Applied Catalysis A: General 271 (2004) 61–68

Hydrodechlorination over Pd–Pt/Al2 O3 catalysts

A comparative study of chlorine removal from dichlorodifluoromethane,
carbon tetrachloride and 1,2-dichloroethane
M. Legawiec-Jarzyna a , A. Śr˛ebowata a , W. Juszczyk a , Z. Karpiński a,b,∗
a Institute of Physical Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, PL-01224 Warszawa, Poland
b Faculty of Mathematics and Natural Sciences, Cardinal Stefan Wyszyński University, ul. Dewajtis 5, PL-01815 Warszawa, Poland

Accepted 21 January 2004

Abstract

A comparative study of hydrodechlorination of dichlorodifluoromethane, carbon tetrachloride and 1,2-dichloroethane over alumina-
supported Pd–Pt catalysts showed several interesting features in the catalytic behavior. Platinum, the metal which binds chlorine and
chlorine-containing organic intermediate species less strongly than palladium is a better catalyst in CCl4 hydrodechlorination. However,
in hydrodechlorinations of CCl2 F2 and 1,2-dichloroethane platinum offers too weak binding with reaction species, and in effect, Pd/Al2 O3
shows a better catalytic performance than Pt/Al2 O3 . Nevertheless, this positive behavior of Pd/Al2 O3 can still be improved by doping it with
small amounts of platinum. The formation of mixed Pd–Pt ensembles leads to an enhancement of the overall activity and selectivity for partial
hydrodehalogenation. Temperature-programmed hydrogenation (TPH) of deposits accumulated on the catalysts during hydrodechlorination
confirms a better resistance of platinum against carbiding. In the case of Pd/Al2 O3 and Pd–Pt/Al2 O3 catalysts, massive amounts of coke (and
chlorine) were found after CCl4 reaction.
© 2004 Elsevier B.V. All rights reserved.

Keywords: Pd–Pt/Al2 O3 ; Hydrodechlorination; Dichlorodifluoromethane; Carbon tetrachloride; 1,2-Dichloroethane; Synergistic effects

1. Introduction (HFCs) [4], whereas Pt seems better than Pd in a gas phase

hydrodechlorination of carbon tetrachloride to chloroform
Catalytic hydrodechlorination of organic wastes contain- [5,8,12]. Apart from variations in the selectivity, these
ing a variety of toxic and ozone-depleting compounds has metals often exhibit different durability; e.g. palladium
recently attracted increasing interest [1,2]. Several catalysts catalysts show a rather short lifetime in carbon tetrachlo-
were tested in fundamental studies, and then proposed in ride hydrodechlorination carried out in the gas phase [12].
patent applications (references in [3]). Among the catalytic Our reason to perform comparative studies of hydrodechlo-
metals, platinum and palladium seem to play the most im- rination of different chlorine-containing compounds was
portant role in chlorine removal from organic molecules two-fold. First, it was interesting to find out what can be
[4–16]. Supported on various carriers (like Al2 O3 , AlF3 , achieved by combining various functions of multicompo-
active carbon, silica, magnesia, etc.), these metals appeared nent catalysts. Quite often significant synergistic effects
very effective in chlorine elimination from chlorofluoro- were detected in such cases [17]. Second, if one metal is
carbons (CFCs) and chloroalkanes. One has, nevertheless, better than the other in one catalytic application and the
to note some differences in the catalytic behavior of these situation is reversed for another application, one would be
metals. For instance, Pd is a unique catalyst in the selec- interested in preparation of a more versatile catalyst, which
tive hydrodechlorination of CFCs to hydrofluorocarbons could be used in a catalytic treatment of a multicomponent
chlorine-containing waste. With these ideas in mind, we
decided to test alumina-supported palladium-platinum cat-
∗ Corresponding author. Tel.: +48 22 6324593; fax: +48 22 6325276. alysts in hydrodechlorination of CCl2 F2 (CFC-12), carbon
E-mail address: [email protected] (Z. Karpiński). tetrachloride and 1,2-dichloroethane.

