, because contam- at high concentrations (several thousand ppm)
ination with such other substances as tetra- or [1063 – 1065]. Hepatotoxicity can result from
pentachloroethane may have caused the reported rather low exposures; therefore, low TLVs and
effect. MAK’s have been recommended. It has a solvent
All three of these chlorinated ethanes must be effect on the skin and eyes but its high volatility
handled to control exposure and possible liver probably precludes absorption through the skin
injury. in most situations. Exposure should be care-
Vinyl Chloride. Vinyl chloride [75-01-4] is fully controlled. The effect on the liver is quite
the only chlorinated hydrocarbon that unques- marked on repeated exposure of animals. Al-
tionably has caused cancer (angiosarcoma of the though not a teratogen, it does cause injury to
liver) in humans. As a result, there are numerous embryos and fetuses of exposed animals at lev-
regulations and laws with regard to its produc- els causing injury to the pregnant mothers. The
tion and use that are intended to minimize ex- metabolites of vinylidene chloride are at most
posure. These should effectively eliminate any weakly mutagenic in bacterial test systems, and
other toxic effects of vinyl chloride as well as tests in mammalian systems are negative. It is
the possibility of cancer. probably not carcinogenic based on the weight
Because vinyl chloride is a gas, ingestion is of evidence, for only one out of 14 tests has been
not likely in an industrial setting [1063 – 1065]. marginally positive. It is important that human
Skin and eye contact appear to be of concern exposure be carefully controlled to prevent liver
only from evaporative freezing. Even at ade- injury.
quate protection of the respiratory tract to pre- 1,2-Dichloroethylene. Most toxicological
vent inhalation, some vinyl chloride may be ab- testing has been on mixed isomers [1063]. It is
sorbed through the skin, but the total contribu- not clear from available data on the isomers how
tion seems to be slight, even at high concentra- they compare in toxicity. Most results indicate a
tions. moderate oral toxicity to rats. A typical solvent
When inhaled in high concentrations (10 effect on the skin and eyes is expected although
000 ppm), anesthetic effects can occur. At even data are not available to verify this conclusion.
higher concentrations, the effects increase and Exposure should be controlled.
deaths have been reported from massive expo- Most studies on animals indicate a rather low
sures. Odor provides little warning of excessive toxicity by inhalation, with little effect on the
exposure. liver. Anesthesia occurs at higher levels, but the
Many other effects have been alleged to occur data are inconsistent as to the actual levels re-
as a result of excessive exposure to vinyl chlo- quired.
ride, but only a few are clearly the direct result The effects of repeated exposure are not clear
of exposure. It is hepatotoxic, possibly muta- either. One reference reported no adverse effect
genic, and has caused angiosarcoma of the liver. on 7-h daily exposure for six months to 500 or
A condition known as acroosteolysis with scle- 1000 ppm, but a second reported rather marked
 Chlorinated Hydrocarbons 151

effects at 200 ppm after 14 weeks. No data were genic but much of the testing is suspect due to
found on teratogenesis or carcinogenesis, but impurities (stabilizers) present in the samples.
very limited data indicate no mutagenic effect. Trichloroethylene appears to increase the
Trichloroethylene [79-01-6]. There is a number of liver tumors in certain mice given
tremendous amount of literature on trichloro- massive doses by gavage and lung tumor in one
ethylene because of its use as a degreasing sol- strain of mice by inhalation, but it has gener-
vent and even more so of its use as an anesthetic ally been negative in rats and other rodent stud-
have resulted in considerable human exposure ies. The significance to human cancer is not
[1063 – 1065]. With such a vast literature, con- clear [1064]. Several rather small epidemiolog-
flicting conclusions are possible. The toxicity ical studies have failed to show an increase in
is generally considered low to moderate. Liver human liver cancer of exposed workers.
and kidney injury do not appear to be a common Tetrachloroethylene [127-18-4]. Although
response even after excessive exposures which it is not a potent anesthetic, depression of the
cause anesthesia. Trichloroethylene has a typi- central nervous system (incoordination) is the
cal solvent (defatting) action on the skin and eyes most common response to tetrachloroethylene
and exposure should be controlled. Absorption at concentrations above 200 ppm [1063 – 1065].
through the skin may occur but is not likely a Liver and kidney injury does not appear to be
significant source of exposure. When inhaled, it a common response even after excessive expo-
can have a pronounced anesthetic effect (depres- sure. It is moderate to low in oral toxicity, has
sion of the central nervous system), which may a solvent action on the skin and eyes, and is
become evident as incoordination at concentra- poorly absorbed through the skin. Exposure of
tions of 400 ppm or more. Visual disturbances, the skin and eyes should be carefully controlled.
mental confusion, fatigue, and sometimes nau- The odor begins to be objectionable at about 400
sea and vomiting are observed at higher levels. ppm for most people. When inhaled at high con-
The nausea is not nearly as marked as with car- centrations, it may cause nausea and gastroin-
bon tetrachloride or ethylene dichloride. Sen- testinal upset in addition to the anesthesia and
sitization of the heart to adrenalin may occur, incoordination. It is much weaker in producing
but it does not appear to be significant unless nausea than carbon tetrachloride and ethylene
markedly anesthetic concentrations are reached dichloride.
(several thousand ppm). Reports of human injury are uncommon de-
Deliberate sniffing has been a problem, al- spite its wide usage in dry cleaning and degreas-
though physical dependence does not appear to ing. Sensitization of the heart to adrenalin does
be involved. A peculiar vascular dilation of the not appear to be a likely consequence.
face, neck and trunk, known as “degreaser’s Tetrachloroethylene is not extensively me-
flush,” occasionally occurs when alcohol is con- tabolized and most of the absorbed dose is ex-
sumed during or following exposure. Although creted unchanged in the expired air. Analysis
upsetting, the flush does not appear to be serious. of metabolites in urine is therefore of even less
Urinary metabolites, trichloroacetic acid and value than with trichloroethylene.
trichloroethanol, are measured in several coun- Tetrachloroethylene is not teratogenic in
tries to monitor workers’ exposure, but this standard tests in animals; it does not appear
procedure has severe disadvantages. Urinary to be significantly mutagenic and increases tu-
metabolites are more related to chronic (total) mors in certain strains of mice. Like many of the
exposure than they are to acute (peak) exposure. chlorinated hydrocarbons, the significance of the
Thus, the worker may have excessive peak ex- mouse liver tumor to human cancer is question-
posures which could result in anesthesia, inco- able.
ordination and possible accidents, and yet their Dichloroacetylene [7572-29-4]. This sub-
urinary metabolites remain within accepted lim- stance is discussed only because it is a highly
its at the end of the day. toxic and pyrophoric substance formed by de-
Trichloroethylene has not shown teratogenic hydrochlorination of trichloroethylene [1063].
effects in animals. It possibly is weakly muta- This has occurred when trichloroethylene va-
pors (or the liquid) are passed over soda – lime
152 Chlorinated Hydrocarbons

or caustic soda. Much of the experience comes 10.1.4. Chlorobutadienes

from the use of Hopcalite in rebreathing anes- 2-Chloro-1,3-butadiene [126-99-8],
thesia machines or in closed environmental sys- chloroprene, is a rather toxic, highly flamma-
tems. Exposure to as little as 19 ppm is reported ble monomer used to produce synthetic rubber
to cause the death of half of the mice (LC50 ) [1063]. The toxicity of various samples appears
in a 4-h exposure. Repeated exposure caused to have been influenced by reaction products
kidney injury and muscular paralysis. Dichloro- because chloroprene reacts with oxygen to form
acetylene is reported to cause headache, nausea, peroxides. It also dimerizes. It must be handled
and nerve, liver, and kidney injury in humans or carefully to prevent these reactions. Liver injury
animals. is possible, as is hair loss. The hair loss ap-
pears to be caused by a reaction of chloroprene
10.1.3. Chloropropanes and Chloropropenes with the hair itself, since regrowth occurs when
2-Chloropropane [75-29-6], isopropyl exposure ceases. The vapors cause respiratory
chloride, has had little use or study [1063]. irritation, as well as pain and irritation in the
Its flammability has probably discouraged its eyes. The pure material did not cause teratogen-
use, although it appears to be of low toxicity ic effects. It is mutagenic in some bacterial test
in animals. When fed by gavage to rats, a dose systems. Early reports of cancer among work-
of 3 g/kg was survived. Ten repeated applica- ers have not been confirmed in more carefully
tions of the liquid on the skin of a rabbit was conducted studies, and animal studies have been
very slightly irritating if allowed to evaporate negative [1064].
and slightly more irritating if confined under a Hexachlorobutadiene [87-68-3] has been
bandage. Exposure of the skin and eyes should used as a pesticide, but it is a largely unwanted
be prevented. Data on the effects of inhalation byproduct made during chlorination of hydro-
appear to be limited. According to one study, carbons [1063]. It is highly toxic and, unlike the
repeated exposure of rats to 250 ppm caused no other substances discussed in this section, of low
effect, but 1000 ppm did. Another study claimed volatility. The literature on hexachlorobutadiene
no effect in rats, mice, rabbits, guinea pigs, and has been reviewed [1072], and a summary of the
monkeys exposed 7 h/d 5 d/week for 6 months data is found in reference [1063]. There were no
to 500 or 1000 ppm. Limited data suggest that references to human exposure. In animals, hex-
isopropyl chloride caused a mutagenic response achlorobutadiene has caused liver injury after
in bacteria, but no data were found on teratoge- single exposure and liver and kidney injury, as
nesis or carcinogenesis. well as kidney tumors, after repeated ingestion.
1,2-Dichloropropane [78-87-5], propylene The kidneys are the primary target organ on re-
dichloride, appears to be low to moderate in toxi- peated exposure.
city on single exposure, but moderately toxic on Precautions must be taken to minimize expo-
repeated exposure [1063 – 1065]. It has a sol- sure to hexachlorobutadiene by skin, ingestion,
vent effect (defatting action) on the eyes and and inhalation.
skin. Exposure should be prevented. Absorption
of the liquid through the skin may occur, par-
ticularly on repeated contact. When inhaled by 10.1.5. Ecotoxicology and Environmental
mice, respiratory injury rather than liver toxic- Degradation
ity appeared to be the primary cause of death Aquatic Toxicity. Most common aliphatic
following single exposure. There appears to be chlorinated hydrocarbons have been tested for
little recent data on the effect of repeated inhala- their acute toxicity by both static and flow-
tion by animals; hence, the recommended TLV through methods using vertebrates (fish) and
and MAK are based on old studies. invertebrates (water fleas). According to these
The National Toxicology Program (NTP) has studies the compounds tested were either non-
a carcinogenic study under way, but no report toxic or slightly toxic as defined by the EPA (Ta-
has been issued. No data were found in regard ble 61) [1076].
to teratogenic effects, but minimal data indicate
it may be mutagenic in bacterial test systems.
 Chlorinated Hydrocarbons 153
Table 61. Aquatic toxicity of aliphatic chlorinated hydrocarbons (LC50 , mg/L) [1073]

