1654 Znd. Eng. Chem. Res.

1994,33, 1654-1656

Decrease in Carbonyl Sulfide in the Feed to Claus Converters by Shift

Catalysts
T. A. Gens
BOC Group Technical Center, 100 Mountain Avenue, Murray Hill, New Jersey 07974

Alumina or commercial shift catalysts were used downstream of a Claus burner to shift carbon
monoxide to carbon dioxide before it could react t o form carbonyl sulfide. The shift catalysts were
effective in preventing formation of carbonyl sulfide, thereby decreasing sulfur losses.

Introduction 3H,S 1.50, -+ 3s 3H2O (3)

The principal reaction in the burner in a Claus plant is where much of reaction 2, called the Claus reaction, occurs
the combustion of part of the hydrogen sulfide to form downstream of the burner and reaction 3 is the sum of 1
sulfur dioxide, which can react with more hydrogen sulfide and 2. This equimolar carbon dioxide-hydrogen sulfide
to form sulfur. The Claus catalytic converters downstream mixture in the feed, therefore, produced a product gas
from the burner bring this sulfur-forming reaction close from the Claus converter, which, after condensation of
to equilibrium, where nearly quantitative recovery as sulfur, was very close to equimolar in carbon dioxide and
condensed sulfur is possible. In practice, both the burner water. The gas temperature in the reactor was measured
and converter effluents contain much carbonyl sulfide by a thermocouple, sheathed in a sintered alumina tube
(COS) and carbon disulfide, which cannot be efficiently and placed just above the porous aluminadisc. The reactor
converted by the Claus catalysts and which must be was wound with heating tape and insulation to decrease
removed by additional costly treatment. These com- the rate of cooling. This produced a temperature drop
pounds originate from homogeneous reactions of sulfur between the combustion zone above the porous disc, at
vapor with carbon dioxide or hydrocarbons at burner temperatures measured as high as 970 OC, and the reactor
temperatures. The conventional treatment for removal exit, where the effluent gas was approximately 300 OC.
of these compounds occurs downstream of the Claus Runs were made with the reactor empty, except for the
converters and involvescatalytic reduction with hydrogen alumina disc, or filled either with small activated alumina
or reducing gas mixtures to convert the sulfur content to spheres (Alcoa, surface area about 250 m2/g) or with shift
hydrogen sulfide, as in the Beavon sulfur removal process catalysts. Two kinds of shift catalysts, both obtained from
(Beavon and Fleck, 1975)and the SCOT process (Swaim, United Catalyst Company, were used: one was principally
1975). A principal route for making COS is the reaction iron and chromium oxide and the other was principally
of carbon monoxide and sulfur vapor below 500 "C (Weil, cobalt and molybdenum oxide. In runs withshift catalysts,
1983). 5 g of alumina spheres, which would not sinter in the hot
Luinstra and d'Haene (1989) observed that alumina at zone, was loaded into the hot lower part of the reactor and
1000 O C effectively decomposes carbonyl sulfide and 22 g of shift catalyst was loaded above the alumina. A
carbon disulfide in the effluent gases from a Claus burner volume of about 4 cm3 remained empty above the shift
and upstream of the Claus converters. The nature of the catalyst. All runs were made at 6 atm absolute pressure.
decomposition reaction was not discussed. Laboratory Pressure was needed to prepare the feed for a pressurized
results presented below indicate that alumina can catalyze Claus reaction operated at 120 "C under water. Results
the water-gas shift reaction at rates that are fast enough with this novel Claus converter have been described
to actually prevent the formation of COS. Further work elsewhere (Gens et al., 1989). Analyses were made on the
using shift catalysts not only supports this possibility but product gas from the Claus converter, after sulfur was
also suggests use of the shift catalysts to improve upon removed, using a Hewlett Packard 5880-A gas chromato-
alumina in preventing formation of COS. Thermody- graph equipped with a 13X molecular sieve column for
namics show that competing shift and COS formation are the lighter nonpolar gases and an Altech Super Q column
both favorable reactions, suggesting that the shift reaction for other gases.
could be encouraged by use of selective catalysts. Results ShowingThatAlumina Affects the Water-
Gas Reaction. The reactants and products of the water-
Experimental Section gas reaction
The reactor was a vertical stainless steel tube 0.4 in. i.d.
by 1 f t long with a volume of 25 cm3. A heated porous
alumina disc (Coor's, 100-pm pores, 40% porosity) of 114
CO + H,O - CO, + H, (4)

