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Mechanisms of CO and COS Formation in the Claus Furnace
Peter D. Clark, Norman I. Dowling, M. Huang, William Y. Svrcek, and Wayne D. Monnery
Ind. Eng. Chem. Res., 2001, 40 (2), 497-508• DOI: 10.1021/ie990871l • Publication Date (Web): 21 December 2000
Downloaded from http://pubs.acs.org on April 28, 2009

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Ind. Eng. Chem. Res. 2001, 40, 497-508 497

APPLIED CHEMISTRY

Mechanisms of CO and COS Formation in the Claus Furnace


Peter D. Clark,*,† Norman I. Dowling,† M. Huang,† William Y. Svrcek,‡ and
Wayne D. Monnery‡
Alberta Sulphur Research Ltd., c/o Department of Chemistry, and Department of Chemical and Petroleum
Engineering, The University of Calgary, 2500 University Drive N.W., Calgary, Alberta, Canada T2N 1N4

The aim of this study was to determine the major pathways leading to COS and CO formation
and consumption during the processing of H2S and CO2 in the partially oxidizing conditions of
the Claus furnace. Both species were found to be produced by a multitude of pathways, which
include the direct reaction of H2S with CO2 to form COS and H2O and the reaction of CO2 with
S2, one of the major primary products in a Claus furnace. This last reaction produced SO2 and
CO as the major products, with COS being formed in lesser quantities. The dissociation of H2S
to H2 and S2 at high temperatures (>1000 °C) was shown to promote a further cascade of reactions
stemming from the reduction of COS and CO2, both of which lead to CO. Because of the known
formation of CS2 from hydrocarbon carry-over into the furnace, the reactions of CS2 with CO2,
H2O, and SO2 were also studied as potential CO- and COS-forming reactions. Reaction with
CO2 was slow at <1200 °C, but reaction with either H2O or SO2 was fast above 900 °C. Conversion
of CS2 by H2O led to CO, H2, H2S, S2, and CO2, whereas reaction with SO2 resulted in CO2 and
S2 as the major products. Similar observations were made for the reactions of COS with H2O
and SO2. The summary of pathways presented in Scheme 5 shows a complex interlinkage among
many reactions involving H2S, CO2, CO, COS, SO2, and S2, leading to the conclusion that previous
explanations of the production of COS from CO + S2 and CO from incomplete combustion
dramatically oversimplifies the formation/consumption for these compounds. It also shows that
modeling of individual kinetic rate expressions is somewhat impractical.

Introduction and CS2. This is because, unless the formation and


Background. The modified Claus process is the destruction of these species can be controlled precisely,
mainstay of the refining and gas processing industries either within the furnace or by hydrolysis back to acid
for conversion of H2S to elemental sulfur and H2O. It gases in the first converter, it is difficult to achieve the
consists of a high-temperature partial combustion step, high sulfur recovery currently demanded by legislation.
forming sulfur, SO2, and H2O, followed by a series of Paskall and co-workers suggested a multitude of reac-
catalytic stages to convert the uncombusted H2S and tions for the Claus furnace but emphasized that COS
SO2 produced in the furnace. Some recently published formation might arise by reaction of CO with sulfur in
papers provide comprehensive reviews of the process the furnace chamber and in the waste heat boiler
basics.1-4 (WHB).5-9 Field measurements at the exit of the WHB
The partial oxidation step, which results in temper- have shown that COS and CS2 are often found in
atures exceeding 1000 °C, is a key element of the Claus commercial operations, but thermodynamic modeling of
process, as it provides as much as 70% conversion, the furnace and WHB has proved inadequate to predict
establishes the proper H2S/SO2 ratio for downstream the COS and CS2 levels. In particular, calculations by
catalytic stages, and deals with destruction of contami- Monnery et al.10 showed that results of equilibrium
nants. However, the partially oxidizing conditions lead calculations and field measurements of COS did not
to a variety of side reactions and unwanted byproducts correlate at all. Overall, it is highly desirable that COS
with the hydrocarbon and CO2 impurities invariably and CS2 formation be understood more precisely as
present in the feed acid gases. In the case of acid gas these species make a major contribution to the sulfur
obtained from the processing of sour natural gas, the emissions from a Claus plant.
mixture fed to the furnace can contain as much as 75 Recent papers by Behie et al.11,12 present a kinetic
vol % CO2 with the consequence that CO2/sulfur species model for COS formation from CO and S2 and suggest
chemistry can dominate the reactions in the furnace. that most COS is formed during the quenching of the
Much of the previous interest in the area of CO2 furnace gases in the WHB, as per earlier studies by
furnace chemistry has focused on the formation of COS Sames et al.13 The work of Behie et al. does not consider
* Author to whom correspondence may be addressed. E- the sources of the required CO in any detail, but as will
mail: asrinfo@ucalgary.ca. Fax: 403-284-2054. be noted from the body of the work reported herein,
† Alberta Sulphur Research Ltd. several pathways lead to CO. Moreover, it would appear
‡ Department of Chemical and Petroleum Engineering. that the COS/CO/S2 kinetic relationship is insufficient
10.1021/ie990871l CCC: $20.00 © 2001 American Chemical Society
Published on Web 12/21/2000
498 Ind. Eng. Chem. Res., Vol. 40, No. 2, 2001