Fathead minnow Daphnia magna

96-h 96-h
static flow 48-h
through static

Dichloromethane 310 193 224

Trichloromethane 131* – 28.9
Tetrachloromethane 53.2*∗ 43.1 35.2
1,1,1-Trichloroethane 105 52.8 >530
Trichloroethylene 66.8 40.7 85.2
Tetrachloroethylene 21.4 18.4 17.7

* [1074]
∗∗
[1075]

Table 62. Tropospheric residence time of aliphatic chlorinated

Presence in Water. According to analyses hydrocarbons
carried out in Western Europe, typical concen-
trations of 1,1,1-trichloroethane, trichloroeth- Compound Time, a

ylene, and perchloroethylene in surface water Dichloromethane 0.23

range from 0.1 to 3 µg/L [1077]. Trace con- Trichloromethane 0.33
Tetrachloromethane > 30.0
centrations of the common chlorinated hydro- 1,1,1-Trichloroethane 2.7
carbons have been found in drinking water. Di- Trichloroethylene 0.01
chloromethane has not been detected in natural Tetrachloroethylene 0.18
waters, oceans, sediments, or fish [1078]. Tri-
chloromethane is often formed at sub-ppm lev- Atmospheric concentrations of chlorinated
els in the disinfection of drinking water because solvents are highly dependent on the site of mea-
chlorine reacts with natural humic substances. surement. In urban areas, the concentration of
The concentrations of common chlorinated sol- dichloromethane is 30 – 100×10−6 mL/m3 and
vents in drinking water are typically below 0.3 the concentrations of 1,1,1-trichloroethane, tri-
µg/L [1077]. chloroethylene, or perchloroethylene are 100 –
Presence and Degradation in Air. During 600 ×10−6 mL/m3 . In areas remote from indus-
their use the common aliphatic chlorinated hy- trial and populated regions, background concen-
drocarbons escape into the atmosphere [1079]. trations are typically in the range of a few ppt
Simple chlorinated hydrocarbons are destroyed (10−6 mL/m3 ), except for 1,1,1-trichloroethane
in the troposphere, primarily by reaction of their which has been reported to occur at 100 –200 ×
hydrogen atoms or double bonds with hydroxyl 10−6 mL/m3 [1081].
radicals (HO ·) that are naturally present in the Most of the traces of chlorinated hydrocar-
troposphere. However, carbon tetrachloride and bons found in the atmosphere appear to be of
some of the fluorochloroalkanes (CFC 11, CFC anthropogenic origin. For methyl chloride, how-
12, and CFC 113) resist significant attack by hy- ever, and possibly for some other halomethanes,
droxyl radicals; therefore, these materials have the largest source is natural. Thus, methyl chlo-
much longer half-lifes than other common chlo- ride results from forest fires, agricultural burn-
rinated solvents (Table 62) [1080]. The degra- ing, chemical reactions in seawater, and possibly
dation of most commercially used chlorinated from marine plants [1082].
hydrocarbons in the atmosphere leads to HCl,
chlorides, CO2 , and H2 O, which represent no
significant threat to the general environment.
154 Chlorinated Hydrocarbons

10.2. Chlorinated Aromatic zene has been shown to accumulate in animals

Hydrocarbons and humans [1087, 1088].
Hexachlorobenzene has been suggested to
10.2.1. Chlorinated Benzenes produce immunotoxic effects in experimental
animals, i.e., alterations of cell-mediated im-
Acute Toxicity. Table 63 shows the LD50 ’s of mune responses [1063].
chlorinated benzenes. According to these data, Effects in Humans. Monochlorobenzene
the acute oral toxicity of chlorinated benzenes produced unconsciousness, vascular paraly-
is low to moderate. Absorption through the skin sis, and heart failure in a child after acciden-
seems to be minimal, but most of the compounds tal oral uptake [1063]. o-Dichlorobenzene pro-
have some local irritant potency. In experimen- duced depression in conditioned reflex activity,
tal animals, most chlorinated benzenes induce demonstrating a cerebral – cortical effect. Ery-
microsomal liver enzymes and cause porphyria, thropoiesis was significantly depressed. Symp-
hypertrophy, and centrolobular necrosis of the toms of intoxication include headache, nausea,
liver. The chlorinated benzenes can induce kid- throat irritation, and stinging of the eyes. Skin
ney damage, changes in mucous membranes, irritation is also reported [1064].
and irritation of the upper respiratory tract, de- No data are available on the effects of tri-
pending on the route and time of administration chlorobenzenes in humans. Only minimal eye
and on the dose applied. In addition, mono-, di-, and throat irritation at 3 – 5 ppm in certain peo-
and trichlorobenzenes are known to act as cen- ple are reported [1064]. An outbreak of cutanea
tral nervous depressants, causing anesthesia and tarda porphyria in Turkey in 1955 was attributed
narcosis at higher doses [1063, 1064]. to the uptake of grain treated with hexachloro-
benzene as fungicide [1063].
Table 63. Oral LD50 s of chlorobenzenes [1083] Regulations. The following occupational
Compound LD50 (rat, oral),
exposure limits have been established (MAK
mg/kg 2001, TLV 1985):
Monochlorobenzene 2 910
o-Dichlorobenzene 500 Monochlorobenzene: MAK 10 ppm TLV 75 ppm
p-Dichlorobenzene 500 o-Dichlorobenzene: MAK 10 ppm TLV 50 ppm
1,2,4-Trichlorobenzene 756 p-Dichlorobenzene: Carcinogen in TLV 75 ppm
animal experiments
1,2,4,5-Tetrachlorobenzene 1 500
1,2,4-Trichlorobenzene: Suspected
Pentachlorobenzene 1 080
carcinogen
Hexachlorobenzene 10 000

Chronic Effects. Hexachlorobenzene pro-

10.2.2. Chlorotoluenes
duced tumors in studies with mice and ham-
sters [1063]. There is no evidence for the car- Little is known about the toxicity of chlori-
cinogenicity of the other chlorobenzenes. None nated toluenes. The toxicity of o-chlorotoluene
of the compounds showed mutagenic activity is considered to be relatively low and in the
in validated test systems. No data concerning range of that of the chlorinated benzenes. The
teratogenic or embryotoxic effects of the chlo- oral LD50 in rats is greater than or equal
rinated benzenes are available for most of the to 1600 mg/kg [1064]. Sublethal doses of
compounds. p-Dichlorobenzene has been tested o-chlorotoluene given orally to rats produce
in several species and produced no primary em- marked weakness; higher doses produce vasodi-
bryotoxic or teratogenic effects [1084]. latation. Inhalation of 14 000 ppm for 6 h caused
Metabolism. Usually the chlorinated ben- loss of coordination, vasodilatation, labored res-
zenes are partially hydroxylated to yield the piration, and narcosis in rats; 175 000 ppm was
corresponding phenols or are partially dechlo- fatal to one of three rats [1064]. o-Chlorotoluene
rinated and then excreted in the urine and the produces moderate skin irritation and conjunc-
feces. In contrast to rodents, sulfur-containing tival erythema in rabbits [1064].
metabolites cannot be found in monkeys and hu- p-Chlorotoluene induced no gene conversion
mans [1063, 1085, 1086]. Only hexachloroben- in Saccharomyces cerevisiae [1089]. No data are
 Chlorinated Hydrocarbons 155

available on chronic effects or effects on repro- The PCBs failed to show positive response
duction caused by chlorinated toluenes. in validated mutagenicity test systems. The in-
In humans, no cases of poisoning or skin irri- terference of polychlorinated biphenyls with re-
tation caused by chlorinated toluenes have been production could be demonstrated in numerous
reported [1064]. studies with mammals. The compounds pass
Regulations. o-Chlorotoluene TLV 50 ppm through the placental barrier and exhibit embry-
otoxic effects [1069].
Absorption, Metabolism, and Excretion.
10.2.3. Polychlorinated Biphenyls Polychlorinated biphenyls are readily absorbed
from the gastrointestinal tract after ingestion
Acute Toxicity. The acute toxicity of mix-
or from the lung after inhalation. The rates
tures of polychlorinated biphenyls (PCB) seems
of metabolism and excretion decrease and the
to depend on the chlorine content. Table 64
storage in body fat increases with increasing
demonstrates the influence of the chlorine con-
chlorine content. The compounds are generally
tent in mixed isomers of PCBs, in addition to
metabolized by selective hydroxylation. In pri-
their relatively low acute oral toxicity.
mates, most of the metabolites are excreted as
conjugates in the urine, whereas excretion of free
Table 64. Acute oral toxicity of PCBs [1090] metabolites in the feces is the major route in ro-
dents [1093].
Chlorine content, wt % LD50 (rat, oral),
g/kg
Other Effects. Immunosuppressive action of
polychlorinated biphenyls in mammals could be
21 3.98
32 4.47
evidenced by a decrease in infectious resistance
42 8.65 with atrophy of the spleen, cortical thymus atro-
48 11.0 phy, and dose-dependent decreased in the pro-
62 11.3 duction of specific antibodies [1063, 1069]. In
68 10.9
hens, growth retardation, high mortality, and
subcutaneous edema could be observed. These
The administration of acute or subacute doses findings were accompanied by focal necrosis
results in liver enlargement, mainly due to en- of the liver, hydroperitoneum, and epicardial as
zyme induction; when the doses were increased, well as lung edema (chicken edema disease)
fatty degeneration and central atrophy of the [1063, 1069].
liver occurred. In addition, hyperplasia and Experience in Humans. Accidental acute in-
hemosiderosis of the spleen were also observed toxications with PCBs are not reported [1069].
[1091, 1092]. Polychlorinated biphenyls are not With workers handling these compounds, acne-
likely to possess a substantial local irritating po- form dermatitis was observed, in addition to liver
tential. Nevertheless, they seem to be readily ab- damage with necrosis [1063, 1069].
sorbed through the skin, exerting such systemic In 1968, a subacute intoxication of more than
effects as liver damage. 1000 people in Japan by contaminated rice oil
Chronic Effects. After oral application, se- was reported (Yusho disease). Initial symptoms
vere liver damage (hypertrophy, fatty degener- were, for instance, swelling of the eye lids, fa-
ation, and centrolobular necrosis) is most likely tigue, and gastrointestinal disturbances. Later
to be observed. The skin is also often affected on, discoloration of the skin and mucous mem-
(hyperplasia, hyperkeratosis, and cystic dilata- branes, headache, signs of sensory nerve injury,
tion) [1069]. Polychlorinated biphenyls can in- diarrhea, and jaundice were found. Cases of in-
terfere with heme metabolism as shown by an fluence on human fetuses have been attributed
increased porphyrin content of the liver in rats to this high PCB exposure [1063, 1069].
[1069]. Hepatocellular tumors are produced in Polychlorinated biphenyls accumulate in fat
rats and mice after long-term oral application of and adipose tissue. They have been demon-
PCBs [1066], vol. 20. However, the tumor for- strated in human milk. Because the PCB level
mation is regarded as a response to tissue dam- was found to be higher in infant blood but lower
age rather than triggered by a genotoxic mecha- in umbilical blood in comparison to maternal
nism.
156 Chlorinated Hydrocarbons

