CARBON ISULFIDE PR

Effect of Catalysts on Reaction of Methane with Sulfur

CARLISLE M. THACKER AND ELMER MILLER
The Pure Oil Company, Chicago, Ill.

High yields of carbon disulfide can be obtained by the reac- mine equilibrium conversions for six reactions of methane with
tion of methane with sulfur at 700' C. and below when the sulfur which appeared most likely to occur under the conditions
reaction is carried out in the presence of a suitable cata- of the investigation. Calculations were also made to determine
lyst. Catalysts of the activated clay types give much the equilibrium for the reaction of hydrogen sulfide with methane
higher yields under given conditions than do other types to produce carbon disulfide. The seven reactions considered
of catalysts, such as metallic oxides, metallic sulfides, were as follows:
activated charcoal, etc. Catalysts particularly suitable for
carbon disulfide production from methane include silica
gel, activated alumina or promoted activated alumina, and
Florite. With activated alumina containing a small
amount of chromium oxide, a conversion to carbon disul-
fide of over 90% of the charged methane can be effected
The free energies of these reactions are given in Table I.
below 700' C.
The theoretical conversions a t equilibrium are shown in Figure 1.
With the exception of curve 7, the figure defines onlv the limits
of equilibrium conversions possible, since a t least three re-

I N 1736 Lampadius first synthesized carbon disulfide by

heating sulfur with charcoal. The manufacture of carbon
disulfide by this reaction is now a well established industry.
Two methods are now in use in this country-the retort and the
actions are taking place simultaneously due to the presence of
the three molecular species of sulfur. Figure 1 shows practically
complete conversion of methane to carbon disulfide and hydrogen
electrothermal. In the first, reaction takes place in direct- sulfide in the range 500' to 700" C. Below 700" C. the equi-
fired retorts of cast iron or refractory firebrick. The electro- librium is not so favorable for conversion to carbon disulfide
thermal process involves internal heating by an electric current and hydrogen. The equilibrium is even less favorable for car-
passing through the bed of charcoal. T o obtain a sufficiently bon disulfide production a t 700' C. from methane and hydrogen
high reaction rate, temperatures of 800" to 1000' C. are required; sulfide.
rapid deterioration of equipment results in the retort process, MATERIALS AND CATALYSTS
and high consumption of electrical energy in the electrothermal
The methane was 92% grade, obtained from Carbide and
process. Both methods require specially prepared charcoal Carbon Chemicals Corporation. Specifications require the
which materially adds to the cost of manufacture. following: Not less than 92% methane by volume, not more than
Methane and many other hydrocarbons offer possibilities as 4.5% air, not more than 2% ethane, and not more than 2%
cheap raw materials for carbon disulfide manufacture. A nitrogen. Prior to use, this methane was passed a t 300' C. over
number of patents have been issued on proposed processes freshly reduced copper turnings to remove oxygen. I n earlier
utilizing methane or other hydrocarbons. De Simo ( 7 ) recently work, commercial sulfur flowers was used; later, sublimed sulfur
patented a catalytic process for converting methane with sulfur was employed to reduce fouling of check valves in the sulfur
vapors into carbon disulfide at 800' to 1000' C. It has also
pump. There was no detectable difference in the reaction with
been proposed to produce carbon disulfide by the reaction of the two grades of sulfur. All catalysts were in granular form
methane with hydrogen sulfide ( 6 , 10). Such methods require of 8 t o 14 mesh size, as follows:
temperatures of 800" to 1000" C. for successful conversions of
saturated hydrocarbons. The use of acetylene and other 1. Manganese dioxide (25% by weight) on kieselguhr. Pre-
unsaturates (4, 5 ) permits low-reaction temperatures, but these pared from manganous chloride by chlorine oxidation in the
raw materials have not been used in commercial operations, presence of sodium hydroxide, followed by water washing until
probably because side reactions result in a low efficiency of con- free of chlorides.
2 . Alumina-manganese, approximately 20 to 1. Prepared
version to carbon disulfide. from manganese nitrate and Alorco, grade A, by addition of am-
This article is based on investigations to develop catalysts monium sulfide.
that would cause high rates of reaction a t or below 700" C., 3. Alumina-vanadium, approximately 20 to 1. Prepared by
a temperature range much lower than had previously proved impre nating Alorco, grade A, with ammonium metavanadate.
4. Surified. silica gel. Prepared by extracting silica gel, com-
feasible for reactions of methane with sulfur. The more favor- mercial grade, with hydrochloric acid, followed by washing with
able catalysts to be discussed were disclosed in a recent patent (8). water.
5. Alumina-chromium ap roxiniately 20 to 1. Prepared by
THEORETICAL CON SIDERATIONS impregnating Alorco, grade 1,
with chromic acid.
I n the temperature range 500" to 700" C. calculations are
complicated by the various modifications of sulfur that are
present in the vapors. Although no appreciable amounts of I. FREEENERGIES
TABLE PRODCCING
OF REACTIONS CARBON
monatomic sulfur are present in this range, a t 500" C. sulfur
vapors contain three molecular species, Sa,Se,and SZ. As the
temperature rises, the concentrations of the heavier modifica-
Temp.
OK.
- DISULFIDE
1
FROM METHANE