to account for field COS trends, indicating that other It is well-known that hydrocarbons (methane, aro-
mechanisms must be involved in COS formation. Behie matics) contaminate the acid gas fed to a Claus furnace
et al.11,12 comment that no systematic study has been because of their solubility in the amines used to separate
published on mechanisms involving H2, CO, COS, and the acid gases from hydrocarbon mixtures. Earlier work
CS2 formation/consumption in the Claus furnace. Con- done in our laboratories20,21 has resolved the question
sequently, we report the results of our research on this of CS2 formation in the Claus furnace, as we have shown
topic, which shows that COS can be formed by several that it is the hydrocarbon impurities that react with S2,
pathways, requiring that an intrinsic kinetic model for or other sulfur species, to form the CS2. An extensive
COS formation and destruction in a commercial furnace series of experiments20 showed that CO2 does not react
include much more than simply the reaction of CO with with H2S to give CS2; only COS is produced in this
S2. reaction.21 However, CS2 concentrations in the gases
Potential Pathways to COS. The Claus furnace can leaving the reaction furnace are known to rapidly
be divided into two distinct chemical regions: a partially increase and then decrease depending on the temper-
oxidizing flame zone with the highest concentrations of ature and residence time in that unit. Because COS
O2 near the burner tip and temperatures as high as could be formed by decomposition of CS2 under reaction
2500 °C and an anoxic region with temperatures in the furnace conditions, it is important to consider such
range of 900-1200 °C depending on the H2S content of reactions in the modeling of COS. Possible CS2 conver-
the acid gas and whether O2 enrichment is being sion reactions are as follows:
applied. In the case of a mixed acid gas (H2S and CO2),
a series of reactions can ensue from the thermal CS2 + H2O H COS + H2S (7)
decomposition of H2S and the reaction of H2S with CO2
in the anoxic region. CS2 + CO2 H 2COS (8)

2H2S H 2H2 + S2 (1) CS2 + SO2 f COS + SO + 1/2S2 (9)

H2S + CO2 H H2O + COS (2) CS2 + SO f COS + S2 (10)


CS2 + 4H2 H CH4 + 2H2S (11)
Although reaction 2 leads to COS and is well-known in
both the forward and reverse sense,14,15 the actual
concentration of COS will be affected by consecutive Of these reactions, 7 is well-known to occur over an
reactions involving H2, formed by H2S dissociation alumina or titania catalyst in the first catalytic stage
(reaction 1), and the thermal decomposition of COS. of the Claus process and has been invoked to explain
the conversion of CS2 at high temperatures in the
H2 + COS H CO + H2S (3) furnace.22 However, no work has been reported to
determine whether reactions 8-11 have any influence
2COS H 2CO + S2 (4) on CS2 and COS levels in the Claus furnace process gas.
In addition to the production of COS by these CS2
Because H2S is always present in high concentrations conversion pathways, it is probable that the COS so
and undergoes significant dissociation in the furnace to formed could react further with H2O and SO2 as follows:
H2 and sulfur (10-25%) at the temperatures of inter-
est,16 reaction 3 can have a considerable effect on the COS + H2O H H2S + CO2 (12)
final COS concentration. As such, the recombination of
H2 with sulfur species in the WHB will cause readjust- COS + SO2 f CO2 + SO + 1/2S2 (13)
ment of the equilibrium reactions involving COS (e.g.,
reaction 3).
COS + SO f CO2 + S2 (14)
Partial combustion of H2S also results in the forma-
tion of H2O and S2, both of which can react with the Reaction 12 is simply the reverse of reaction 2, but
species generated in reactions 1-4. Hence, the following reactions 13 and 14 represent distinct chemical path-
reactions must also be considered as part of the COS ways that could affect the final COS levels in the Claus
system: furnace.
Reactions 1-14 have been written as molecular
CO + H2O H CO2 + H2 (5) processes, but it is important to note that the Claus
furnace has two major regions, the flame and anoxic
2CO2 + S2 H COS + CO + SO2 (6) zones, that can promote radical and molecular path-
ways, respectively. Most certainly, reactions at flame
Reaction 5 is the very well known water gas shift zone temperatures (>2000 °C) will occur via radical
reaction and will influence CO concentrations.17 Reac- intermediates and involve S1 as the major elemental
tion 6 might be particularly interesting because, if it sulfur species. Reactions in the anoxic zone (900-1200
has a significant rate under furnace conditions, it could °C), particularly those involving CO2 and CO, will
control the formation of COS in the combustion of acid involve molecular species only. The dominant sulfur
gas containing high levels of CO2. Also, we must species in the 900-1200 °C range is S2, although it
consider the reverse of reaction 6 to be a means of both should be appreciated that S3 (equilibrium concentration
CO and COS removal under Claus furnace conditions. is 2.3 mol % at 1000 °C) and larger sulfur species
Previous work by both Sames et al.18 and us19 shows (equilibrium concentration of S4 at 1000 °C is 0.14 mol
that the final concentration of COS results from a %) must be involved in the chemistry to a small extent.
complex formation/destruction sequence, first increasing For the sake of brevity and to limit speculation as to
with temperature, passing through a maximum, and individual radical pathways, we have written the reac-
then decreasing with temperature at a given residence tions as simple molecular transformations utilizing S2
time. as the reacting sulfur species. Also, it should be noted
Ind. Eng. Chem. Res., Vol. 40, No. 2, 2001 499

Figure 1. Schematic of experimental apparatus.

Table 1. Equilibrium Constants for Possible Overall Reactions within the Anoxic Region of a Claus Furnace
Kp
reaction 900 °C 1000 °C 1100 °C 1200 °C
2H2S H 2H2 + S2 (1) 1.25 × 10-3 5.36 × 10-3 1.85 × 10-2 5.33 × 10-2
H2S + CO2 H H2O + COS (2) 4.59 × 10-2 6.18 × 10-2 7.98 × 10-2 9.98 × 10-2
H2 + COS H CO + H2S (3) 30.1 29.6 29.0 28.4
2COS H 2CO + S2 (4) 1.14 4.69 15.5 43.1
CO + H2O H CO2 + H2 (5) 0.72 0.55 0.43 0.35
2CO2 + S2 H COS + CO + SO2 (6) 1.57 × 10-4 3.95 × 10-4 8.84 × 10-4 1.81 × 10-3
CS2 + H2O H COS + H2S (7) 109 83.3 66.8 55.4
CS2 + CO2 H 2COS (8) 4.98 5.15 5.33 5.53
2CS2 + SO2 H 2COS + 3/2 S2 (9 + 10) 1.68 × 105 1.45 × 105 1.26 × 105 1.11 × 105
CS2 + 4H2 H CH4 + 2H2S (11) 2.70 0.34 5.74 × 10-2 1.28 × 10-2
COS + H2O H CO2 + H2S (12) 21.8 16.2 12.5 10.0
2COS + SO2 H 2CO2 + 3/2 S2 (13 + 14) 6.78 × 103 5.48 × 103 4.45 × 103 3.63 × 103
2CO + SO2 H 2CO2 + 1/2 S2 (15 + 16 + 17) 5.96 × 103 1.17 × 103 2.87 × 102 84.2