blood, the transfer of PCBs via the milk is proba- 1-Chloronaphthalene and 1,2,3,4-tetra-
bly much more important than placental transfer chloronaphthalene, when tested for point mu-
[1063, 1094]. tations in the Salmonella assay (Ames test),
Regulations. The following exposure limits exhibited no positive results [1097, 1098]. No
have been established: data are available on the effects of chlorinated
naphthalenes on reproduction.
Chlorine content 42 %: MAK 0.1 ppm
Metabolism. Chlorinated naphthalenes are
Chlorine content 54 %: MAK 0.05 ppm readily absorbed. Metabolism occurs by con-
jugation or via hydroxylation to the respective
naphthols or dihydrodiols. The metabolites are
Polychlorinated biphenyls are considered excreted with the urine or the feces [1063, 1096].
as possible teratogens [1095] and carcinogens Effects in Humans. The main health problem
[1069]. arising from use and handling of chlorinated
naphthalenes is chloracne, which usually occurs
from long-term contact with the compounds or
10.2.4. Chlorinated Naphthalenes exposure to hot vapors. The penta- and hex-
achloro derivatives are suggested to have the
Monochlorinated naphthalenes are of low to greatest potential to generate acne [1063].
moderate acute toxicity, as shown by their oral In accidental intoxications, liver damage oc-
LD50 (Table 65). Subacute to subchronic uptake curred independently from chloracne. After loss
of mixtures of higher chlorinated naphthalenes of appetite, nausea, and edema of the face and
(predominantly penta- and hexachloronaphtha- hands, abdominal pain and vomiting followed;
lene) resulted in liver injury [1063]. In gen- later on jaundice developed. Autopsy in cases of
eral, the toxicity of chlorinated naphthalenes in- fatal intoxication revealed yellow atrophy of the
creases with the degree of chlorination [1064]. liver [1096].
Chlorinated naphthalenes irritate the rabbit Regulations. The following exposure limits
skin [1063]. Ingestion of lubricants containing have been established:
chloronaphthalenes resulted in injury to farm
animals (X disease). Marked hyperkeratosis of Trichloronaphthalene: MAK 5 mg/m3 ,
the skin, degenerations of the cells in pan- TLV 5 mg/m3
creas, liver, and gall bladder, and damage of Tetrachloronaphthalene: TLV 2 mg/m3
the renal cortex could be observed. Cattle Hexachloronaphthalene (skin): TLV 0.2 mg/m3
Pentachloronaphthalene: TLV 0.5 mg/m3
poisoned with highly chlorinated naphthalenes Octachloronaphthalene (skin): TLV 0.1 mg/m3
show a rapid decline in vitamin A plasma lev-
els [1063]. Octachloronaphthalene fed to rats
also greatly enhances the loss of vitamin A
from the liver [1096]. Mixtures of penta- and 10.2.5. Benzyl Chloride
hexachloronaphthalenes can produce the so-
called chicken edema disease, characterized The acute oral toxicity (LD50 ) of benzyl chlo-
by hydropericardium and ascites in chickens ride in rats is 1231 mg/kg and in mice 1624
[1096]. mg/kg [1083]. The subcutaneous LD50 (in rats)
of benzyl chloride in oil solution is 1000 mg/kg
[1099]. Exposure of rats and mice to benzyl
Table 65. Oral LD50 s of monochlorinated naphthalenes [1083]
chloride concentrations of 100 –1000 mg/m3 for
Compound Species LD50 (oral), 2 h caused irritation of the mucous membranes
mg/kg and conjunctivitis [1066], vol. 11. Benzyl chlo-
1-Chloronaphthalene rats 1540
ride is a strong skin-sensitizing agent for guinea
mice 1019 pigs [1100]. Benzyl chloride acts weakly muta-
2-Chloronaphthalene rats 2078 genic in validated test systems [1101, 1102].
mice 886 Subcutaneous injection of weekly doses of 80
mg/kg for 1 year followed by a post-observation
period resulted in local sarcomas with lung
 Chlorinated Hydrocarbons 157
Table 66. Acute toxicity of side-chain chlorinated xylenes [1083]

Compound Species Route LD50 ,

mg/kg

m-Xylylene dichloride mice intravenous 100

o-Xylylene dichloride mice intravenous 320
p-Xylylene dichloride rats oral 1780

metastases in rats. The mean induction time was potential of benzoyl chloride to humans [1066],
500 d [1099]. After dermal application of ben- vol. 29.
zyl chloride, skin carcinomas were observed in
mice [1103].
Metabolism. Benzyl chloride is readily ab- 10.2.7. Benzotrichloride
sorbed from the lungs and gastrointestinal tract.
The compound reacts with tissue proteins af- The acute oral toxicity of benzotrichloride is
ter subcutaneous injection and is metabolized 2180 mg/kg in male rats and 1590 mg/kg in fe-
into N-acetyl-S-benzylcysteine [1100]. After male rats. The inhalative LC50 s are higher than
oral administration, mercapturic acid and ben- 600 mg/m3 in male rats and about 500 mg/m3
zoic acid (free or conjugated with glycine) are in female rats after a 4-h exposure [1108]. Ben-
excreted in the urine [1104]. zotrichloride irritates the skin and eyes [1109].
Effects in Humans. A concentration of 16 The compound proved to be mutagenic in bac-
ppm of benzyl chloride in air is reported to be terial test systems [1101]. Dermal application of
intolerable to humans within 1 min. The com- benzotrichloride resulted in elevated tumor inci-
pound is a potent lachrymator, strongly irritat- dence in mice [1103].
ing to the eyes, nose, and throat and capable of In humans, benzotrichloride vapors are re-
causing lung edema [1064]. ported to be strongly irritating to the skin and
Regulations. The exposure limits of benzyl mucous membranes [1107]. An increase in lung
chloride are: MAK 1 ppm; TLV 1 ppm. Ben- tumors has been reported in industrial plants that
zyl chloride should be considered as a possible produce several chlorinated aromatic hydrocar-
carcinogen [1069]. bons [1110, 1111]. In the Federal Republic of
Germany, and in Japan, benzotrichloride is con-
sidered as a possible carcinogen [1069, 1103].
10.2.6. Benzoyl Chloride

Benzoyl chloride is of low acute oral toxicity in 10.2.8. Side-Chain Chlorinated Xylenes
rats (LD50 2529 mg/kg). It is more toxic by in- Table 66 shows some acute toxicity data of side-
halation (LC50 230 ppm, 4 h in male rats and chain-chlorinated xylenes. No data are available
314 ppm, 4 h in female rats). The compound is on other toxic effects in animals or humans.
irritating to skin, mucous membranes, eyes, and
the respiratory tract [1105, 1106].
When benzoyl chloride or solutions of ben-
zoyl chloride in benzene were applied to the skin
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Fernholz, H. Wendt). DE-OS 1 768 367, 1968 (O. Fruhwirth, L.
161. ICI, BE 654 985, 1965. Schmidhammer, E. Pichl).
162 Chlorinated Hydrocarbons