2
Reaction Number
3 4 6 6 7
700 -27,780 -17,900 -17,820 -1120 3,860 3,860 25,450
tions decrease, and the result is a gas that is almost free of Sa 800 -28,170 -23,290 -23,890 -3790 -1,360 -1.650 20,510
900 -28,580 -28,740 -30,060 -6520 -6,600 -7,260 15,450
and Ss at 700' C., a t or below atmospheric pressures. 1000 -28,990 -34,190 -36,230 -9290 -11,890 -12,910 10,310
From free energy data (3, 9) calculations were made to deter-
182
February, 1944 INDUSTRIAL AND ENGINEERING CHEMISTRY 183
6. Florite (activated bauxite). commercial grade. from Flori-
. I - I
with sodium hydroxide, followed by washing with water until
din Company. neutral to litmus.
7. Purified Florite. Prepared by extracting No. 6 with hy-
drochloric acid, followed by washing with water. After drying and screening, the general procedure followed
8. Alorco (activated alumina), grade A, obtained from
Aluminum Company of America. was to heat the catalyst in nitrogen a t reaction temperature
for several hours before use.
100
APPARATUS AND PROCEDURE
The reaction was carried out in an electrically heated 18-8
stainless tube furnace, with a heatin section 18 inches long.
Methane was fed into the bottom of t f e furnace and preheated
as it passed up to the top, where it met sulfur vapors preheated
to reaction temperature. The mixed vapors then passed down
through an inner tube containing the catalyst. The outside tube
serving as a preheater for methane was 2 inches inside diameter
with a 3/le-inch wall; the inner tube containing the catalyst
was 11/2 inches inside diameter with a 1/8-inch wall. I n most
cases about 100 cc. of catalyst were used. The temperature of
the furnace was held constant to 1 3 " C. by a Micromax regula-
tor. Temperatures were determined by a chromel-alumel ther-
mocouple in a stainless steel tube passing through the catalyst
bed.
At the higher temperature there was considerable corrosion of
the 18-8 reactors. I n later experiments (not reported here) a
25-20 alloy withstood the corrosive gases much better than the
original equipment.
Figure 2 gives a flowsheet of the experimental unit. Molten
0 sulfur, a t about 130" C., was pumped from a reservoir t o a
heated coil where it was vaporized and preheated to reaction
TMERATURE, 0 C. temperature. The rate of sulfur feed was determined by cali-
brating the pump before and after each run.
Figure 1. Equilibrium Conversions of Methane to Because of the peculiar viscosity characteristics of liquid sul-
Carbon Disulfide fur, care was exercised in maintaining the temperature of the
sulfur reservoir and transfer lines t o the pump within specified
9. Molybdenum-chromium, approximately 3 to 1, on pumice. limits. As the temperature is raised above the melting point, the
Prepared by impregnating purified pumice with ammonium viscosity of liquid sulfur ( I ) slow:y decreases with increasing tem-
molybdate and chromic acid. Pumice was purified by extracting peratureuntil about 160' C. isreached. Between 160' and 188' C.
the commercial grade
- with hydrochloric acid, followed by wash- the viscosity rapidly increases and reaches a maximum of
ing with water. 93,200 centipoises a t 186-188" C. Further increase in tempera-
10. Alumina-manganese, approximately 20 t o 1. Prepared ture decreases the viscosity. Operation of the sulfur reservoir
by impregnating Alorco, grade A, with manganous chloride. and transfer lines a t about 130' C. was satisfactory, since this
The material was then chlorinated in an alkaline solution, fol- temperature is sufficiently above the melting point of sulfur and
lowed by water washing until free of chlorides. below the high viscosity range t o prevent trouble by small tem-
11. Manganese dioxide-potassium carbonate on kieselguhr. perature gradients in the system.
Prepared by adding 1% by weight of potassium carbonate to The vaporized sulfur met the stream of preheated methane
catalyst 1. and passed through the catalyst bed to a condenser held a t 130' C.
12. Alumina-iron, approximately 20 to 1. Prepared by im- to remove unreacted sulfur. A t high flows a small portion of
pregnating Alorco, grade A, with ferric nitrate. the sulfur passed through the sulfur condenser as a dust and
13. Iron sulfide. Made from the material commonly used
for generating hydrogen sulfide in the laboratory. After breaking settled out in the lines. On leaving the sulfur condenser, the
and screening, it was heated a t 600" C. for 18 hours in hydrogen the gases were passed through a trap cooled with dry ice and
prior to use. methanol where the carbon disulfide and some hydrogen sulfide
14. Cobalt-tungsten, approximately 1 to 10 on purified pum- were condensed. Hydrogen sulfide remaining in the gas was re-
ice. Prepared by im-
pregnating purified
pumice with cobalt ni-
trate and a m m o n i u m
tungstate. Pumice was % Calibration Point
purified as outlined for -w- Valves
catalyst 9.
15. Silica gel, com-
mercial grade. ~