that the cooler anoxic zone of the furnace makes up the partial oxidation and steam reforming of methane or
largest region in the furnace. Thus, molecular reactions other hydrocarbons entering the furnace. The objective
might have a dominating effect in establishing the final of this work was to determine the dominant mechanistic
product composition, as radical intermediates transform pathways to COS and CO under Claus furnace condi-
to molecular species on departure from the flame zone tions to allow for a logical approach to the kinetic
and react to establish the equilibrium composition at modeling of these species.
the cooler conditions of the anoxic zone.
Because a large number of reactions can potentially Experimental Section
lead to or assist in the formation/destruction of COS and
CO within the Claus furnace, equilibrium constants for Gases and Materials. All gases were obtained from
these reactions were calculated in order to determine standard suppliers and had >99.9% purity according to
the most likely pathways. These values are given in the gas chromatographic procedures described below.
Table 1 for reactions 1-17, in some cases as overall Water was distilled before use.
reactions. Although this type of analysis can be used to Experimental System. A schematic of the system
examine the relative likelihood of different reactions to used in the experiments is given in Figure 1. Two types
act as a given pathway, it should be remembered that of reactor were used: one constructed of fully dense
it does not provide any information about the relative alumina (supplier, Vesuvius McDanel) with dimensions
rates of these processes. Nonetheless, the range of Kp of 19 mm o.d × 12.7 mm i.d. × 74 cm length and the
values listed, for the reactions as written, are suf- other fabricated from quartz with the same dimensions.
ficiently large that all of the listed reactions should be The purpose of using two reactor types was to establish
considered. The large values of the equilibrium con- the catalytic nature of the surface on some of the
stants for the reactions of CS2, COS, and CO with SO2, reactions suggested as possible COS formation path-
in particular, suggest that these reactions might rep- ways. Temperature profiles for these externally heated
resent major pathways for conversion of these species reactors were measured under a nonreactive flow of
in the Claus furnace, barring any kinetic limitations. argon using an alumina sheathed S-type thermocouple.
The smaller Kp values for reactions 1, 2, and 6 also do These profiles presented an initial ramp-up section,
not exclude these reactions from the anoxic chemistry, (∼400 °C to reaction temperature) corresponding to 20%
as these processes represent the starting points or of the length of the reactor, followed by an isothermal
primary reactions for this chemistry. hot-zone section, and finally, a cool-down section. Noted
Clearly, the number of reactions that can lead to COS residence times for the experiments given in the data
and CO could be quite large and, for CO, would include tables refer to the hot-zone section of the furnace and
500 Ind. Eng. Chem. Res., Vol. 40, No. 2, 2001

Table 2. Effect of Reactor Type on Product Yield for the Reaction of a 50% H2S/50% CO2 Feed Mixture
equilibrium, quartz, and R- alumina product yields(mol of product per 100 mol of reactant)
T °C tres (ms) H2 CO COS SO2 S2 H2O
600 3200 0.6 0.18 0.14 1.8 0.11 0.63 4.1 0 3.2 0 0 0 1.3 0.25 0.5 6.0 0.32 4.1
700 2870 1.3 0.22 1.1 4.2 0.12 1.5 4.2 0.2 5.8 0 0 0 2.7 0.25 1.0 8.5 0.48 6.7
800 2600 2.4 2.4 3.3 7.9 0.2 6.0 3.8 0.4 5.3 0 0 0 5.0 1.4 3.4 11.7 0.8 8.7
900 2400 4.0 5.9 4.3 12.3 1.3 8.6 3.1 0.7 5.5 0 0 0 8.0 4.4 5.2 15.4 3.3 11.5
1000 2230 5.8 7.6 5.5 16.9 3.7 11.5 2.5 1.0 5.4 0.09 0 0 11.1 6.2 8.6 19.2 5.8 17.0
1100 2070 7.5 6.7 6.7 21.0 14.7 14.8 1.9 3.3 6.1 0.2 0 0 13.9 11.2 10.7 22.6 19.0 20.8
1200 1930 9.3 7.4 6.74 24.9 20.5 16.9 1.4 3.7 7.1 0.4 0 0 16.3 13.9 11.4 25.4 24.1 23.1
1300 1800 10.9 7.9 6.0 28.1 23.1 17.9 1.1 3.4 8.0 0.7 0 0 18.3 15.6 12.1 27.7 26.7 26.2
1400 1700 12.2 8.2 6.3 30.8 25.6 20.2 0.9 3.3 8.0 1.3 0 0 19.5 17.0 13.2 29.1 29.2 28.1