185. Dynamit Nobel AG, DE-OS 2 128 329, 1974 201. R. W. McPherson et al., Hydrocarbon
(A. Hoelle). Process. 3 (1979) 75.
Bayer, DE-OS 2 743 975, 1979 (S. Hartung); 202. J. A. Buckley, Chem. Eng. (N.Y.) 73 (1966)
DE-OS 1 905 517, 1969 (R. Wesselmann, W. no. 29, 102.
Eule, E. Köhler). P. H. Spitz, Chem. Eng. Prog. 64 (1968) no.
186. S. N. Balasubramanian, Ind. Eng. Chem. 3, 19.
Fundam. 5 (1966) 184. E. F. Edwards, F. Weaver, Chem. Eng. Prog.
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(1951) 613. E. M. De Forest, S. E. Penner, Chem. Eng.
Hydrocarbon Process. 44 (1965) 198. (N.Y.) 79 (1972) no. 17, 54.
Knapsack AG, DE-OS 1 905 517, 1969. 203. D. Burke, R. Miller, Chem. Week 5 (1964)
188. Società Italiana Resine S.p.A., US no. 8, 93.
3 911 036, 1975 (L. Di Fiore, B. Calcagno). 204. Y. Onoue, K. Sakurayama, Chem. Eng. Rev.
Union Carbide, US 2 929 852, 1960 (D. B. 4 (1969) no. 11, 17.
Benedict). 205. L. F. Albright, Chem. Eng. (N.Y.) 74 (1967)
189. Lummus Co., US 3 917 727, 1975 (U. Tsao);
no. 8, 219.
US 3 985 816, 1976 (U. Tsao).
206. E.g. The Distillers Company Ltd., DE-OS
Allied, US 3 941 568, 1976 (B. E. Kurtz, A.
1 443 703, 1970 (A. F. Millidge, C. W. Capp,
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Stauffer, DE-OS 2 652 332, 1984 (R. G. P. E. Waight).
Campbell, W. E. Knoshaug). 207. Mitsui Toatsu Chemical, GB 1 189 815,
190. E. Lundberg, Kem. Tidskr. 10 (1984) 35. 1970 (K. Miyauchi et al.).
Hoechst, EP 80 098, 1984 (J. Hundeck, H. 208. VEB Chemische Werke Buna, DD 157 789,
Hennen). 1982 (J. Koppe et al.).
191. B. F. Goodrich, GB 1 233 238, 1971 (R. C. 209. BASF, DE-OS 2 651 974, 1978 (P. R.
Campbell). Laurer, J. Langens, F. Gundel).
Stauffer, US 4 000 205, 1976. Società Italiana Resine S.p.A., DE-OS
192. Dynamit Nobel AG, DE-OS 3 340 624, 1984 2 543 918, 1976 (R. Canavesi, F. Ligorati, G.
(H. Leuck, H.-J. Westermann). Aglietti).
193. C. M. Schillmoller, Hydrocarbon Process. 3 Produits Chimiques Pechiney-Saint-Gobain,
(1979) 77. US 3 634 330, 1972 (M. Michel, G.
194. R. Remirez, Chem. Eng. (N.Y.) 75 (1968) no. Benaroya, R. Jacques).
9, 142. Vulcan Materials Co., US 3 926 847, 1975
Kureha Chemical Ind., NL 6 504 088, 1965. (W. Q. Beard, Jr., P. H. Moyer, S. E. Penner).
195. ICI, DE-OS 2 012 898, 1970 (N. Diamond Shamrock Corp., BE 859 878,
Colebourne, P. R. Edwards). 1978 (F. C. Leitert, C. G. VinsonJr.,
196. F. F. Braconier, Hydrocarbon Process. 43 M. W. Kellog Co., US 3 114 607, 1963 (T.
(1964) no. 11, 140. H. Milliken).
Société Belge de l’Azote, GB 954 791, 1959 B. F. Goodrich Co., GB 938 824, 1961.
(F. F. A. Braconier, H. Le Bihan). Distillers Co., GB 932 130, 1961 (C. W.
197. Shell Development Co., US 2 099 231, 1935 Capp, D. J. Hadley, P. E. Waight);
(J. D. Ruys, J. W. Edwards). GB 971 996, 1962.
A. A. F. Maxwell, US 2 441 287, 1944. Chem. Werke Hüls AG, FR 1 421 903, 1965.
198. N. N. Semenov: Some Problems in Chemical 210. Shell Oil Co., US 3 892 816, 1975 (A. T.
Kinetics and Reactivity, vol. 1, Princeton Kister).
University Press, Princeton 1958, p. 211. 211. FMC, US 3 360 483, 1963 (L. H. Diamond,
L. F. Albright, Chem. Eng. (N.Y.) 74 (1967) W. Lobunez).
no. 7, 123. Shell Oil Co., US 3 210 431, 1965 (W. F.
199. Montecatini, IT 755 867, 1967 (C. Renato, F. Engel).
Gianfranco, C. Angelo). Stauffer, US 3 657 367, 1972 (R. J. Blake, G.
200. R. V. Carrubba, Thesis Columbia University,
W. Roy).
1968.
212. Petro-Tex Chemical Corp., US 4 025 461,
R. P. Arganbright, W. F. Yates, J. Org. Chem.
1977 (L. J. Croce, L. Bajars, M. Gabliks);
27 (1962) 1205.
4 046 821, 1977 (L. J. Croce, L. Bajars, M.
H. Heinemann, Chem. Tech. (Heidelberg) 5
Gabliks).
(1971) 287.
 Chlorinated Hydrocarbons 163

213. Toyo Soda Ltd., GB 1 016 094, 1963. 233. W. E. Wimer, R. E. Feathers, Hydrocarbon
214. Hoechst, FR 1 440 450, 1965. Process. 3 (1976) 83.
215. B. F. Goodrich Co., US 3 488 398, 1970 (J. 234. Chem. Eng. News 44 (1966) 76.
W. Harpring et al.). Chem. Week 99 (1966) no. 13, 93.
216. E. Gorin et al., Ind. Eng. Chem. 40 (1948) 235. M. L. Spektor et al., Chem. Eng. News 40
2128. (1966) no. 44, 76;
217. Vulcan Materials Co., GB 980 983, 1963 Ind. Eng. Chem. Process Des. Dev. 6 (1967)
(US 3 184 515, 1962) (S. E. Penner, E. M. no. 3, 327.
De Forest). H. Heinemann, Erdöl Kohle Erdgas
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Dunn, Jr., B. Posey, Jr. F. Friend et al., Adv. Chem. Ser. 70 (1968)
219. Pechiney, FR 1 286 839, 1961 (F. Lainé, G. 168.
Wetroff, C. Kaziz). Chem. Ind. (Düsseldorf) 19 (1967) no. 3,
220. Stauffer, US 4 206 180, 1980 (R. G. 124.
Campbell et al.). 236. Distillers Co., GB 958 458, 1962 (C. W.
221. Toa Gosei Chemical Ind., US 3 699 178, Capp, D. J. Hadley, P. E. Waight).
1968 (S. Yoshitaka, T. Atsushi, K. Hideo). Union Carbide, BE 664 903, 1965 (J. W.
222. Chem. Week 99 (1966) no. 20, 56. Clark et al.).
W. A. Holve et al., Chem. Anlage + PPG, NL 6 401 118, 1964.
Verfahren 11 (1972) 69. National Distillers and Chemical Corp., US
223. B. F. Goodrich Co., US 4 226 798, 1980 (J. 3 720 723, 1973 (E. G. Pritchett).
A. Cowfer et al.). Pullman Inc., US 3 159 455, 1964 (G. T.
PPG, GB 1 220 394, 1968 (A. P. Muren, L. Skaperdas, W. C. Schreiner, S. C. Kurzius);
W. Piester, R. M. Vancamp). 3 536 770, 1970 (G. T. Skaperdas, W. C.
224. PPG, US 3 679 373, 1972 (R. M. Vancamp, Schreiner).
P. S. Minor, A. P. Muren, Jr. Ethyl Corp., FR 1 398 254, 1964 (M. D.
225. B. F. Goodrich Co., DE-OS 1 518 930, 1965 Roof).
(J. W. Harpring et al.); 237. Monsanto, NL 6 515 254, 1966.
1 518 933, 1965 (J. W. Harpring, A. E. van 238. Monsanto, NL 6 151 253, 1966.
Antwerp, R. F. Sterbenz). 239. Allied, DE-OS 2 449 563, 1975 (B. E. Kurtz
226. Pechiney, GB 959 244, 1962; et al.).
US 3 190 931, 1965 (F. Lainé, C. Kaziz, G. 240. Shell Development Co., US 2 442 285, 1948
Wetroff). (H. A. Cheney).
227. Dow Chemical, US 3 966 300, 1976. 241. N. Singer, DD 110 032, 1974.
228. PPG, GB 2 119 802, 1983 (J. S. Helfand, T. 242. D. H. R. Barton, P. F. Onyon, J. Am. Chem.
G. Taylor). Soc. 72 (1950) 988.
229. Hoechst, DE-OS 2 300 844, 1974 (W. Kühn 243. Ethyl Corp., US 2 765 350, 1955 (F.
et al.). Conrad).
Dow Chemical, FR 2 134 845, 1972; 244. S. Okazakiand, M. Komata, Nippon Kagaku
CA 941 329, 1974 (J. E. Panzarella). Zaishi 1973, no. 3, 459.
BASF, DE-OS 2 400 417, 1975 (D. 245. N. K. Taikova et al., Zh. Org. Khim. 4 (1968)
Lausberg). 1880.
Hooker Chemical Co., NL 6 614 522, 1967. 246. I. Mochida, Y. Yoneda, J. Org. Chem. 33
230. Mitsui Toatsu Chemical, JP 45–32406, 1970; (1968) 2161.
JP 46–43367, 1971; 247. W. B. Crummett, V. A. Stenger, Ind. Eng.
JP 46–33010, 1971; Chem. 48 (1956) 434.
GB 1 189 815, 1970 (K. Miyauchi et al.). 248. W. L. Archer, E. L. Simpson, I and EC Prod.
PPG, FR 1 220 394, 1971. Res. and Dev. 16 (1977) no. 2, 158.
P. Reich, Hydrocarbon Process. 3 (1976) 85. 249. L. Bertrand et al., Int. J. Chem. Kinet. 3
R. G. Markeloff, Hydrocarbon Process. 11 (1971) 89.
(1984) 91. 250. Dow Chemical, US 1 870 601, 1932 (E. C.
231. Mitsubishi Chemical, DE-OS 2 422 988, Britton, W. R. Reed).
1974 (Y. Kageyama). 251. Ethyl Corp., US 3 019 175, 1959 (A. J.
232. Stauffer, US 3 892 816, 1972 (A. T. Kister). Haefner, F. Conrad).
164 Chlorinated Hydrocarbons