16. Alfrax. commer-

cial grade.
17. Super F i l t r o l ,
commercial grade. An
activated clay used as
received.
18. Activated char-
coal obtained from Car-
bide and Carbon
Chemicals Corporation.
19. Cobalt-tungsten,
approximately 3 to 1 on
purified pumice. Pre-
pared as described for
catalyst 14.
-
20. Thorium nickel,
approximately 3 to 1.
Prepared from thorium
nitrate and nickel ni-
trate by precipitating Figure 2. Flow Sheet of Laboratory Unit for Reaction of Methane with Sulfur
 184 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 36, No. 2

other catalysts investigated; these catalysts belong to the general

class of activated clays. Results in Table I1 as well as miscel-
laneous results in Table I11 are typical of all data obtained in
00 this study of many catalysts. They show clearly that the acti-
vated clay types are excellent catalysts for the reaction of methane
N with sulfur to produce carbon disulfide. Alfrax, metallic oxides
u1
0 or sulfides supported on pumice, nickel sulfide on thoria, acti-
R Bo vated charcoal, etc., are inferior to the clay-type catslysts
reported.
8
f3
40
TABLE111. L t h C E L L . 4 N E O U S DATAOK P R O D T C T I O K O F C A R B O N
*
W
X D I S U L F I D E FROM LIETHANE

w. hIole 70
20 Space Ratio, CHa Con-
Catalyst T:mp., Veloc- CHI: verted to
C, SILICA G a NO. Composition C. ity S1 cs2
4 Silica gel, purified 500 845 0.5 16 5
2 Alz03:lIn = 20: 1 500 810 0.5 8 5
0 8 Alorco 550 690 0.5 26 5
500 550 600 650 700 600 690 0.7 54.0
TEMPWXTJRS, 0 C. 1.3 Silica gel 550 690 0.5 44.8
16 Alfrax 550 715 0.5 0.8
Figure 3. Effect of Temperature on Methane 682 875 0.4 27.D
17 Super Filtro 560 965 0.4 24.5
Conversion to Carbon Disulfide 596 I050 0.4 44.0
18 Activated charcoal 600 915 0.4 36.7
7 Purified Florite 600 800 0.5 59.4
moved by scrubbing with a dilute solution of sodium carbonate. 19 Co:W = 1 : 3 , o n p u m i c e 645 1030 0.4 20.4
20 Th:Ni = 3 : l 648 985 0.4 25.8
The unabsorbed gas, mainly methane, was metered and a sample
taken for analysis.
ANALYTICAL METHODS. The condensate from the dry ice- TABLE
IJ'. EFFECTO F TEMPERATURE
ON R E A C T I O N USING
methanol trap was carefully stabilized in a low-temperature ap- CATALYST
5
paratus to remove most of the hydrogen sulfide. A portion of (Space velocity 870, ratio, C H I : & = 0.5)
the residue was weighed and then diluted with thiophene-free
benzene. This mixture was analyzed by the method of Bell and Run No. 1 2 3 4
Temperature, O C. 548 604 667 680
Agruss ( 2 ) for the following constituents: carbon disulfide, hy- Mole % CH4 converted to CSz 25.2 66.4 75.5 93.5
drogen sulfide, mercaptan sulfur, sulfide sulfur, disulfide sulfur, Stabilized liquid, % sulfur as
and sulfur (nonvolatile material a t 110' C.). gas 1.45 0.81 0.74 0.87
Trace 0 0 0
The gases obtained were analyzed by the usual absorption and 0.03 0.02 0.03 0.04
combustion technique. 0.18 0.10 0.25 0.12
No analyses Tere made on the sulfur recovered.. On solidify- 0 0.60 0.10 0.30
82.8 82.5 82.7 83.1
ing, there was a slight darkening which indicated only small
traces of tarlike materials associated with recovered sulfur.