can therefore be used for relative comparisons between the system comprising reactants and all potential
different reactions. products. The list of species included consisted of N2,
Although some reaction is unavoidable within the COS, CS2, CO, CO2, SO2, H2O, H2S, H2, S2, S3, S4, S5,
initial ramp-up zone, use of a reactor design to imple- S6, S7, and S8. Thermodynamic data in the form of the
ment a separate reactant entry and preheat was con- Gibbs energy function, [G° - H°(298.15)]/T, and the heat
sidered but not implemented. While this approach of formation at 298.15 K, ∆H°f, for these species were
appears to have merit, it is limited by the ability of obtained from the JANAF Thermochemical Tables,24
several of the reactants (notably H2S and COS) to and the program was constructed using the approach
undergo unimolecular decomposition. Subsequent reac- described by Holub and Vanka25 for the White-Johnson-
tion within the cool-down section of the reactor was Dantzig method.
minimized by employing a quench system with a quench Equilibrium constants, Kp, for the reactions listed in
time on the order of 20-100 ms from reaction temper- Table 1 were also determined from the results of these
ature to ca. 400 °C. Quenching of the gases was achieved free energy minimization calculations.
by withdrawal of gas samples through a quartz capillary
connected to a pumping system. Reactants were me- Results and Discussion
tered using mass flow controllers with reactant compo-
sitions being checked by gas chromatography (see The H2S/CO2 Reaction. The basic data for reaction
below). In experiments using sulfur as a reactant, the of H2S and CO2 in both quartz and fully dense alumina
reactant gas mixture was passed through liquid sulfur reactors are given in Table 2, along with the equilibrium
at 330 °C with the quantity being taken up ascertained values predicted by free energy calculations. It is clear
by cooling the hot gas to 20 °C to condense and trap that H2S does react with CO2 under Claus furnace
the sulfur carried by the gas. conditions, although surface effects might have a con-
Experimental Procedures. A typical experiment siderable effect on many of the reactions involved in this
consisted of stabilizing the reactor system at the desired system. In the quartz reactor, formation of COS was
temperature, passing the feed mixture through the very slow below 1000 °C such that equilibrium conver-
reactor, and analyzing the dried (P2O5) product gas. sions were not obtained (Figure 2). However, above 1050
Several samples were collected for each condition, with °C, COS formation appeared to exceed equilibrium,
average data being presented in the tables (absolute suggesting, perhaps, that decomposition of COS to CO
error is estimated to be <2% of the quoted values). and S2 is a rate-limited process. Thus, immediately it
Gas Chromatographic Methods. To avoid any is seen that the final product distribution from reaction
unwanted reactions due to the presence of condensed of H2S with CO2 depends not just on the initial reaction
water during sampling of the product gases, a P2O5 drier but on consecutive reactions of the initial products. The
was always placed in front of the syringe. The temper- apparent levels of COS above those predicted by equi-
ature of the sampling position was also maintained at librium at 1050 °C and beyond could also be explained
approximately 150 °C. In this way, both water and by recombination of CO and sulfur during quenching
sulfur were removed from the gas stream prior to of the products from these higher temperatures. As will
collection of the sample, while all other components be seen later, however, the reaction of S2, produced by
were collected and analyzed by dual gas chromato- H2S dissociation, with CO2 (reaction 6) could also
graphs. Analysis of H2, CO, and N2 was performed on a contribute to COS formation above predicted levels,
Haysep A column (Ar carrier, 15 mL/min), while all of provided that COS decomposition was slow. Interest-
the other components were analyzed on a Chromosorb ingly, in the alumina reactor, COS formation appeared
108 column with He as carrier (28 mL/min). to exceed equilibrium predictions at all temperatures
In all of the systems examined, N2 or argon was above 600 °C, indicating that the reaction of CO2 with
always maintained as the balance component in the feed H2S (reaction 1) is catalyzed quite efficiently at an
composition. This allowed these inert species to be used R-alumina surface and again suggesting that COS
as an internal standard in the GC analysis. In this way, decomposition or indeed, other COS-consuming reac-
the product yield of each component after reaction in tions are rate-limited.
units of moles per 100 moles of reactant was obtained As discussed as part of the Introduction, the inde-
from the GC data. Because water and sulfur were pendent dissociation of H2S and the subsequent reaction
removed prior to collection of the sample, the yields of of H2 with other species could have a significant effect
these components were calculated from H and S mass on the overall product composition in the H2S/CO2
balance equations, respectively. system. Because H2 formation is close to the predicted
Free Energy Calculations. Equilibrium composi- equilibrium value in both quartz and alumina reactors
tions and yields for the various reactions examined were at temperatures up to 1100 °C, dissociation of H2S must
calculated using Gibbs free energy minimization23 for either be catalyzed equally by the two reactor surfaces
Ind. Eng. Chem. Res., Vol. 40, No. 2, 2001 501

Figure 3. Comparison of predicted COS yields in the absence of


COS decomposition with the true equilibrium and experimental
alumina reactor results.

tion from occurring in the calculations, by omitting CO


as a product species, is akin to imposing rate-limiting
behavior for this process. These curves show that this
results in increasing COS yields at higher temperatures
rather than the declining levels expected by proper
equilibrium. The super-equilibrium levels of COS ob-
served experimentally could therefore be readily ex-
plained by differential reaction rates for the initial H2S/
CO2 reaction and secondary COS decomposition.
Overall, these observations pose a very important
question as to the kinetic data that would be the most
useful for modeling the chemistry of the Claus furnace.
This is due to the fact that commercial systems are lined
with alumina refractory, which, according to our data,
could have a significant impact on the CO2/H2S chem-
Figure 2. Product yields from the reaction of H2S and CO2 (1:1) istry occurring in the anoxic region of the furnace. Thus,
in quartz and alumina reactors. any model based on purely gas-phase kinetic data might
not be sufficient for prediction of the behavior of a
commercial system. Because our goal was to examine
or proceed readily, uncatalyzed, in the gas phase. the possible reaction pathways under conditions as close
However, the observation that H2 yields are significantly as possible to those found in the Claus furnace, all
below equilibrium predictions in both types of reactors further reactions were carried out in the fully dense
above 1100 °C again suggests possible loss of H2 by alumina reactor.
recombination with sulfur during quenching and sam- The CO2/S2 Reaction. To our knowledge, no studies
pling of the reaction gases. The effect of quenching on on this reaction have been published, and it has not
this type of reverse reaction would be expected to have been considered to be important in Claus furnace
a greater influence on final product distributions at chemistry. However, the results of experiments reported
higher temperatures. in Table 3 and partially depicted in Figure 4 show that
CO yields, like those of COS, appear to be strongly the reaction proceeds at significant rates above 1100 °C.
affected by the nature of the reactor surface at temper- The major products were CO, COS, and SO2, suggesting
atures below 1000 °C such that little CO was observed that this chemistry could have a significant impact on
below 1000 °C over a quartz surface. Several interpreta- the CO and COS concentrations during the combustion
tions can be offered to explain these data; however, it of high-CO2-content acid gases. The limited degree of
is likely that CO yields merely depend on the observed reaction below 1100 °C (Table 3) indicates that most
COS yields in both types of reactors, whether by direct CO2/S2 chemistry would occur in the flame zone or in
COS decomposition (reaction 4) or by reduction of COS its immediate vicinity, although flame zone reactions
by H2 (reaction 3). Insignificant CO yields below 1000 would, presumably, involve reaction of atomic sulfur
°C in quartz might be due to the lack of catalysis of the with CO2 as opposed to S2 as shown in reaction 6.
initial H2S/CO2 reaction over this surface and conse- The results of equilibrium calculations carried out on
quent corresponding insignificant yields of COS. the same feed examined experimentally are also pre-
The apparent catalysis of the H2S/CO2 reaction under sented in Table 3 and Figure 4. These calculations show
these same conditions over an R-alumina surface and that CO2 conversion is strongly limited by equilibrium
the attendant COS yields in excess of equilibrium even when CO2 is the limiting reactant within the
(Figure 2) can be explained by the results of equilibrium system, the origin of which is the small Kp value
calculations shown in Figure 3. This plot compares the reported for this reaction in Table 1. This conversion
COS yields obtained by artificially restricting COS also occurs predominantly to form CO only at temper-
decomposition in the equilibrium calculations with those atures above 1100 °C, suggesting yet again that decom-
of the true equilibrium and experimental alumina position of COS is likely slow below this temperature.
reactor results. Artificially preventing COS decomposi- This conclusion is arrived at given that decomposition
502 Ind. Eng. Chem. Res., Vol. 40, No. 2, 2001