Pechiney-Saint Gobain, FR 1 390 398, 1964 267. PPG, DE-OS 1 443 033, 1961 (H. J. Vogt).
(A. Antonini, C. Kaziz, G. Wetroff);. BASF, DE-OS 1 230 418, 1961 (H.
Dynamit Nobel, DE-OS 2 026 671, 1970 (H. Ostermayer, W. Schweter).
Richtzenhain, R. Stephan). Dynamit Nobel, GB 997 357, 1962.
252. Z. Přsil, Radiochem. Radioanal. Lett. 38 Feldmühle AG, GB 893 726, 1962.
(1979) 103. 268. Dow Chemical, US 2 209 000, 1937 (H. S.
253. T. Migita et al., Bull. Chem. Soc. Japan 40 Nutting, M. E. Huscher).
(1967) 920; Solvay, BE 569 355, 1961.
Dynamit Nobel, DE-OS 1 231 226, 1963 (R.
M. Kosugi et al., Bull. Chem. Soc. Japan 43
Stephan, H. Richtzenhain).
(1970) 1535;
269. FMC, US 3 776 969, 1973 (W. Lobunez).
T. N. Bell et al., J. Phys. Chem. 38 (1979) 270. Dynamit Nobel, DE-OS 1 235 878, 1963 (R.
2321. Stephan).
254. Dow Chemical, GB 2 121 416, 1983 (J. C. 271. M. D. Rosenzweig, Chem. Eng. (N.Y.) 10
Stevens, J. Perettie). (1971) 105.
255. ICI, DE-OS 2 835 535, 1979 (C. S. Allen). 272. Vulcan Materials Co., DE-OS 1 518 166,
256. A. P. Mantulo et al., DE-OS 3 033 899, 1982; 1963 (J. I. Jordan, Jr., H. S. Vierk);
FR 8 020 077, 1980. US 3 304 337, 1967 (J. I. Jordan, Jr., H. S.
257. ICI, DE-OS 1 950 995, 1969 (A. Campbell, Vierk).
R. A. Carruthers). 273. Vulcan Materials Co., DE-OS 2 046 071,
258. Ethyl Corp., GB 843 179, 1963. 1970 (K. F. Bursack, E. L. Johnston).
Monsanto, US 3 138 643, 1961 (K. M. 274. Ethyl Corp., US 3 012 081, 1960 (F. Conrad,
Taylor, G. L. Wofford). A. J. Haefner).
PPG, US 3 059 035, 1960 (F. E. Benner, D. Société d’Ugine, FR 1 514 963, 1966.
H. Eisenlohr, D. A. Reich). 275. Detrex Chem. Ind. Inc., CA 116 460, 1971
ICI, DE-OS 2 002 884, 1970 (A. Campbell, (C. E. Kircher).
R. A. Whitelock). 276. Ugine Kuhlmann, DE-OS 1 668 760, 1971
259. Ethyl Corp., GB 1 106 533, 1965; (A. Goeb, J. Vuillement).
DE-OS 1 518 766, 1965 (A. O. Wikman, L. 277. W. G. Rollo, A. O’Grady, Can. Paint and
B. Reynolds). Finish. 10 (1973) 15.
260. ICI, DE-OS 1 950 996, 1969 (A. Campbell, W. L. Archer, Met. Prog. 10 (1974) 133.
R. A. Carruthers). R. Monahan, Met. Finish. 11 (1977) 26.
P. Goerlich, Ind.-Lackier-Betr. 43 (1975)
261. Montecatini Edison SpA, GB 1 170 149,
383.
1967;
J. C. Blanchet, Surfaces 14 (1975) 51.
FR 1 524 759, 1967 (G. Pregaglia, B. L. Skory et al., Prod. Finish. (Cincinnati) 38
Viviani, M. Agamennone). (1974) .
262. Dow Chemical, US 3 971 730, 1976 (G. L. H. A. Farber, G. P. Souther, Am. Dyest. Rep.
Kochanny, Jr., T. A. Chamberlin); 57 (1968) 934;
3 872 176, 1975 (G. L. Kochanny, Jr., T. A. G. P. Souther, Am. Dyest. Rep. 59 (1970) 23.
Chamberlin). J. J. Willard, Text. Chem. Color. 4 (1972) 62.
263. Consortium f. Elektrochem. Ind., US H. Hertel, Kunststoffe 71 (1981) 240.
1 921 879, 1933 (W. O. Herrmann, E. 278. Dow Chemical, US 2 838 458, 1955 (H. J.
Baum). Bachtel);
Saint Gobain, US 2 674 573, 1949 (M. J. L. 2 923 747, 1958 (D. E. Rapp);
Crauland). 2 970 113, 1957 (H. J. Bachtel);
Distillers Comp., US 2 378 859, 1942 (M. 3 049 571, 1960 (W. E. Brown);
Mugdan, D. H. R. Barton). 3 364 270, 1965 (M. J. Blankenship, R.
264. I.G. Farbenindustrie, GB 349 872, 1930. McCarthy);
Bataafsche Petroleum M., GB 638 117, 3 384 673, 1966 (M. J. Blankenship, R.
1948. McCarthy);
3 444 248, 1969 (W. L. Archer, E. L.
265. Dow Chemical, US 2 610 214, 1949 (J. L.
Simpson, G. R. Graybill);
Amos).
3 452 108, 1969 (W. L. Archer, E. L.
266. Ethyl Corp., US 2 989 570, 1959 (F. Conrad,
Simpson, G. R. Graybill);
M. L. Gould). 3 452 109, 1969 (W. L. Archer, E. L.
Simpson, G. R. Graybill);
 Chlorinated Hydrocarbons 165

3 454 659, 1969 (W. L. Archer, E. L. 281. PPG, US 3 344 197, 1967 (Ch. R. Reiche, J.
Simpson); M. Jackson).
3 467 722, 1967 (W. L. Archer, G. R. 282. Toa Gosei Chemical Ind. Co., DE-OS
Graybill); 1 944 212, 1969 (Y. Suzuki, R. Saito);
3 468 966, 1969 (W. L. Archer, E. L. 2 000 424, 1970 (T. Kawaguchi et al.).
Simpson); 283. J. C. Martin, E. H. Drew, J. Am. Chem. Soc.
3 472 903, 1969 (W. L. Archer, E. L. 83 (1961) 1232;
Simpson); M. L. Poutsma, J. Am. Chem. Soc. 85 (1963)
3 546 305, 1970 (W. L. Archer, E. L. 3511.
Simpson); Y. H. Chua et al., Mech. Chem. Eng. Trans. 7
3 681 469, 1972 (W. L. Archer, E. L. (1971) 6.
Simpson); 284. ICI, GB 1 388 660, 1972 (J. S. Berrie, I.
4 469 520, 1984 (N. Ishibe, W. F. Richey, M. Campbell).
S. Wing); Solvay and Cie., DE-OS 2 505 055, 1984.
GB 916 129, 1961; 285. Bataafsche Petroleum, GB 627 119, 1947.
Shell Development Co., US 2 621 153, 1947
NL 6 919 176, 1969.
(R. H. Meyer, F. J. F. van der Plas).
Ethyl Corp., US 3 002 028, 1958 (A. J.
Toa Gosei Chem. Ind., DE-OS 2 000 424,
Haefner, L. L. Sims);
1970.
3 060 125, 1958 (L. L. Sims);
Dow Chemical, US 2 174 737, 1963 (G. H.
3 074 890, 1958 (G. N. Grammer);
Coleman, G. V. Moore).
3 189 552, 1963 (L. L. Sims); 286. British Celanese Ltd., GB 599 288, 1945 (P.
3 238 137, 1961 (G. N. Grammer, P. W. J. Thurman, J. Downing).
Trotter); 287. Dow Chemical, US 2 140 549, 1937 (J. H.
3 629 128, 1968 (J. H. Rains). Reilly).
Vulcan Materials Co., FR 1 369 267, 1963. 288. PPG, US 3 065 280, 1960 (H. J. Vogt).
Solvay Cie., BE 743 324, 1969; Hoechst, FR 1 318 225, 1962.
755 668, 1970. PPG, US 3 173 963, 1960 (Ch. R. Reiche, H.
PPG, US 3 000 978, 1959 (R. H. J. Vogt).
Fredenburg); FMCI, FR 1 491 902, 1966 (S. Berkowitz,
3 070 634, 1960 (D. E. Hardies, B. O. Pray); A. R. Morgan, Jr.
3 128 315, 1961 (D. E. Hardies); 289. Produits Chimiques Péchiney-Saint-Gobain,
3 192 273, 1961 (W. E. Bissinger); FR 1 552 820, 1969 (G. Benaroya, M. Long,
3 281 480, 1961 (D. E. Hardies); F. Lainé);
BE 613 661, 1962 (D. E. Hardies). 1 555 518, 1969 (A. Antonini, P. Joffre, F.
ICI, FR 1 372 972, 1963; Lainé).
1 372 973, 1963; Rhône-Poulenc Ind., US 4 057 592, 1977 (A.
DE 1 243 662, 1962 (P. Rathbone, Ch. W. Antonini, P. Joffre, F. Lainé).
Suckling); 290. Consortium Elektrochem. Ind., FR 690 767,
1 941 007, 1969 (A. Campbell, P. Robinson, 1930.
J. W. Tipping); I.G. Farben, FR 690 655, 1930;
US 3 336 234, 1964 (J. H. Speight); DE 489 454, 1927.
GB 1 261 270, 1969 (G. Marsden, J. W. British Celanese Ltd., GB 571 370, 1943 (P.
Tipping). J. Thurman, J. Downing).
Dynamit Nobel, FR 1 371 679, 1967; Hoechst, FR 1 318 225, 1962.
1 393 056, 1965; 291. Asahi Kasei Kogyo, FR 1 417 810, 1964.
DE 1 246 702, 1962 (R. Stephan, H. Vulcan Materials Corp., GB 980 983, 1963.
Richtzenhain). Central Glass Co., JP 42–9924, 1965.
292. Produits Chimiques Péchiney-Saint-Gobain,
PCUK, FR 1 555 883, 1967 (J. Vuillemenot).
FR 1 552 821, 1969 (A. Antonini, G. du
Diamond Shamrock Corp., DE-OS
Crest, G. Benaroya);
2 102 842, 1971 (N. L. Beckers, E. A. Rowe,
1 552 824, 1969 (A. Antonini, P. Joffre, C.
Jr.
Vrillon).
279. D. H. R. Barton, J. Chem. Soc. 1949, 148.
293. Donauchemie, DE 865 302, 1944 (O.
280. A. Suzuki et al., Kogyo Kagaku Zasshi 69
Fruhwirth).
(1966) 1903.
Du Pont, US 2 461 142, 1944 (O. W. Cass).
166 Chlorinated Hydrocarbons

294. Knapsack-Griesheim AG, DE 939 324, 1954 2 320 915, 1974 (L. Schmidhammer, D.
(K. Sennewald, F. Pohl, H. Westphal). Dempf, O. Sommer);
295. D. H. R. Barton, K. E. Howlett, J. Chem. 2 239 052, 1974 (S. Nitzsche, L.
Soc. 1951, 2033. Schmidhammer).
296. Toa Gosei Chem. Ind. Ltd., FR 2 057 606, 314. Monsanto Chem. Co., US 2 846 484, 1954
1971; (J. E. Fox).
US 3 732 3422, 1973 (T. Kawaguchi). Produits Chimiques Péchiney-Saint-Gobain,
Asahi Glass Co., JP 75–34 0003, 1975. DE-OS 1 768 485, 1968 (G. du Crest, G.
Detrex Chemical Ind., US 3 304 336, 1967 Benaroya, F. Lainé);
(W. A. Callahan). 1 768 494, 1968 (A. Antonini, P. Joffre, C.
D. Gillotay, J. Olbregts, Int. J. Chem. Kinet. Vrillon);
8 (1976) 11. 1 768 495, 1968 (A. Antonini, C. Kaziz, G.
FMC, DE-OS 1 928 199, 1969 (S. Wetroff);
Berkowitz). FR 1 552 825, 1969 (A. Antonini, C. Kaziz,
297. V. A. Poluektov et al., SU 195 445, 1976. G. Wetroff);
298. I. G. Farben DE 530 649 (1929). 1 552 826, 1969 (A. Antonini, C. Kaziz, G.
299. L. E. Horsley, Azeotropic Data in Adv. Wetroff).
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D.C., 1952. 316. Japan Atomic Energy Research Inst., JP
300. S. Tsuda, Chem. Eng. (N.Y.) 74 (May 1970). 42–13842, 1967.
301. ICI, FR 2 003 816, 1969. 317. Knapsack-Griesheim, GB 749 351, 1954.
302. K. S. B. Prasa, L. K. Doraiswamy, J. Catal. 318. G. Kalz, Plaste Kautsch. 18 (1971) 500.
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306. Hooker Chemical Co., NL 6 614 522, 1965. (1962) 75.
307. T. Kawaguchi et al., Ind. Eng. Chem. 62 322. Kali-Chemie, DE 712 784, 1938 (F.
(1970) 36. Rüsberg, E. Gruner).
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328. M. Lederer, Angew. Chem. 71 (1959) 162.
311. Produits Chimiques, Péchiney-Saint-Gobain
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Y. Correia);
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330. R. West, W. H. Glaze, J. Org. Chem. 26
US 4 148 832, 1979 (Y. Correia);
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DE-OS 1 817 193, 1975 (Y. Correia, J. C.
331. Dow Chemical, US 4 147 733, 1979 (T. R.
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Fiske, D. W. Baugh, Jr.
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332. R. E. Lynn, K. A. Kobe, Ind. Eng. Chem. 46
312. Kanto Denka Kogyo Ltd., DE-OS 1 568 912,
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1966 (A. Suzuki et al.).
Société Belge de l’Azote, US 2 779 804,
313. Wacker, DE-OS 2 023 455, 1971 (L.
1954 (F. F. A. Braconier, J. A. R. O. L.
Schmidhammer, O. Fruhwirth);
Godart).
 Chlorinated Hydrocarbons 167