are all present in a burner in a Claus plant, so this reaction

in. diameter by 112 in. length in the bottom gas entrance might be expected to influence the final product composi-
served to mix and ignite a mixture of oxygen and feed gas tion. This reaction was investigated by measuring the
containing hydrogen sulfide. This disc had been dipped hydrogen and carbon monoxide content of the product
in dilute potassium permanganate solution to aid ignition gases leaving the Claus converter.
and combustion. The feed was an equimolar mixture of Alumina spheres in the reactor caused a large increase
carbon dioxide and hydrogen sulfide with oxygen adjusted in the Hp/CO ratio, as compared to this ratio with the
(at about 20 % ) for maximum conversion to sulfur: empty reactor (Figure 1, feed flow rate of 3.5 L/min). The
3H,S --
+ 1.50, 2H,S + SO, + H,O
2H,S + SO, 3 s + 2H,O
(1)
increased ratio was observed at reaction temperatures
exceeding 700 O C , measured just above the porous alumina
disc, and the ratio increased with the disc temperature.
(2) The alumina apparently caused reaction 1 to be shifted
QSSS-5SS5/94/2633-1654$Q4.50/0 0 1994 American Chemical Society
 Ind. Eng. Chem. Res., Vol. 33, No.7,1994 1655
12 5

10
.. .