Table 3. Distribution of Products from the Reaction of CO2 with S2


products (mol per 100 mol of reactant) conversion (%)
T °C tr (s) CO2 S2 CO COS SO2 CO2 S2
effect of temperaturea,b
800 1.0 7.4 (6.9) 7.2 (6.9) 0.0 (0.34) 0.02 (0.19) 0.01 (0.27) 0.3 (7.1) 0.2 (3.2)
900 1.0 7.4 (6.6) 7.2 (6.9) 0.0 (0.67) 0.03 (0.16) 0.01 (0.42) 0.4 (11.3) 0.3 (4.1)
1000 1.0 7.4 (6.2) 7.1 (6.8) 0.04 (1.1) 0.03 (0.14) 0.04 (0.64) 0.9 (17.2) 0.5 (5.4)
1100 1.0 6.9 (5.6) 7.0 (6.7) 0.55 (1.7) 0.02 (0.11) 0.31 (0.91) 7.6 (24.5) 2.3 (7.2)
1200 1.0 6.1 (4.9) 6.7 (6.5) 1.25 (2.4) 0.15 (0.09) 0.71 (1.3) 18.7 (33.8) 6.0 (9.4)
1300 1.0 5.1 (4.2) 6.4 (6.3) 2.08 (3.1) 0.26 (0.08) 1.20 (1.6) 31.4 (43.0) 10.2 (11.7)
1400 1.0 4.3 (3.5) 6.2 (6.2) 2.84 (3.8) 0.32 (0.06) 1.60 (2.0) 42.3 (52.4) 13.3 (14.1)
1500 1.0 3.1 (2.9) 5.8 (6.0) 3.87 (4.5) 0.49 (0.05) 2.19 (2.3) 58.5 (60.9) 18.7 (16.2)
effect of residence timec
1100 0.45 7.6 4.3 0.11 0.00 0.05 1.4 0.6
0.75 7.4 4.2 0.27 0.01 0.11 3.6 1.4
1.0 7.3 4.2 0.37 0.02 0.16 5.1 2.1
1200 0.45 7.2 4.2 0.48 0.04 0.23 6.7 3.1
0.75 7.0 4.1 0.67 0.04 0.34 9.2 4.4
1.0 6.8 4.1 0.83 0.06 0.42 11.6 5.6
1.5 6.6 4.0 1.01 0.08 0.51 14.3 6.9
2.0 6.3 3.9 1.33 0.06 0.69 18.1 8.7
1300 0.45 6.3 4.0 1.32 0.02 0.68 17.5 8.2
0.75 6.1 3.8 1.5 0.12 0.80 21.1 10.8
2.0 5.7 3.8 1.78 0.16 0.94 25.4 12.8
effect of CO2/S2 feed ratiod
1200 1.0 0.9 4.3 0.13 0.00 0.06 12.9 0.7
2.4 4.2 0.31 0.02 0.17 12.3 2.2
4.5 4.1 0.59 0.02 0.33 12.1 4.1
6.8 4.1 0.83 0.05 0.42 11.4 5.5
9.3 4.0 1.09 0.06 0.59 11.1 7.6
14.1 3.9 1.45 0.07 0.69 9.7 8.8
a Values in parentheses are calculated equilibrium. b Feed for these experiments was CO , 7.45 mol %; S 7.17 mol %; balance Ar.
2 2,
cFeed for these experiments was CO2, 7.68 mol %; S2; 4.30 mol %; balance Ar. d Feed for these experiments was S2, 4.3 mol % and 1.03,
2.68, 5.07, 7.68, 10.42, 15.61 mol % CO2, respectively; balance Ar.