333. Société Belge de l’Azote, GB 954 791, 1959 353. Institut für Chemieanlagen, FR 1 441 148,
(F. F. A. Braconier, H. Le Bihan). 1966;
334. Chemische Werke Hüls AG, GB 709 604, DD 51 850, 1968 (K. Roland, C. Gerber, G.
1957; Voigt).
BASF, GB 769 773, 1955; 354. Institut für Chemieanlagen, GB 1 174 147,
Produits Chimiques de 1969;
Péchiney-Saint-Gobain, FR 1 361 884, 1963 FR 1 553 573, 1968;
(F. Lainé, C. Kaziz, G. Wetroff). DD 60 303, 1968 (K. Roland).
355. Institut für Chemieanlagen, DD 50 593,
335. Knapsack AG, DE-OS 2 053 337, 1972 (A.
1966 (K. Roland);
Lauke).
DE 1 260 416, 1968 (K. Roland).
336. F. J. Gattys-Verfahrenstechnik GmbH, 356. Grupul Industrial de Petrochimie Borzesti,
DE-OS 2 646 129, 1979 (F. J. Gattys). FR 7 202 582, 1972 (T. Has et al.);
337. D. H. R. Barton, M. Mugdan, J. Soc. Chem. Knapsack AG, DE-OS 1 254 143, 1967 (G.
Ind. 69 (1950) 75; Rechmeyer, A. Jacobowsky).
F. Patat, P. Weidlich, Helv. Chim. Acta 32 357. Kureha Kagaku Kogyo Kabushiki Kaisha,
(1949) 783. GB 1 149 798, 1969;
338. Yu. A. Pasderskii, SU 686 279, 1984. FR 1 558 893, 1968.
339. K. Washimi, Y. Wakabayashi, Kogyo Kagaku Japan Gas-Chemical Co. Inc., FR 1 465 296,
Zasshi 68 (1965) 113; 1967.
R. D. Wesselhoft et al., AlChEZ. 5 (1959) 358. Solvay and Cie., BE 698 555, 1967;
361. US 3 506 727 (J. Mulders).
340. VEB Chemische Werke Buna, DD 159 985, 359. N. L. Volodin et al., DE-OS 2 026 429, 1975;
1981 (J. Glietsch et al.). US 4 014 947, 1977;
FR 2 045 822, 1971.
341. VEB Chemiefaserwerk Friedrich Engels, 360. B. J. Pope, US 3 864 409, 1975.
DD 150 880, 1981 (H. E. Steglich et al.); 361. S. Gomi, Hydrocarbon Process. 43 (1964)
200 017, 1983 (H. E. Steglich et al.); 165;
VEB Chemische Werke Buna, DD 126 454, K. Washimi, M. A. Kura, Chem. Eng. (N.Y.)
1977 (G. Henke); 73 (1966) no. 10, 133; no. 11, 121;
132 711, 1978 (H. Stolze et al.); Y. Onoue, K. Sakurayama, Chem. Econ.
149 212, 1981 (J. Glietsch, W. Linke). Eng. Rev. 4 (1969) 17.
342. Marathon Oil Co., GB 1 138 669, 1969. 362. F. J. Gattys Ingenieurbüro, DE-OS
343. Monsanto, GB 600 785, 1945; 2 820 776, 1980 (F. J. Gattys);
757 661, 1954. DE 2 905 572, 1983 (F. J. Gattys).
344. Air Reduction Co., US 2 448 110, 1946 (H. 363. H. J. Pettelkau, DE 3 007 634, 1982.
S. Miller). 364. K. E. Howlett, Trans. Faraday Soc. 48
345. Gevaert Photo Production N.V., GB 655 424, (1952) 25;
1947. L. K. Doraiswamy et al., Br. Chem. Eng. 5
346. Gevaert Photo Production N.V., GB 643 743, (1960) 618;
G. A. Kapralova, N. N. Semenov, Zh. Fiz.
1947.
Khim. 37 (1963) 73;
347. Wacker, DE-OS 1 277 845, 1968 (O.
P. G. Ashmore et al., J. Chem. Soc., Faraday
Fruhwirth, H. Kainzmeier).
Trans. 1 1982, 657.
348. VEB Chemische Werke Buna, DD 139 976, 365. Chemische Werke Hüls AG, DE-OS
1980 (R. Adler et al.). 2 130 297, 1975 (G. Scharein, J. Gaube).
349. Hoechst, DE 2 558 871, 1984 (W. Gerhardt, 366. E. V. Sonin et al., FR 2 082 004, 1971;
H. Scholz). GB 1 225 210, 1969;
350. VEB Chemische Werke Buna, DD 139 975, DE 1 953 240, 1984.
1980 (K. Hartwig et al.); 367. Allied, DE-OS 2 319 646, 1973 (B. E. Kurtz
143 367, 1980 (K. Hartwig et al.). et al.).
351. Chemische Werke Hüls AG, DE 1 205 705, 368. BASF, DE-OS 2 349 838, 1974 (G. Krome).
1964 (W. Knepper, G. Höckele); 369. BP Chemicals Intern. Ltd., GB 1 337 326,
DE-OS 2 054 102, 1970 (H. Maiwald, G. 1973 (N. F. Chisholm).
Höckele, H. Sauer). 370. BP Chemicals Ltd., FR 2 099 466, 1972 (D.
352. H. Bremer et al., DD 84 182, 1971. P. Young);
DE-OS 2 135 248, 1972 (D. P. Young);
US 3 896 182, 1975.
168 Chlorinated Hydrocarbons

371. Mitsui Chem. Ind., JP 42 22921, 1967. 381. ICI, GB 1 405 714, 1975;
372. BP Chemicals Ltd., GB 1 494 797, 1977 (R. Wacker, DE-OS 3 009 520, 1981 (L.
W. Rae, W. F. Fry). Schmidhammer, R. Straßer);
373. Magyar Asvanyolaj es Földgaz Kiserleti Solvay and Cie., EP 101 127, 1983 (A.
Intezet, DE-OS 2 223 011, 1973 (L. Szepesy Closon).
et al.); 382. Deutsche Gold- und Silberschmiedeanstalt,
2 225 656, 1973 (I. Vendel et al.); DE-OS 2 438 153, 1976 (G. Vollheim et al.).
Hoechst, NL 7 503 850, 1974; 383. Solvay and Cie, FR 1 602 522, 1970;
Knapsack AG, DE-OS 2 313 037, 1974 (G. US 3 801 660, 1974 (G. Coppens).
384. Dow Chemical, US 3 723 550, 1973 (R. T.
Rechmeier, W. Mittler, R. Wesselmann);
McFadden).
B. F. Goodrich Co., GB 938 824, 1961.
385. Monsanto, US 3 125 607, 1964 (H. M.
374. BASF, DE-OS 3 147 310, 1973 (W. Hebgen
Keating, P. D. Montgomery);
et al.). Hoechst, DE-OS 2 903 640, 1980 (G.
375. Hoechst, DE-OS 2 907 066, 1980 (A. Rechmeier, U. Roesnik, H. Scholz).
Czekay et al.); 386. Monsanto, US 3 142 709, 1964 (E. H.
3 013 017, 1981 (R. Krumböck et al.); Gause, P. D. Montgomery).
Hoechst and Uhde GmbH/Hoechst AG, EP 387. Monsanto, US 3 125 608, 1964 (D. W.
14 920, 1980 (A. Czekay et al.); McDonald).
21 381, 1980 (G. Link et al.). 388. Continental Oil Co., US 3 830 859, 1974 (R.
376. Halcon Intern. Inc., FR 1 505 735, 1967 (B. Gordon et al.).
J. Ozero); 389. VEB Chemische Werke Buna, DD 143 368,
Knapsack AG, NL 6 612 668, 1967; 1980 (H. Hauthal et al.).
Knapsack AG, DE-OS 1 250 426, 1966 (H. 390. Rhône-Progil S.A., DE-OS 2 429 273, 1976
Krekeler et al.); (Y. Correia, J.- C. Lanet).
1 910 854, 1972 (G. Rechmeier, A. 391. Rhône-Progil, FR 2 241 519, 1973 (Y.
Jacobowsky, P. Wirtz); Correia, J.-C. Lanet).
The Lummus Co., DE-OS 2 501 186, 1975 392. BASF, DE-OS 3 122 181, 1982 (E. Danz, G.
(R. Long, H. Unger); Krome).
Hoechst AG, DE 3 024 156, 1983 (A. 393. Goodyear Fire and Rubber Co., US
Czekay et al.); 4 042 637, 1977 (E. J. Glazer, E. S. Smith).
BASF, DE-OS 3 140 892, 1983 (W. Hebgen 394. M. Rätzsch et al., DD 112 603, 1975.
395. Continental Oil Co., US 3 917 728, 1975 (R.
et al.).
D. Gordon).
377. Hoechst, GB 2 054 574, 1981 (J. Riedl, W.
396. Hydrocarbon Process. 44 (1965) 290.
Fröhlich, E. Mittermaier). 397. Wacker, DE 1 135 451, 1960 (O. Fruhwirth).
378. PPG, NL 6 613 177, 1967; 398. Wacker, DE-OS 2 156 943, 1973 (O.
BASF, DE 3 219 352, 1984 (E. Birnbaum, E. Fruhwirth, L. Schmidhammer, H.
Palme). Kainzmeier).
379. Solvay and Cie., BE 746 270, 1970; 399. Pullman Corp., GB 1 152 021, 1969;
DE-OS 1 288 594, 1969 (G. Coppens); Monsanto, FR 1 515 554, 1968 (R. L.
2 101 464, 1971 (G. Coppens). Hartnett).
380. Knapsack AG, DE-OS 1 959 211, 1971 (P. 400. Wacker, DE-OS 2 239 051, 1975 (S.
Wirtz et al.); Nitzsche, L. Schmidhammer);
Kanegafuchi Kagaku Kogyo K.K., DE-OS Shell Internat. Research, NL 6 610 116,
2 426 514, 1975 (T. Ohishi, N. Yoshida, T. 1968.
Hino); 401. FMC, DE-OS 1 928 199, 1969 (S.
Allied, NL 7 711 904, 1977; Berkowitz).
Wacker, DE-OS 2 754 891, 1979 (L. 402. B. F. Goodrich Co., EP 0 002 021, 1979 (A.
Schmidhammer, H. Frey); J. Magistro).
BASF, 2 307 376, 1974 (G. Krome); 403. The Lummus Co., DE-OS 1 806 547, 1976
Dynamit Nobel AG, DE 3 135 242, 1984; (H. D. Schindler, H. Riegel);
(R. Stephan et al.); 2 502 335, 1975 (H. D. Schindler).
BASF, DE-OS 3 140 447, 1983 (W. Hebgen 404. J. Wolfrum et al., DE 2 938 353, 1983;
EP 0 027 554, 1981.
et al.).
K. Kleinnermanns, J. Wolfrum, Laser Chem.
2 (1983) 339.
 Chlorinated Hydrocarbons 169