YIELDS WITH VARIOUS CATALYSTS Table IV illustrates the effect of temperature when using B
Table IIA gives results with a number of catalysts when chromium oxide-activated alumina catalyst (No. 5 ) . EXects
operating a t a space velocity of 825 and a methane-sulfur ratio of temperature when using this and other catalysts are shown
of 0.5. Space velocity is defined here as the total volume of in Figure 3. Table IV also gives analyses of the liquid products
gases at 0" C. and 760 mm. passed through a unit volume of obtained in the four runs with catalyst 5 ; they are typical of
catalyst space per hour. I n calculating the total gas volume, analyses obtained on liquid products from all runs outlined i n
i t is assumed that all sulfur present is in the diatomic form. this article.
Results in Table IIB were obtained under similar conditions Wide ranges of space velocities, with other conditions held
but additional catalysts are included. constant, are not reported here because difficulties were en-
Under the conditions employed, silica gel, activated alumina, countered in adjusting the sulfur pump to give the desired
promoted activated alumina, and Florite are superior to the feed ratios at low flows. Sufficient data are presented, however,
to show a n increase in conversion with decrease in space velocity.
As would be expected, increase in temperature increases the
conversion to carbon disulfide decidedly.
TABLE
11. EFFECT
OF CaTALYSTS O N Y I E L D O F C A R B O N Analysis of the data shows that the reaction of sulfur with
DISULFIDE methane under the conditions described Droceeds without
Mole 70CHI Converted appreciable side reaction according to the equation: CH, -I- 45 =
Catalyst
No. Composition 550' C.
to CSa
60OrC.
CSz +2HzS.
A. Space Velocity 825 : Molal Ratio, CHI: Sz = 0.5
LITERATURE CITED
1 M n0a on kieselguhr 7.1 12.9
2
3
Al2Os:Mn = 2 0 : l
AlqOa: V = 20: 1
....
.... 55.3
51.8
(1) Bacon and Fanelli, J . Am. Chem. SOC.,65, 639-48 (1943).
4 Silica gel 42.1 69.6
(2) Bell and Agruss, IND. ENG.CHEM.,A N ~ LED.,. 13, 297-9 (1941).
5 A1aOs:Cr = 2 0 : l 26.4 65.7 (3) Kelley, U. S. Bur. Mines, Bull. 406 (1937).
6 Florite 23.8 63.9 (4) Komlos, Komlos, and Engelke, Brit. Patent 265,994 (Oot. 27,
7 Purified Florite .... 59.4 1927); German Patent 469,839 (Dec. 29, 1928).
....
8
E.
Alorco 27.4
Space Velocity 775; Molal Ratio, CHI:& - 0.6
(5) Maihle, Chinzie & industrie, 31, 255-61 (1934).
(6) Rakovski and Kamnava. J. Applied Chem. (U.S.S.R.), 13,
1436-41 (1940).
9 hlo: Cr = 3 :1, on pumice 1.0 5.7
10 Al208:h,ln = 2O:l 57.8 (7) Simo, de (to Shell Development Co.), U. S. Patent 2,187,393
11 25% hfnOz-l% KzCOa 7.5 (Jan. 16, 1940).
o n kieselguhr
12 A1zOa:Fe = 2O:l 50.6 (8) Thaoker (to Pure Oil Co.), U. S. Patent 2,330,934 (Oot. 5, 1943).
13 Iron sulfide 4.8 (9) Thacker, Folkins, and Miller, IND.ENO.CHDM.,33, 584-90
14 C o : W = l O : l , on pumice 6.7 (1941).
(10) Waterman and Vlodrop, J . SOC.Chem. Ind., 58, 1Q9-10 (1939).