0926-860X/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2004.01.036
62 M. Legawiec-Jarzyna et al. / Applied Catalysis A: General 271 (2004) 61–68

2. Experimental mixture) were purified by passing through drying traps with

final purification over MnO/SiO2 .
2.1. Catalyst preparation and characterization
2.2. Catalytic tests
The monometallic, 1 wt.% metal-loaded, palladium
and platinum catalysts were prepared by incipient wet- The reactions of hydrodechlorination of 1,2-dichloro-
ness impregnation of alumina (Alumina Catalyst Shell ethane, carbon tetrachloride and dichlorodifluoromethane
S618, 240 m2 /g, pore volume 0.8 cm3 /g, 75–120 mesh, acid were carried out at atmospheric pressure, in glass flow re-
washed and precalcined at 550 ◦ C). Before each impreg- actors equipped with fritted disks to place a catalyst charge.
nation the support was dried in an air oven at 100 ◦ C for Prior to reactions, all catalysts were reduced in flowing
20 h. The Pd/Al2 O3 was prepared from an aqueous solution 10% H2 /Ar (25 cm3 /min), ramping the temperature from
of palladium dichloride (analytical reagent from POCh, 20 to 400 ◦ C (at 8 ◦ C/min) and kept at 400 ◦ C for 3 h. All
Gliwice, Poland). For preparation of the Pt/Al2 O3 , chloro- reactions were followed by gas chromatography (HP 5890
platinic acid was used. It was prepared by dissolving Pt wire Series II with FID, a 5% Fluorcol/Carbopack B column
(Johnson Matthey Grade 1) in a hot mixture of hydrochloric (10 ft) from Supelco). The results of GC analysis were
and nitric acids (volume ratio 1:10, both of analytical purity elaborated using HP Chemstation.
from POCh, Gliwice, Poland). During impregnation and In the catalytic conversion of 1,2-dichloroethane (HPLC
preliminary drying with infrared lamps, a good mixing was grade, 99.8% pure from Sigma–Aldrich, Germany) the flows
assured by the rotary motion of a beaker containing catalyst of all gases, except 1,2-dichloroethane, were fixed by us-
precursor components. Then, the solids were further dried ing Bronkhorst Hi-Tec mass flow controllers. After reduc-
overnight at an air oven at 90 ◦ C. tion, the catalysts were cooled to 200 ◦ C, then contacted
A series of bimetallic Pd–Pt/Al2 O3 catalysts were pre- with the reaction mixture, i.e. with a flow of hydrogen
pared by incipient wetness coimpregnation of alumina with + argon at 41.2 cm3 /min and 1,2-dichloroethane, provided
appropriate amounts of dissolved palladium dichloride and from a saturator kept at 0 ◦ C (to give the partial pressure
chloroplatinic acid. After impregnation and preliminary dry- of 1,2-dichloroethane of 2.9 kPa). The partial pressure ratio
ing in the rotating beaker, the Pd–Pt catalyst precursors were PH2 /PC2 H4 Cl2 was 1:1. The mass of catalysts used ranged
dried overnight at 90 ◦ C and stored in a desiccator. All the between 16 and 33 mg, depending on the catalyst in order to
catalysts prepared in this work are listed in Table 1. not exceed conversion levels beyond 10% (at steady state).
The prepared catalysts were reduced in flowing 85% In all kinetic runs, the activities of most catalysts declined
H2 /Ar (25 cm3 /min), ramping the temperature from 20 with time-on-stream. A typical run lasted ∼24 h.
to 400 ◦ C (at 8 ◦ C/min) and kept at 400 ◦ C for 3 h. After A similar reaction protocol was adopted for CCl4 and
a subsequent purge in argon flow at 400 ◦ C for 1 h, the CCl2 F2 hydrodechlorinations. CCl4 (analytical reagent from
catalysts were characterized by H2 chemisorption (results POCh, Gliwice, Poland, purity >99.6%) was fed in the same
in Table 1). Hydrogen chemisorption experiments were fashion as 1,2-C2 H4 Cl2 , i.e. from a saturator kept at 0 ◦ C,
performed in a pulse-flow system at 70 ◦ C, as described whereas in the case of CCl2 F2 , the reactant was supplied
elsewhere [18]. The thermal conductivity detector (TCD, from a gas tank (Galco S.A., Belgium; purity 99.9%). The
Gow-Mac) was kept at 0 ◦ C, providing constant response flows of gases (H2 , Ar, CCl2 F2 ) were fixed by MKS mass
during each run. All the gases used (H2 , Ar and 85% H2 /Ar flow controllers to obtain feed partial pressures: 2 kPa for
CCl2 F2 and 20 kPa for H2 , in an argon carrier. Hydrogen and
argon were purified by MnO/SiO2 , and the overall flow rate
Table 1 of the reactant gas mixture was 100 cm3 /min. In the case of
Alumina-supported Pd–Pt catalysts used in this work
CCl4 hydrodechlorination the CCl4 /H2 ratio was 1:7 (with
Catalyst Overall metal Metal Metal the total flow of ∼29 cm3 /min).
designationa loading (wt.% fraction particle Blank experiments with alumina showed very low activity
Pd + Pt) exposedb sizec (nm)
in the temperature range used for screening Pd/Al2 O3 cat-
Pd100 1.0 0.77 1.5
alysts, i.e. ≤200 ◦ C for 1,2-C2 H4 Cl2 and CCl2 F2 reactions,
Pd95Pt5 1.1 0.63 1.8
Pd90Pt10 1.2 0.44 2.5 and ≤90 ◦ C for CCl4 hydrodechlorination.
Pd80Pt20 1.45 0.60 1.9
Pd50Pt50 2.8 0.49 2.3 2.3. Temperature-programmed hydrogenation of used
Pd20Pt80 1.1 0.36 3.1 Pd–Pt/Al2 O3 catalysts
Pt100 1.0 0.54 2.1
a In the notation PdXPtY, X and Y denote atomic percentages of Pd
After kinetic runs the catalysts were investigated by a
and Pt (X + Y = 100%). temperature-programmed hydrogenation (TPH) to detect
total , where Mtotal = Pdtotal
b From hydrogen chemisorption as H/M
species which can be removed by hydrogen from used
+ Pttotal .
c Based on H/M
total from H2 chemisorption (dnm = 1.12/(H/Mtotal ),
catalysts. Progress of TPH runs, using a 10% H2 /He flow
[19]. (25 cm3 /min) at a 10 ◦ C/min ramp, was followed by mass
 M. Legawiec-Jarzyna et al. / Applied Catalysis A: General 271 (2004) 61–68 63