405. Kanegafuchi Kagaku Kogyo Kabushiki 417. Produits Chimiques Péchiney-Saint-Gobain,

Kaisha, FR 1 556 912, 1969. FR 1 552 849, 1969 (A. Antonini, G. Stahl,
406. M. Sittig: Vinyl Chloride and PVC C. Vrillon).
Manufacture, Noyes Data Corp., Park Ridge, 418. British Petroleum Co. Ltd., DE-OS
New York 1978. 2 540 067, 1976 (J. L. Barclay).
407. Akzo, US 4 256 719, 1981 (E. van Andel); B. F. Goodrich Co., DE-OS 2 613 561, 1976
E. van Andel, Chem. Ind. (London) 1983, no. (W. J. Kroenke, P. P. Nicholas);
2, 139. US 4 100 211, 1978 (A. J. Magistro);
408. European Chem. News 46 (1229) June 9, p. 4 102 935, 1978 (W. J. Kroenke, R. T.
4, 1986. Carroll, A. J. Magistro);
409. Montecatini S.G., IT 761 015, 1967 (M. 4 102 936, 1978 (A. J. Magistro);
Mugero, M. Boriningo). 4 119 570, 1978 (W. J. Kroenke, P. P.
410. Hitachi Zosen Kabushiki Kaisha, NL Nicholas);
6 604 833, 1966. CA 1 096 406, 1981 (A. J. Magistro).
411. Badger Co. Inc, DE-OS 2 629 461, 1978 (H. Monsanto, DE-OS 2 852 036, 1979 (T. P.
R. Sheely, F. F. Oricchio, D. C. Ferrari). Li);
Pullmann Inc., GB 1 177 971, 1970 (B. E. CA 1 111 454, 1981 (T. P. Li).
Firnhaber). ICI, GB 2 095 242, 1982 (D. R. Pyke, R.
412. Ethyl Corp., US 2 681 372, 1951 (P. W.
Reid);
Trotter);
2 095 245, 1982 (D. R. Pyke, R. Reid);
Hoechst, DE 1 003 701, 1954;
DE-OS 3 226 028, 1983 (D. R. Pyke, R.
National Distillers, US 2 896 000, 1955 (F.
Reid).
D. Miller, D. P. Jenks);
Société Belge de l’Azote, GB 889 177, 1959 419. Owens-Illinois Inc., US 4 042 639, 1977 (T.
(P. J. Leroux, F. F. A. Braconier); H. Gordon, H. F. Kummerle);
ESSO Research and Engin. Co., FR Princeton Chemical Research Inc., FR
1 344 322, 1962 (J.-M. Guilhaumou, M. 1 595 619, 1970 (N. W. Frisch, R. I.
Prillieux, P. Verrier); Bergmann).
S. Tsutsumi, GB 956 657, 1962; 420. O. A. Zaidman et al., DE-OS 2 853 008,
Union Carbide, FR 1 385 179, 1964; 1980;
Toyo Koatsu Ind., BE 637 573, 1963; GB 2 036 718, 1980.
658 457, 1965 (T. Takahashi et al.). 421. Princeton Chemical Research Inc., DE-OS
413. ESSO Research and Engin Co., US 1 806 036, 1969 (R. I. Bergmann);
3 670 037, 1972 (J. J. Dugan); Produits Chimiques Péchiney-Saint-Gobain,
ICI, DE-OS 2 837 514, 1979 (J. D. Scott); US 3 923 913, 1975 (A. Antonini et al.).
Shell Intern. Research, NL 6 611 699, 1968; 422. Monsanto, NL 6 515 252, 1966.
Allied, US 4 039 596, 1977 (W. M. Pieters, 423. Ethyl Corp., US 3 658 933, 1972 (W. Q.
E. J. Carlson); Beard, Jr.
Du Pont, US 2 308 489, 1940 (O. W. Cass); 3 658 934, 1972 (W. Q. Beard, Jr.
ICI, FR 1 330 367, 1962; 3 629 354, 1971 (W. Q. Beard, Jr.
1 359 016, 1963; 424. The Lummus Co., DE-OS 1 693 042, 1974
Hoechst, BE 662 098, 1965; (H. Riegel);
Osaka Kinzoku Kogyo, US 3 267 161, 1963 1 812 993, 1974 (H. Riegel, H. Schindler);
(R. Ukaji et al.). 1 952 780, 1970 (H. Riegel et al.);
414. ICI, DE-OS 1 277 243, 1968 (B. Hancock, 2 230 259, 1973 (H. Riegel);
L. McGinty, I. McMillan). 2 314 786, 1973 (U. Tsao);
415. Diamond Shamrock Corp., US 4 115 323, 2 335 949, 1974 (H. Riegel et al.);
1978 (M. F. Lemanski, F. C. Leitert, C. G. 2 336 497, 1974 (H. D. Schindler et al.);
Vinson, Jr. 2 509 966, 1975 (H. Riegel);
416. Hoechst, DE-OS 1 931 393, 1971 (H.
2 536 286, 1976 (U. Tsao);
Krekeler, H. Kuckertz);
US 3 920 764, 1975; (H. Riegel et al.);
British Petroleum Co. Ltd., DE-OS
3 935 288, 1976 (H. Riegel);
1 907 764, 1972 (G. H. Ludwig);
3 937 744, 1976 (H. Riegel);
GB 1 213 402, 1970 (G. H. Ludwig);
Marathon Oil Co., US 3 501 539, (D. H. 3 796 641, 1974 (H. Riegel et al.);
Olson, G. M. Bailey). FR 1 574 064, 1969 (M. C. Sze);
170 Chlorinated Hydrocarbons

1 574 705, 1969 (H. Riegel); 2 160 944, 1938 (G. H. Coleman, J. W.
1 576 909, 1969 (H. Riegel, H. D. Zemba);
Schindler); Ethyl Corp., FR 1 308 101, 1961 (A. J.
1 577 105, 1969 (H. Riegel); Haefner, E. D. Hornbaker).
GB 1 258 750, 1971. 442. R. J. Williams, J. Chem. Soc. 1953, 113;
425. Ethyl Corp., US 2 838 579, 1954 (F. Conrad, K. Feramoto et al., Kogyo Kagaku Zasshi 67
M. L. Gould, C. M. Neher); (1964) 50.
Monsanto, US 3 166 601, 1961 (K. M. 443. J. Svoboda et al., Petrochemia 22 (1982) 21.
Taylor); 444. BASF, DE-OS 1 230 418, 1966 (H.
Du Pont, US 3 234 295, 1961 (J. W. Sprauer, Ostermayer, W. Schweter).
S. Heights). 445. ICI, DE-OS 2 225 512, 1972 (G. A.
426. PPG, GB 996 323, 1962 (W. K. Snead, R. H. Thompson, J. W. Tipping).
Chandley); 446. ICI, GB 1 453 509, 1976 (I. S. McColl, A. C.
998 689, 1965; P. Pugh, G. A. Thompson).
FR 1 341 711, 1962 (A. C. Ellsworth); 447. Detrex Chemical Industries Inc., US
Princeton Chemical Research Inc., DE-OS 3 725 486, 1973 (W. L. McCracken et al.).
1 929 062, 1969 (N. W. Frisch); 448. Toa Gosei Chem. Ind. Co., Ltd., JP 56/104
The British Petroleum Co. Ltd., DE-OS 826, 1981.
2 006 262, 1971 (G. H. Ludwig). 449. PPG, DE-OS 2 651 901, 1980 (J. D.
427. Ethyl Corp., US 2 765 349–352, 1955 (F. Mansell).
Conrad); 450. S. A. Devinter, FR 2 131 896, 1973.
2 803 677 1955 (C. M. Neher, J. H. Dunn); 451. Continental Oil Co., US 3 664 966, 1972 (R.
2 803 678–680 1955 (F. Conrad). D. Gordon).
428. Air Reduction Co. Inc., US 3 506 552, 1970 452. Kanegafuchi Chemical Industry Co., Ltd., JP
(J. P. Russell). 48/92312, 1973.
429. Allied, US 4 155 941, 1979 (H. E. Nychka, 453. Dow Chemical, US 3 984 489, 1976 (R. F.
R. E. Eibeck). Mogford).
430. PCUK Produits Chimiques Ugine 454. Continental Oil Co., US 3 869 520, 1975 (R.
Kuhlmann, FR 2 529 883, 1982 (G. A. Olah). D. Gordon).
431. ICI, EP 15 665, 1980 (C. S. Allen). 455. Dow Chemical, US 2 293 317, 1941 (F. L.
432. PPG, GB 2 121 793, 1982 (D. R. Nielsen). Taylor, L. H. Horsley).
433. Central Glass Co. Ltd., DE 2 818 066, 1982 456. Asahi-Dow Ltd., JP 56/57722, 1981.
(K. Yagii, H. Oshio). 457. E. W. Sonin et al., DE-OS 1 952 770, 1973.
434. Amer., US 3 558 453, 1971 (J. S. Mayell). 458. K. Nagai, M. Katayama, Bull. Chem. Soc.
435. ICI, FR 2 064 406, 1971; Japan 51 (1978) 1269.
ZA 706 583, 1969 (C. Neville, P. R. 459. Chemische Werke Hüls AG, DE-OS
Edwards, P. J. Craven). 2 135 908, 1974 (H. Rassaerts, G. Sticken,
436. Gulf R a D Co., US 3 577 471, 1971 (J. G. W. Knepper).
McNulty, W. L. Walsh). 460. Dow Chemical, US 4 119 678, 1978 (T. S.
437. Seymour C. Schuman, US 3 377 396, 1968. Boozalis, J. B. Ivy).
438. SRI International, Chem. Econ. Handbook, 461. Mitsui Toatsu Chemicals Co., Ltd., JP
Marketing Research Report on PVC Resins, 47/18088, 1972.
Menlo Park, 1982. 462. Wah Young Lee et al., Hwahak Konghak 14
SRI International, Vinyl Chloride Report, (1976) 169;
Menlo Park, 1982. Chem. Abstr. 85 142517 c.
Eur. Chem. News 44 (1985) no. 1169. 463. I. Mochida et al., Sekiyu Gakkai Shi 21
439. Eur. Chem. News 45 (1985) no. 1194, 4. (1978) 285;
Chem. Week (1985) 30. Chem. Abstr. 90 22226 p.
440. Hydrocarbon Process., HPI Construction 464. I. Mochida et al., JP 51/133207, 1976.
Boxscore, October 1984; Eur. Chem. News 465. ICI, DE-OS 2 257 107, 1973 (M. H. Stacey,
44 (1985) no. 1167. T. D. Tribbeck);
441. Dow Chemical, US 2 136 333, 1936 (G. H. PPG, DE-OS 2 849 469, 1979 (W. H.
Coleman, J. W. Zemba); Rideout);
2 136 349, 1938 (R. M. Wiley); US 4 144 192, 1979 (A. E. Reinhardt II).
 Chlorinated Hydrocarbons 171