Figure 4. Comparison of equilibrium and experimental results Figure 5. Comparison of equilibrium and experimental conver-
for the CO2 + S2 reaction (tr ) 1 s). sions for COS decomposition (tr ) 0.5 s).

is thermodynamically favored even at these lower Scheme 1. Pathways for Reaction of CO2 with S2
temperatures (see also Figure 5). The comparison of the
experimental and equilibrium conversions for this sys-
tem in Figure 4 further shows good agreement only at
the high-temperature extreme of this plot, attesting to
the slow rate of reaction at lower temperatures.
Interestingly, the reaction of CO2 with either S or S2
gives another pathway for the shuttling of oxygen from
CO2 to sulfur, forming both COS and SO2, species, which
can then undergo further chemistry leading back to
sulfur and H2O. The actual mechanism of reaction 6 is
open to debate, as at least two potential pathways can
be written (Scheme 1, A and B). Both pathways involve as work done on the combustion of sulfur compounds
unstable sulfur oxides (SO and S2O), which cannot be has suggested that this species would be a less likely
observed by standard analytical methods, and each intermediate at high temperatures compared to SO.26
correctly predicts the reaction products. It is likely, The data in Table 3 also show that the COS postulated
however, that the scheme involving S2O is less probable, to be formed must undergo dissociation to S2 and CO
Ind. Eng. Chem. Res., Vol. 40, No. 2, 2001 503

Table 4. Distribution of Products from the Reaction of CO + SO2


feed mole
ratio products (mol per 100 mol of reactant) % CO
T (°C) tr (s) SO2 CO SO2 CO CO2 COS S2 conversion
effect of temperaturea
800 0.5 5 2 4.95 (4.01) 1.90 (0.01) 0.09 (1.99) 0.01 (0) 0.02 (0.49) 5.0 (99.4)
900 0.5 5 2 4.90 (4.02) 1.81 (0.03) 0.19 (1.96) 0 (0) 0.05 (0.49) 9.5 (98.4)
1055 0.5 5 2 4.27 (4.05) 0.54 (0.11) 1.46 (1.89) 0 (0) 0.37 (0.47) 73.0 (94.7)
1155 0.5 5 2 4.18 (4.10) 0.36 (0.19) 1.64 (1.80) 0 (0) 0.41 (0.45) 82.0 (90.4)
1255 0.5 5 2 4.14 (4.16) 0.27 (0.31) 1.72 (1.69) 0 (0) 0.43 (0.42) 86.5 (84.4)
effect of residence time
1055 0.3 5 2 4.45 0.85 1.11 0.04 0.26 57.5
1055 0.4 5 2 4.35 0.67 1.29 0.04 0.31 66.5
1055 0.6 5 2 4.24 0.48 1.52 0 0.38 76.0
1055 1.0 5 2 4.10 0.24 1.76 0 0.45 88.0
effect of SO2/CO feed ratio
1055 0.5 2 2 1.14 0.28 1.72 0 0.43 86.0
1055 0.5 2 5 0.29 1.54 3.42 0.12 0.86 69.2
1055 0.5 2 7.5 0 3.10 4.14 0.25 0.88 58.6
1055 0.5 2 10 0 5.23 4.23 0.44 0.78 47.8
a Values in parentheses are calculated equilibrium.

Table 5. Distribution of Products from the Reaction of COS + SO2


feed mole
ratio products (mol per 100 mol of reactant) % COS
T °C tr (s) SO2 COS SO2 CO CO2 COS S2 conversion
effect of temperaturea
1055 2.0 5 2 4.20 (4.07) 0.59 (0.14) 1.41 (1.86) 0 (0) 1.4 (1.46) 100 (99.8)
1155 2.0 5 2 4.10 (4.12) 0.49 (0.24) 1.51 (1.76) 0 (0.01) 1.5 (1.43) 100 (99.7)
1255 2.0 5 2 4.10 (4.20) 0.48 (0.39) 1.52 (1.60) 0 (0.01) 1.5 (1.40) 100 (99.7)
effect of residence time
1055 0.3 5 2 4.60 0.20 0.83 0.97 0.7 51.5
1055 0.4 5 2 4.45 0.28 1.10 0.62 1.0 69.0
1055 0.5 5 2 4.30 0.32 1.44 0.24 1.2 88.0
1055 1.0 5 2 4.25 0.45 1.50 0.05 1.4 97.5
1055 1.5 5 2 4.20 0.50 1.50 0 1.4 100
effect of SO2/COS feed ratio
1055 2.0 20 2 19.2 0.33 1.67 0 1.4 100
1055 2.0 10 2 9.2 0.39 1.61 0 1.4 100
a Values in parentheses are calculated equilibrium.

(reaction 4), as COS is found in lower, and CO in higher, The absence of any significant amount of COS also
molar quantities than predicted by eq 6. In addition, suggests that the reaction might proceed by the follow-
the two pathways in Scheme 1 indicate that the CO2/S2 ing sequence:
system is reversible by reaction of SO2 with either CO
or COS. These reactions were tested by passing these SO2 + CO f SO + CO2 (15)
reagents through the fully dense alumina reactor at
>1000 °C. SO + CO f CO2 + [S] (16)
The CO/SO2 Reaction. Although this reaction has
been examined at low temperatures (<600 °C) over [S] + [S] f S2 (17)
various catalysts in connection with SO2 removal from
flue gases,27-29 only limited work has been done at This would further imply that COS might not form from
temperatures over 1000 °C. Most recently, Russian the reaction of CO with [S], if, indeed, reaction 16 is an
workers have published the results of static experiments important pathway and might only form via reaction
in quartz at 827-1077 °C, finding sulfur, CO2, and COS with S2 (the reverse of eq 4) when CO is present in large
to be formed as the major products.30 Our experiments, quantities.
carried out in a flowing regime (Table 4), yielded sulfur The COS/SO2 Reaction. The feed ratios chosen for
and CO2 as the major products, with COS being formed these experiments were based on the rationale that
only at high CO/SO2 feed ratios and only in small there is always much more SO2 in the Claus furnace
amounts relative to the other products. This type of than COS. In particular, we wished to determine
product distribution was also found from the results of whether the relative kinetics of COS decomposition and
equilibrium calculations carried out on this system and its reaction in the presence of excess SO2 would permit
also reported in Table 4. This too showed that COS was decomposition to also occur. The data obtained from
expected to be formed only at higher CO/SO2 feed ratios, these experiments (Table 5) show that the reaction with
and even then only in relatively small amounts. This SO2 could be a major pathway for the destruction of COS
result can be taken as an indication of the thermody- in the furnace, as quantitative conversion was found at
namic preference for the 2CO + S2 H 2COS equilibrium 1055 °C for residence times of >1 s, similar to those
to sit largely on the side of CO and S2 at the reaction found in commercial furnaces. The major products of
temperatures studied. the reaction were CO2 and sulfur, with only around 25%
504 Ind. Eng. Chem. Res., Vol. 40, No. 2, 2001