spectrometry (MA200, Dycor-Ametek, Pittsburgh). Several 100 60

masses were monitored during the experiment, but major
changes were seen only for m/z 15 and 16 (methane evolu- 50
80
tion). Attention was also focused at changes in m/z 36 and
38, which are suggestive of HCl liberation from used cata-

Selectivity for CHClF2, %

Selectivity for CHCl3, %

40
lysts. Only the results of testing the catalysts after CCl2 F2 60
and CCl4 reactions were analyzed. The use of very small
30
catalysts charges in 1,2-C2 H4 Cl2 reaction (16–33 mg) re-
sulted only in some hardly visible changes in the respective 40
mass spectra and will not be discussed here. 20

20
10
3. Results
0 0
Prepared Pd–Pt/Al2 O3 catalysts showed a significant de- 0 20 40 60 80 100
gree of metal dispersion (fraction exposed (FE) = 0.36–0.77, Atom % Pt
Table 1). The monometallic Pd100 showed the highest metal
Fig. 2. The effect of Pd–Pt alloying on CHCl3 selectivity in CCl4 hy-
dispersion (FE = 0.77), whereas the rest of samples exhib- drodechlorination at 90 ◦ C (circles) and CHClF2 selectivity in CCl2 F2
ited roughly similar metal dispersion, FE = 0.51 ± 0.15. It hydrodechlorination at 180 ◦ C (squares).
means that the monometallic Pd100 catalyst would be char-
acterized by mean metal particle size of ∼1.5 nm (≈1.12/FE, 100 25
[19]), whereas the other samples should contain metal parti-
cles 2–3 nm in size (Table 1). This fact, in combination with
low metal loading and high background from ␥-alumina, 80 20
precluded use of X-ray diffraction for studying the metal
Selectivity for C2H5Cl, %
Selectivity for CH2F2, %

phase. In addition, very small difference in the lattice pa-

rameter of Pd (0.389 nm) and Pt (0.392 nm) in fact ruled 60 15

out diffraction methods from diagnosing the composition of

bimetallic Pd–Pt phases.
40 10
All catalysts showed a marked deactivation during the ini-
tial period of reaction. Steady-state data (typical results pre-
sented in Table 2) were used for further interpretation and 20 5
are shown in Figs. 1–5. The main attention was paid to the
effect of Pd–Pt alloy composition on the activity and selec-
0 0
0 20 40 60 80 100

0.06 0.025 Atom % Pt

Fig. 3. The effect of Pd–Pt alloying on C2 H5 Cl selectivity in 1,2-di-

0.05 chloroethane hydrodechlorination at 200 ◦ C (circles) and CH2 F2 selectivity
0.020 in CCl2 F2 hydrodechlorination at 180 ◦ C (squares).
TOF, s-1 (CCl2F2, CCl4)

0.04
TOF, s-1 (C2H4Cl2)

0.015 tivity. These important catalytic measures were compared for

0.03 hydrodechlorination of three different chlorine-containing
organic compounds: dichlorodifluoromethane, carbon tetra-
0.010
0.02
chloride and 1,2-dichloroethane.