."
0
m 400 6M) 8W 1W
am 7m (UIO om rm TEMPERATURE(C)
TEMPEMTURE IC1 ABOVE POROUS PLUG

1 - EuPp(0.n) -1
ILOMEO Wrm MUUNA (Wll

Figure 2. Reactions of CO with either sulfur or water M favored

Figure I. Aluminacatalyzesthewatergass~reaction.Thereactor below 900 oc.
erittempraturewasabout300~C,wherethevolumeratioofHdC0
would be near 40 at equilibrium. Table 1. Efleet of Catalysts on COS Content.
vol % of each gas in the product stream
in the forwarddirection. Thisshiftislarge,corresponding
to equilibrium in reaction 4 at a temperature not much p flow max bed
more than 100 O C above the 300 "C gas exit temperature. catalyst (L/min) HI CO COS HS SO* T(OC)
(An equilibrium HdCO ratio of 10 would be expected in none 1.9 0.20 0.21 3.12 0.42 0.73
reaction 4 at 420 "C with equal water and earbon dioxide none 3.5 0.21 0.22 2.36 0.02 0.07
partial pressures). It was hypothesized that if reaction 4 none 5.0 0.43 0.81 6.07 0.15 0.05
none 6.3 0.84 1.03 6.35 0.28 0.89
could be shifted sufficiently, the supply of carbon mon- All03 2.5 0.33 0.03 0.31 0.53 0.01 805
oxide, which normally forms in the burner from the Altos 3.5 0.52 0.06 0.29 0.48 0.00 Figure 1
reduction of carbon dioxide, might be depleted enough to CwMo 2.5 0.00 0.01 0.08 0.03 0.01 704
depress the formation of undesirable contaminants, since CwMo 3.5 0.00 0.01 0.13 1.00 0.00 741
carbon monoxidecan reactfurthertomakecabonylsulfide FeCr 2.5 0.07 0.00 0.13 0.01 0.00 797
and possibly other carbon-containing sulfur compounds. FeCr 3.5 0.08 0.01 0.17 0.01 0.00 874
Not only might this explain Luinstra and dHaene's 'Feed was 50%carbon dioxide and 50% hydrogen sulIide with
observation but it would also suggest use of better shift oxygen added o needed to optimize sulfur removal. This produced
catalysts for improved results, since alumina is not a aproductgaswhichwocloseto50% carbondioxideand 50%water
after sulfur removal. The volume of the reactor was 25 ems.
particularly effective shift catalyst.
(sulfur removals of > 99%), provided that the oxygen
Thermodynamics of Competing Reactions of
Carbon Monoxide content of the feed was carefully readjusted to optimize
sulfur removal. In commercial practice, the presence of
The free energy changesforcarbonmonoxidereactions, hydroearbons can cause COS and CS2 concentrations to
either with water in the water-gas reaction or with sulfur increase in theeffluent (Luinstra and dHaene, 1989).The
to form carbonyl sulfide, are both favorable below about absence of this effect here is credited to efficient mixing
900"C, as shown in Figure 2 (free energy data taken from and combustion with the porous alumina disc. Very large
the JANAF Tables). This situation, where both expected heat losses on this small scale permitted operation below
reactions are favorable, is ideal for use of catalysts to try the alumina melting point, even at flow rates several times
to accelerate the desired reaction, which is the water-gas greater than used in this study.
reaction, in preference to the undesired reaction to form
COS, as the gaseous effluent from the reaction furnace is Conclusions a n d Comments
cooled.
These resulta show that alumina, and especially shift
Results Using Shift Catalysts catalysts, were affective in preventing build-up of COS in
the effluent when hydrogen sulfide is combusted in the
Much lower COS concentrations were observed in the presence of carbon dioxide. The ability of these catalysts
product gas from runs using shift catalysts than in runs to preferentially catalyze the water-gas reaction during
using alumina catalyst or, especially, in runs with no the rapid cooling that occurs downstream of the combus-
catalyst in the reactor (Table 1). Either shift catalyst was tion reactions, thereby preventing the reaction of carbon
effective in decreasing the COS concentration. Table 1 monoxide and sulfur to form COS, is presented as the
resultswithaluminawereaveragedfrom thedataofFigure probable explanation. This explanation implies that
1, and similar data, not shown, were taken at the lower prevention of COS formation may be an effective altema-
flow rate of 2.5 L/min. Other data in Table 1 are from tive to the conventional treatments for its removal
individual runs. subsequent to formation.
The addition of about I%,individually, of methane, High removals of sulfur compounds, well above 99%.
ethane, ethylene, or methyl mercaptan to the feed had no were achieved using the shift catalysts. These high
detectable effect upon the product gas over shift catalysts removals were, in part, due to the efficiency of the novel
1656 Ind. Eng. Chem. Res., Vol. 33, No. 7, 1994

Claus converter (Gens et al., 19891, but this converter is Gens, T.; Tucker, M.; Grob, J. Process for the Production of Sulfur
ineffective in converting COS. The avoidance of COS from Hydrogen Sulfide Using High Concentration Oxygen and
through the use of shift catalysts was required in order to Recycle in Combination with a Scrubbing Tower. U.S.Patent
4,844,881, July 4, 1989.
realize the benefit of efficient conversion in the Claus Luinstra, E.; d"aene, P. Catalyst Added to Claw Furnace Reduces
reaction. Conversion by the Claus reaction appears to be Sulfur Losses. Hydrocarbon Process. July 1989, 53-57.
less efficient, in the data of Table 1, for the streams Swaim, C. D. The Shell Clam Ojjgas Treating (SCOT) Process;
containing larger COS concentrations. This is probably Pfeiffer, J. B., Ed.; Advances in Chemistry 139;American Chemical
not actually the case; rather, the larger H2S and SO2 Society: Washington, DC, 1975; pp 111-119.
concentrations in these streams probably originate from Weil, E. D. Sulfur Compounds. In Kirk-Othrner Encyclopedia of
Chemical Technology, 3rd ed.; Grayson, M., Ed.; John Wiley &
hydrolysis of COS downstream of the Claus converter, Sons: New York, 1983; Vol. 22, p 109.
possibly even in the analysis train.
Received for review December 20, 1993
Literature Cited Revised manuscript received March 31, 1994
Accepted April 29, 1994.
Beavon,D. K.; Fleck, R. N. Beavon Sulfur Removal Process for Claus
Plant Tail Gas; Pfeiffer, J. B., Ed.; Advances in Chemistry 139;
American Chemical Society: Washington, DC, 1975; pp 93-99. Abstract published in Advance ACS Abstracts, June 1,1994.