Table 6. Reaction Products from the Reaction of CS2 O2 incorporated for combustion of the hydrocarbons,
with CO2 allowing for formation of CS2 by reaction of the uncom-
feed mole products busted hydrocarbon with S2 or other sulfur species. As
T tr ratio (mol per 100 mol of reactant) % CS2 pointed out in the Introduction, the possible decomposi-
°C (s) CO2 CS2 CO2 CO COS CS2 S2 conversion tion reactions of CS2 are of special interest with respect
effect of temperaturea to COS formation in the Claus furnace and WHB, as
1055 2.0 5.75 1.9 5.63 0.47 0.04 1.37 0.5 27.9 each can lead to CO and COS production. As in some of
1155 2.0 5.75 1.9 5.33 0.90 0.07 1.23 0.6 31.5 the previous work, we have examined the reaction of
1255 2.0 5.75 1.9 4.36 2.14 0.13 0.73 1.1 61.3 CS2 with an excess of the reagent in order to ap-
effect of residence time proximate conditions in Claus furnaces and so, perhaps,
1055 0.5 6.22 1.6 6.06 0.09 0.13 1.48 0.1 7.5 deduce the more important mechanisms of a commercial
1055 1.0 6.78 1.9 6.50 0.39 0.25 1.58 0.3 18.1 system.
1055 1.5 5.76 2 5.57 0.62 0.13 1.55 0.4 21.3 Interestingly, CO2 was found to react with CS2 under
effect of CO2/CS2 feed ratio Claus furnace conditions although relatively more slowly
1055 2.0 20 1.9 19.6 0.91 0.05 1.33 0.5 29.8 (Table 6) when compared to some of the other reactions
1055 2.0 11.1 2 10.7 0.80 0.07 1.52 0.5 24.6 included in this study. Thus, equilibrium calculations
a Equilibrium calculations predict quantitative conversion of predict quantitative conversion of CS2 under the condi-
CS2 under all conditions investigated. tions studied, because pf the excess of CO2 in the feed.
Nevertheless, over 60% CS2 conversion was observed at
of the COS appearing as CO in the experiments showing 1255 °C using a 2-s residence time, giving CO and sulfur
complete COS conversion. This suggests that reaction as major products. Because it is difficult to envisage how
of COS with SO2 is relatively facile and is in reasonable CO2 might be converted directly to CO, it is probable
agreement with equilibrium predictions for this system. that COS is an intermediate product of this reaction
When the data with variable residence time obtained that then undergoes further decomposition to CO in a
at 1055 °C (Table 5) are compared to the model for COS combination of reactions 8 and 4.
kinetics published by Behie et al.,11 it is clear that
reaction of COS with sulfur dioxide is considerably CO2 + CS2 H [2COS] H 2CO + S2
faster than COS decomposition. This conclusion is
reinforced by the data shown in Table 10 for COS The observation of small concentrations of COS in all
decomposition in the reactor system of this study. Thus, experiments and more COS than CO at a 0.5-s residence
overall, the following reaction sequence, which is reac- time at 1055 °C supports the formation of COS as an
tions 13 and 14 given in the Introduction, can be written initial product. The last set of data in Table 6 shows
to describe the major pathway in the SO2/COS system: that the conversion of CS2 by CO2 appears to be
independent of the CO2 concentration (within this
COS + SO2 f CO2 + SO + 1/2S2 (13) limited data set), although a more extensive study of
this reaction would be required to confirm this tentative
COS + SO f CO2 + S2 (14) conclusion.
Most workers have assumed that conversion of CS2
In addition to these processes, direct decomposition of in the Claus furnace occurs by reaction with H2O, which
COS (eq 4) seems to account for approximately 25% of is present in large concentrations. The data in Table 7
the total COS conversion. bear out this supposition, as 100% conversion was
In summary, it can be concluded that the CO2/S2 observed over 2 s even at the relatively low temperature
reaction is an important reaction in the Claus furnace, of 1055 °C. In addition, conversions >90% were obtained
particularly above 1200 °C (i.e., in the flame zone), and over 0.5 s at 1055 °C. Both CO2 and CO were formed as
that it is reversible by reaction of either CO or COS with major products, along with lesser amounts of COS.
SO2. Interestingly, CO2 was the major oxide product at 1055
Reactions of CS2 with H2O, SO2, and CO2. We °C, whereas CO was the predominant oxide at 1255 °C.
have reported data on CS2 formation in earlier publica- These observations, together with the increased CO2/
tions20,21 and shown that it arises whenever hydrocar- CO ratios at higher H2O/CS2 feed ratios, suggest that
bons are present in the feed acid gas. Our laboratory COS is an intermediate product that can undergo either
data indicated that H2S consumed much or all of the decomposition to CO and sulfur or hydrolysis to CO2
Table 7. Reaction Products from the Reaction of CS2 with H2O
feed mole
ratio products (mol per 100 mol of reactant) % CS2
T °C tr (s) H2O CS2 H2S CO2 H2 CO COS SO2 CS2 S2 H2O conversion
effect of temperaturea
1055 2.0 5 2 1.53 1.09 1.71 0.80 0.11 0 0 1.2 1.8 100
1155 2.0 5 2 1.49 0.90 2.00 0.95 0.15 0 0 1.2 1.5 100
1255 2.0 5 2 1.55 0.74 1.88 1.09 0.17 0 0 1.1 1.6 100
effect of residence time
1055 0.5 5 2 1.78 0.95 1.86 0.82 0.08 0 0.15 0.9 1.4 92.5
1055 1.0 5 2 1.81 1.00 1.96 0.81 0.10 0 0.10 1.0 1.3 95.0
1055 1.5 5 2 1.61 0.96 1.85 0.88 0.12 0 0.05 1.1 1.5 97.5
effect of H2O/CS2 feed ratio
1055 2.0 20 2 2.29 1.49 3.22 0.48 0.03 0.16 0 0.8 14.5 100
1055 2.0 10 2 1.90 1.34 2.52 0.62 0.04 0.08 0 1.0 5.6 100
a Equilibrium calculations predict quantitative conversion of CS2 under all conditions investigated.
Ind. Eng. Chem. Res., Vol. 40, No. 2, 2001 505