0.005
0.01
4. Discussion

0.00 0.000 The performance of Pd and Pt, two of the most frequently
Pd 20 40 60 80 Pt investigated metals in catalytic hydrodechlorination, is de-
Atom % Pt pendent on the reactant subjected to chlorine removal. There
Fig. 1. The effect of Pd–Pt alloying on overall activity in hydrodechlori- are reactions in which Pd shows an exceptional performance,
nation of 1,2-dichloroethane at 200 ◦ C (circles), CCl2 F2 at 180 ◦ C, (tri- to such reactions one can include CFCs hydrodechlorina-
angles) and carbon tetrachloride at 90 ◦ C (squares). tion. However, there are also reactions, like the gas phase
64 M. Legawiec-Jarzyna et al. / Applied Catalysis A: General 271 (2004) 61–68

Table 2
Representative kinetic data of hydrodechlorination over Pd–Pt/Al2 O3 catalysts: product selectivities and turnover frequencies
Catalysta Product selectivity (%) Turnover frequencyb (s−1 )

CCl2 F2 hydrodechlorination at 180 ◦ Cc

CH4 CH2 F2 CClF3 CH3 Cl CHClF2 CH2 ClF

Pd100 44.7 46.2 2.8 3.0 1.3 1.8 0.0040

Pd95Pt5 32.1 53.9 3.4 6.3 0.5 2.4 0.0053
Pd90Pt10 34.1 57.5 1.0 2.5 3.0 1.9 0.0107
Pd80Pt20 31.5 59.2 1.3 2.6 3.3 2.1 0.0083
Pd50Pt50 35.4 48.8 0.6 7.5 6.2 1.5 0.0061
Pt100 56 9 0.5 7 28 – 0.00075
CCl4 hydrodechlorination at 90 ◦ C

CH4 C2 H 4 + C 2 H6 C3 H6 + C 3 H8 C4+ d CHCl3

Pd100 20.4 20.3 11.3 33 14.2 0.0020

Pd80Pt20 59.9 9.6 5.1 8 16.7 0.0036
Pd50Pt50 78.9 3.6 1.0 – 16.5 0.0024
Pd20Pt80 59.9 3.2 – – 36.9 0.0054
Pt100 11.1 3.2 – – 88.4 0.0200
ClCH2 –CH2 Cl hydrodechlorination at 200 ◦ Ce

CH4 C2 H4 C2 H6 C2 H5 Cl 1,2-C2 H2 Cl2

Pd100 1.7 0.03 88.7 5.1 3.9 0.0224

Pd95Pt5 1.1 0.02 88.5 9.8 0.5 0.0209
Pd90Pt10 1.0 0.01 88.5 9.8 0.4 0.0326
Pd80Pt20 0.9 – 86.4 12.1 0.5 0.0273
Pd50Pt50 0.3 – 88.1 11.3 0.2 0.0509
Pd20Pt80 1.0 0.04 83.9 10.1 4.9 0.0148
Pt100 1.2 0.1 84.6 3.1 9.4 0.0066
a For catalyst designation see Table 1.
b Based on metal dispersion data shown in Table 1.
c Other minor products are CHF3 , C2 H6 and CH2 Cl2 .
d Higher hydrocarbons and chlorohydrocarbons.
e Other minor products are C2 H3 Cl, C3 H8 and C4 H10 .