466. Asahi-Dow Ltd., JP 55/87730, 1980; Toa 485. Dynamit Nobel, DE 1 174 764, 1958 (E. E.
Gosei Chemical Industry Co., Feder, K. Kienzle);
Ltd., JP 52/31006, 1977. Detrex Chemical Ind., US 2 912 470, 1956
467. Asahi-Dow Ltd., JP 55/87729, 1980. (C. E. Kircher, Jr., R. J. Jones);
468. A. P. Khardin et al., Khim. Prom-st. Moscow M. Szczeszek, H. Chmielarska, Przem.
1982, 208; Chem. 56 (1977) 255.
P. Y. Gokhberg et al., Kinet. Katal. 23 (1982) 486. Wacker, DE 846 847, 1942 (W. Fritz, E.
50–53, 469–473; Schaeffer);
A. P. Khardin et al., Khim. Prom-st. NL 6 600 884, 1966.
(Moscow) 1981, 16. 487. Du Pont, US 2 894 045, 1957 (E. G. Carley);
469. N. Yamasata, Ibaraki Kogyo Koto Semmon Hooker Chemical Co., US 3 100 233, 1960
Gakko Kenkyu Iho 11 (1976) 213; (D. S. Rosenberg);
Chem. Abstr. 89 214 828 n. Donau-Chemie AG, AT 238 699 (F.
470. I. Mochida, J. Mol. Catal. 12 (1981) 359; Samhaber).
488. Donau-Chemie AG, AT 191 859, 1957 (L.
Asahi-Dow Ltd., JP 56/40622, 1981;
Gavanda, A. F. Orlicek);
58/162537, 1983;
ICI, GB 697 482, 1951 (R. T. Foster, S. W.
56/150028, 1981;
Frankish).
56/40622, 1981.
489. The Distillers Co., US 2 378 859, 1942 (M.
471. J. Kobayashi et al., Kenkyu Hokoku–Asahi
Mugdan, D. H. R. Barton).
Garasu Kogyo Gijutsu Shoreikai 37 (1980) 490. Du Pont, US 3 388 176, 1968 (J. L. Sheard);
251; 3 388 177, 1968 (L. J. Todd).
Chem. Abstr. 95 6055 e. 491. Produits Chimiques Péchiney-Saint-Gobain,
472. Kureha Chemical Industry Co., Ltd., JP DE-OS 2 008 002, 1975 (R. Clair, Y.
48/10130, 1973. Correia);
473. L. Espada et al., Ion 37 (1977) 495. Toa Gosei Chem. Ind., DE-OS 1 943 614,
474. Wacker, DE-OS 1 925 568, 1974 (O. 1969 (T. Kawaguchi et al.).
Fruhwirth, E. Pichl, L. Schmidhammer); 492. Detrex Chemical Ind. Inc., DE-OS
Kureha Kagaku Kogyo K.K., DE-OS 1 643 872, 1967 (C. E. Kirchner, Jr., D. R.
2 101 463, 1971 (K. Shinoda et al.); McAllister, D. L. Brothers).
2 135 445, 1973 (K. Shinoda, T. Nakamura). 493. S. Suda, Chem. Eng. (N.Y.) 77 (1970) 74.
475. Asahi-Dow Ltd., JP 56/57721, 1981. T. Kawaguchi et al., Ind. Eng. Chem. 62
476. ICI, DE-OS 2 850 807, 1979 (J. D. Wild). (1970) 36.
477. Dow Chemical, US 3 726 932, 1973 (C. R. 494. Detrex Chemical Ind. Inc., US 3 691 240,
Mullin, D. J. Perettie). 1972 (C. E. Kirchner, D. R. McAllister, D. L.
478. Dow Chemical, US 3 654 358, 1977 (G. C. Brothers).
Jeffrey). 495. Dow Chemical, US 2 140 548, 1938 (J. H.
479. Donau-Chemie, AT 162 391, 1947. Reilly);
480. Knapsack-Griesheim AG, DE 969 191, 1952 Diamond Alkali Corp., GB 673 565, 1952;
(A. Jacobowsky, K. Sennewald); Ethyl Corp., US 2 725 412, 1954 (F.
DE-OS 1 011 414, 1953 (A. Jacobowsky, K. Conrad);
Sennewald); Donau Chemie AG, NL 6 607 204, 1966.
Péchiney, US 3 197 515, 1962 (P. Chassaing, 496. Diamond Shamrock Corp., DE-OS
G. Clerc). 2 061 508, 1970 (J. J. Lukes, R. J. Koll).
481. B. Jakesevic, Tekstil 32 (1983) 321. 497. Ruthner AG, AT 305 224, 1973 (F.
482. C. J. Howard, J. Chem. Phys. 65 (1976) Samhaber);
4771; PPG, US 3 793 227, 1974 (W. K. Snead, F.
J. S. Chang, F. Kaufmann, J. Chem. Phys. 66 Abraham).
498. D. Jaqueau et al., Chem. Ing. Tech. 43 (1971)
(1977) 4989.
184;
483. L. Bertrand et al., J. Phys. Chem. 72 (1968)
J. F. Knoop, G. R. Neikirk, Hydrocarbon
3926;
Process. 59 (1972) 109;
J. Olbregts, Int. J. Chem. Kinet. 11 (1979)
PPG, GB 913 040, 1961 (L. E. Bohl, R. M.
117.
Vancamp); 904 084, 1961 (L. E. Bohl);
484. Wacker, DE 901 774, 1940 (W. Fritz, J. 904 405, 1961 (L. E. Bohl, A. P. Muren, R.
Rambausek). M. Vancamp);
172 Chlorinated Hydrocarbons

916 684, 1961 (R. E. McGreevy, J. E. 511. Rhône-Progil, FR 2 260 551, 1974 (J.-C.
Milam, W. E. Makris); Strini);
969 416, 1962 (A. C. Ellsworth; FMC, ZA 715 780, 1970 (J. S. Sproul, B. R.
1 012 423, 1964 (L. E. Bohl, R. M. Marx).
Vancamp); 512. Diamond Alkali Co., GB 701 244, 1951;
1 027 279, 1963 (L. E. Bohl, R. M. 673 565, 1952;
Vancamp); Hydrocarbon Process. 46 (1967) no. 11, 210.
1 104 396, 1965 (L. W. Piester, R. M. 513. Donau-Chemie AG, DE-OS 1 277 245,
Vancamp); 1965;
Du Pont, GB 1 362 212, 1974, FR 1 525 811, 1966 (F. Samhaber);
US 3 232 889, 1966; NL 6 607 204, 1966.
R. L. Espada, Ion 36 (1976) 595; 514. Donau Chemie AG, GB 1 143 851, 1967 (F.
L. M. Kartashov et al., Khim. Prom-st. Samhaber).
(Moscow) 1983, 587; 515. Diamond Shamrock Corp., US 3 860 666,
Z. Trocsanyi, J. Bathory; Kolor. Ert. 17 1976 (N. L. Beckers).
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L. Dubovoi et al., Khim. Prom.-st. (1967) 1482;
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499. Du Pont, US 3 697 608, 1972 (H. E. Bellis); 255.
4 130 595, 1978 (H. E. Bellis); 517. Dow Chemical, US 2 442 323, 1944 (C. W.
Sumitomo Chemical Co., Ltd., DE-OS Davis, P. H. Dirstine, W. E. Brown);
2 413 148, 1977 (K. Iida, T. Takahashi, S. 2 442 324, 1944 (R. G. Heitz, W. E. Brown);
Kamata); 2 577 388, 1945 (G. W. Warren).
518. Stauffer, US 2 857 438, 1957 (R. P. Obrecht,
Marathon Oil Co., US 3 689 578, 1972 (D.
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178 Chlorinated Hydrocarbons

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874. Hoechst, Krebskosmos GmbH, DE-OS 897. Toray, EP 125 077, 1984 (K. Miwa et al.).
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 Chlorinated Hydrocarbons 181

919. Gesetz über die Beseitigung von Abfällen (O. C. Norman, L. H. Handler); GB
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182 Chlorinated Hydrocarbons

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