hydrodechlorination of carbon tetrachloride, in which plat- tion may follow from simple consequences of the Sabatier
inum shows a more attractive catalytic behavior than pal- principle [22]. If the C–Cl bond dissociation presents a criti-
ladium. Table 2, which collects kinetic data of this work, cal step in hydrodechlorination, then a relatively weak bond-
demonstrates this relation, in agreement with works [1–16]. ing with platinum surface, so advantageous in the case of
In addition, palladium quickly deactivates and exhibits a CCl4 hydrodechlorination, would be less satisfactory for Cl
rather poor selectivity at steady state, giving a variety of removal from those organic compounds in which the C–Cl
products, including longer hydrocarbons. The latter ten- bond is much stronger. In such a case palladium is a more
dency noticed by others [5,10,14–16] was also observed in efficient (than platinum) chlorine abstraction agent. Table 3
this study (Table 2). shows that the dissociation energy of the C–Cl bond is in
The reason for such a distinction may well be a differ- fact higher for CCl2 F2 and 1,2-C2 H4 Cl2 molecules, com-
ent affinity of both metals to chlorine and other intermedi- pared to CCl4 . In line with the above-mentioned interpre-
ate species playing a role in catalytic hydrodechlorination. tation are earlier results of Weiss et al. [8], who studied
Platinum is a more noble metal than palladium, so one can the catalytic hydrodechlorination of C1 compounds: CCl4 ,
expect that both the reactants and reaction intermediates
are less strongly bonded to the surface of platinum than in
the case of palladium catalysts. Accordingly, Erley found Table 3
Dissociation energies of Cl–C bonds in reactants used in this work
that the activation energies of chlorine desorption from Pt
surfaces are considerably lower from the respective values Chlorine–carbon Dissociation Literature
characteristic for Pd single crystals: 199 versus 253 kJ/mol bond energy (kJ/mol) source
for (1 1 1) planes [20] and 249 versus 272 kJ/mol for (1 1 0) Cl–CCl3 305.9 ± 7.5 Ref. [24]
planes [21]. Different affinities of both metals for chlorine Cl–CClF2 346.0 ± 13.4 Ref. [24]
Cl–CH2 CH2 Cl 348.1 ± 9.6 Ref. [25]
suggest that their catalytic performance in hydrodechlorina-
 M. Legawiec-Jarzyna et al. / Applied Catalysis A: General 271 (2004) 61–68 65

sition of Pd–Pt alloys. It is seen that these maxima exist for

CCl2 F2 and 1,2-C2 H4 Cl2 reactions. In the case of CCl4 hy-
drodechlorination, Pt is a much more active catalyst than Pd
and Pd–Pt bimetallic systems. Even though a more rigorous
discussion of this point is complicated due to lack of know-
Pd100 ledge about the surface composition of Pd–Pt alloys (inci-
Mass signal, a.u.

dentally, one can expect a serious surface enrichment in Pd,

[23]), it is worth stressing that the presence of mixed Pd–Pt
ensembles seems to be beneficial for chlorine removal from
Pd80Pt20 those compounds in which chlorine atom is more strongly
Pd50Pt50 bonded. Although a complete analysis of the situation on
the catalyst surface is difficult because of a great variety of
species (chlorine/chloride, carbonaceous deposits, including
Pd20Pt80 halogen-containing polymers) attached more or less strongly
Pt100 on the metal surface, the C–Cl bond dissociation appears to
be a rate-determining step in hydrodechlorination.
100 200 300 400 500 600 700 As mentioned, in the case of CCl4 hydrodechlorination,
Temperature, oC
strengthening dechlorination capability of platinum by mix-
ing it with palladium does not produce good results. The
Fig. 4. HCl (as m/z 36) evolution during temperature-programmed hydro- overall activity decreases rapidly with introducing small
genation of Pd–Pt/Al2 O3 catalysts used in CCl4 reaction. For presenta- amounts of palladium (Fig. 1 and Table 2). Besides, replace-
tion, mass signal intensities were recalculated per metal surface area (i.e.
after considering metal loading and dispersion). For catalyst designation,
ment of only one Cl atom in CCl4 molecule by H atom
overall metal loading and dispersion, see Table 1. (chloroform is a desired reaction product) is more efficiently
achieved with the Pt catalyst than with Pd–Pt supported al-
CHCl3 , CH2 Cl2 and CH3 Cl. It appeared that the last three loys. The selectivity toward chloroform shows similar vari-
compounds (in which the C–Cl bond is stronger than that in ations as TOF with the Pd–Pt alloy composition (Fig. 2). An
CCl4 [24]) were almost unreactive at the conditions of CCl4 increasing amount of Pd in Pd–Pt reinforces dechlorination
hydrodechlorination. strength of the metal surface and results in the formation of
Interestingly enough, introduction of platinum to palla- deeply dechlorinated products (CH4 , C2 -hydrocarbons). In
dium provides a convenient method of tuning dechlorina- accordance with such a behavior, a partial hydrodechlori-
tion capability of metal surface. Fig. 1 shows the presence nation of CCl2 F2 , represented as the selectivity to CHClF2 ,
of maxima in the relation between TOF versus the compo- shows a parallel relation with Pd–Pt composition (Fig. 2).

5e-9

6.0e-8
4e-9

3e-9 5.0e-8
Pd100
Pd100
Mass signal, a.u.

2e-9
Pd95Pt5 4.0e-8
Pd80Pt20
1e-9 Pd90Pt10
Pd50Pt50
Pd80Pt20 3.0e-8
0e+0 Pd50Pt50 Pd20Pt80

Pt100 2.0e-8
-1e-9
Pt100

-2e-9 1.0e-8
0 100 200 300 400 500 100 200 300 400 500 600 700 800
o o
(a) Temperature, C (b) Temperature, C

Fig. 5. Methane evolution during temperature-programmed hydrogenation of used Pd–Pt/Al2 O3 catalysts after hydrodechlorination of CCl2 F2 (a) and
CCl4 (b). Mass 15 was selected for presentation because CH4 liberation observed by monitoring mass 16 is somewhat misinterpreted due to evolution
of water (especially around 100 ◦ C). Comparable catalyst weights (0.1 g) were used.
66 M. Legawiec-Jarzyna et al. / Applied Catalysis A: General 271 (2004) 61–68

In the case of CCl2 F2 the presence of mixed Pd–Pt sites activity as well as the selectivity. This synergistic effect must
is beneficial for reaching a good selectivity for CH2 F2 , a follow from a considerable effect of interaction between pal-
desired product of this hydrodechlorination (Fig. 3). Again, ladium (active component) and platinum (much less active
as in the case of changes in TOF for this reaction (Fig. 1), a component). A similar, although less distinct relation was
considerable enhancement of the selectivity towards difluo- found for the selectivity towards ethyl chloride formation
romethane (from 46 to ∼60%, at 180 ◦ C) is obtained upon from 1,2-C2 H4 Cl2 (Fig. 3). Although reaction mechanisms
introducing small amounts (up to 20 at.%) of platinum to pal- involved in these two processes are probably different (i.e.
ladium. Further increase of platinum content lowers both the adcarbenes in CH2 F2 formation from CCl2 F2 [26,27] and

100

90

80
Conversion, %

o
flow of CCl4 stopped, reduction at 350 C

20

10

0 1000 2000 3000 4000

Time on stream, min

80

60
Product selectivity, %

40

20

0 1000 2000 3000 4000

Time on stream, min

Fig. 6. Time on stream behavior of Pd50Pt50 (0.153 g) in CCl4 hydrodechlorination at 90 ◦ C. Upper section, changes in conversion; bottom section,
changes in product selectivity. Overall conversion (filled circles). Selectivities to: methane (white circles), ethane (white squares), C3+ products (filled
triangles) and CHCl3 (filled reversed triangles). Arrows indicate two short (15 min) periods of catalyst re-reduction at 350 ◦ C.
 M. Legawiec-Jarzyna et al. / Applied Catalysis A: General 271 (2004) 61–68 67

adalkyl species in Cl substitution by H [28] in 1,2-C2 H4 Cl2 ) returns to a level exhibited before the TPH run. Such a result
one can notice that both reactions involve chlorine replace- would suggest that the main reason of a continuous deacti-
ment at one carbon atom. vation is the formation of carbonaceous deposits, not metal
Steady-state catalytic behavior of Pd–Pt/Al2 O3 in hy- surface chloriding. However, changes in the selectivity (bot-
drodechlorination is associated with the extent of catalyst’s tom section of Fig. 6) reveal interesting changes generated
deactivation during reaction. Following other results by short reduction periods. It appears that the selectivity
[15,29,30], we consider that the deactivation would be for CHCl3 is considerably increased (at the expense of
caused by blocking active sites by surface chlorine/chloride methane) just after finishing all reduction periods. Later in
or organic coke. The TPH of used catalysts brought about time, the selectivity toward CHCl3 is noticeably decreased,
some interesting results (Figs. 4 and 5). First, it should be but still keeps a higher value than the respective level before
mentioned that TPH after CFC-12 reaction revealed only re-reduction of the catalyst. Such a behavior suggests that,
minute amounts of chlorine in used Pd–Pt/Al2 O3 cata- although the overall activity is largely determined by the
lysts (not shown). However, TPH of the catalysts tested amount of deposited carbonaceous material, nevertheless
in CCl4 hydrodechlorination showed the presence of Cl in the re-reduction of a coked catalyst may result in some re-
the catalysts, removed from the surface as HCl (Fig. 4). construction of the carbonaceous residues. It seems possible
Although the detailed source of deposited Cl is not obvi- that changes in the structure of coke would lead to the for-
ous (i.e. chlorinated metal species or chlorine associated mation of a variety of active sites associated with a different
with deposited coke), evolution of hydrogen pressure (m/z degree of steric constraints, and contribute to selectivity
2, not presented) clearly shows that desorption of chlorine changes. The presence of different active centers related to
needs hydrogen from the gas phase. Desorption of HCl specific sites in the coke structure has recently been pro-
takes place at ∼200–350 ◦ C, and moreover, the amount posed by Borodziński and co-workers [31,32] in his mech-
of liberated HCl depends on catalyst (Fig. 4). In the case anism of selective hydrogenation of acetylene on palladium
of Pt100, hydrodechlorination of CCl4 leads to deposition catalysts.
of only small amounts of Cl, whereas Pd and Pd–Pt cat-
alysts contain much more surface chlorine. Whether or
not some part of this chlorine originates from alumina, it
5. Conclusions
is not settled (possibly the peculiar shape of TPH peak
of HCl results from the fact that the high temperature
A comparative study of hydrodechlorination of dichloro-
shoulder, at ∼300–350 ◦ C, is due to chlorine removal from
difluoromethane, carbon tetrachloride and 1,2-dichloro-
alumina).
ethane over alumina-supported Pd–Pt catalysts revealed
Methane evolution in the course of TPH runs is associated
several interesting changes in the catalytic behavior. Plat-
with hydrogenation of carbonaceous residues (Fig. 5). Much
inum, the metal which binds chlorine and chlorine-containing
larger amounts of carbon are removed from the catalysts
organic intermediate species less strongly than palladium is
used in CCl4 hydrodechlorination (consider different scales
a better catalyst in CCl4 hydrodechlorination. In the case
of the Y axis in Fig. 5a and b). In addition, the catalysts tested
of Pd/Al2 O3 , the catalyst quickly deactivates. However,
in CCl4 conversion “release” methane at higher temperature
in hydrodechlorinations of CCl2 F2 and 1,2-dichloroethane
than the analogous samples investigated in CCl2 F2 reaction.
platinum offers too weak binding with the reaction inter-
It is considered that an apparent absence (or very negligible
mediates. In effect, in these reactions, Pd/Al2 O3 is a much
amounts) of chlorine on Pd–Pt catalysts used in CCl2 F2
better catalyst than Pt/Al2 O3 . Nevertheless, a marked deac-
reaction make coke hydrogenation easier than in the situation
tivation associated with hydrodechlorination on Pd/Al2 O3
when the metal sites needed for hydrogen activation are still
may be lessened by adding platinum. In addition, due
blocked by chlorine species. Again in the case of deposited
to weakening of the metal-reactant bonds, Pt addition to
chlorine, both in CCl4 and CCl2 F2 reactions, platinum is
Pd leads to some improvement in the selectivity toward
less extensively covered by carbonaceous species than Pd
partial hydrodechlorination. Temperature-programmed hy-
and Pd–Pt bimetallic catalysts.
drogenation of carbonaceous deposits accumulated on
In an attempt to establish reasons of catalyst’s deactiva-
the catalysts during hydrodechlorination run confirms
tion in CCl4 conversion we decided to make use of our TPH
a better resistance of platinum against deactivation by
runs and to reinvestigate the catalytic behavior of one spent
selfpoisoning.
PdPt/Al2 O3 catalyst (Pd50Pt50) after subsequent removal
of chlorine from its surface. According to the TPH spectra
(Fig. 4), deposited chlorine/chloride species should be re-
moved from the catalyst in effect of a short H2 treatment at Acknowledgements
∼350 ◦ C. Accordingly, the Pd50Pt50 catalyst was subjected
to a few chlorine removal operations during its screening in This work was supported in part by the Polish State
CCl4 reaction. Fig. 6 shows the results. It appears that after Committee for Scientific Research (KBN) within Research
returning the flow of CCl4 the overall conversion quickly Project 4 T09B 098 24.
68 M. Legawiec-Jarzyna et al. / Applied Catalysis A: General 271 (2004) 61–68

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