Table 8. Reaction Products from the Reaction of CS2 with SO2


feed mole
ratio products (mol per 100 mol of reactant) % CS2
T °C tr (s) SO2 CS2 SO2 CO CO2 COS CS2 S2 conversion
effect of temperaturea
1055 2.0 5 2 2.99 0.32 1.60 0 0 3.0 100
1155 2.0 5 2 2.89 0.44 1.54 0 0 3.1 100
1255 2.0 5 2 2.84 0.65 1.50 0.05 0 3.1 100
effect of residence time
1055 0.5 5 1.7 2.81 0.38 1.26 0. 0.17 2.5 90
1055 1.0 5 1.8 3.20 0.40 1.49 0.05 0.05 2.7 97
1055 1.5 5 2 2.90 0.44 1.56 0.08 0 3.0 100
effect of SO2/CS2 feed ratio
1055 2.0 20 2 18.65 0.29 1.63 0 0 2.7 100
1055 2.0 11 2 8.35 0.30 1.71 0.07 0 3.2 100
1055 2.0 5 4 0.83 0.78 3.28 0.25 0.10 5.9 97.5
1055 2.0 5 6 0 2.79 2.60 0.94 0.28 7.8 95.3
1055 2.0 5 10 0 3.68 1.62 1.40 3.79 8.0 62.1
a Equilibrium calculations predict quantitative conversion of CS2 under all conditions, except for the 5:10 feed mole ratio of SO2/CS2.

Scheme 2. Conversion of CS2 by H2O at Claus Scheme 3. Pathways for Reaction of CS2 with SO2
Furnace Conditions

and H2S. The appearance of H2 as a significant product


in this reaction at levels above the equilibrium concen-
Reaction of COS with H2O and SO2 and the
tration expected for just dissociation of the H2S product
Direct Decomposition of COS. Because COS is
shows that several mechanistic pathways are operating
implicated as an intermediate in the reaction of CS2
for this “simple” bimolecular reaction (see Scheme 2).
with CO2, H2O, and SO2, data were obtained for the
Interestingly, it is seen that high H2O/CS2 feed ratios
reaction of COS with H2O and SO2. Clearly, the reaction
(bottom set of data in Table 7) result in higher H2 and
of COS with CO2 leads to no net change, but the direct
H2S product levels. This is most likely because of the decomposition of COS might be implicated in the
water gas shift of CO, formed initially by COS decom- reaction of CS2 with CO2 and, hence, was also examined
position, and consumption of sulfur species by the H2 experimentally. The data in Table 9 show that COS
product of that shift. Trends for CO and CO2 levels in reacts rapidly and to completion with H2O, forming CO2
this data set support this conclusion. and H2S as the major products and CO, S2, and H2 in
The data summarized in Table 8 show that SO2 is also lesser quantities. Although H2O was always used in
a very effective agent for conversion of CS2. As with excess in these experiments to mimic Claus furnace
H2O, SO2 promotes complete conversion at 1055 °C over conditions, results at 1055 and 1255 °C show that
2 s and >90% over 0.5 s at the same temperature, in hydrolysis dominates over direct decomposition, even
agreement with the theoretical equilibrium for these at the higher temperature. Interestingly, more CO was
systems. This illustrates that reaction with SO2 could formed by reaction of CS2 with H2O (Table 7) than by
also be an important mechanism for conversion of CS2 reaction of COS with H2O under the same reaction
in the Claus furnace. The major products of the reaction conditions and reagent molar ratios. One explanation
were CO2 and sulfur, with lesser quantities of CO and for this observation is that conversion of CS2 results in
only traces of COS. Only slightly higher quantities of more H2S, which can dissociate to H2 and drive the
CO were observed on increasing the reaction tempera- product CO2 to CO and H2O. Thus, again it is observed
ture from 1055 to 1255 °C, and no increase in CO was that the final product distribution for even relatively
measured for longer residence times at 1055 °C. Only simple bimolecular processes is dependent on numerous,
when the SO2/CS2 feed ratios were decreased did CO linked equilibria.
exceed CO2 as the major carbon oxide product. All of As was shown earlier (Table 5), reaction of COS with
these observations can be explained by reaction of CS2 SO2 is also fast, leading to CO2 and sulfur as major
with SO2 to form COS, elemental sulfur, and SO products with some CO formed, presumably, from direct
(Scheme 3), with rapid conversion of COS by either SO decomposition of COS. Overall, only minor differences
or another molecule of SO2. Only in experiments with in CO2/CO product ratios were noted for low (1055 °C)
small amounts of SO2 in the feed did COS appear as a and high (1255 °C) temperatures, but CO formation was
significant product and have an opportunity to produce limited to some extent when SO2 was present in large
CO and sulfur by direct decomposition. Field observa- excess (see bottom data set of Table 5). The major
tion shows that CS2 concentrations never exceed SO2 reaction under all conditions of this study is the direct
values in commercial furnaces; thus, any conversion of conversion of COS by SO2.
CS2 by SO2 should result in CO2 and sulfur as major Although it has been studied by numerous
products. groups,11,31-35 the decomposition of COS in argon was
506 Ind. Eng. Chem. Res., Vol. 40, No. 2, 2001

Table 9. Reaction Products from the Reaction of COS with H2O


feed mole
ratio products (mol per 100 mol of reactant) % COS
T °C tr (s) H 2O COS H2S CO2 H2 CO COS SO2 CS2 S2 H2O conversion
effect of temperaturea
1055 2.0 5 2 1.28 1.65 0.55 0.35 0 <0.1 0 0.3 3.2 100
1155 2.0 5 2 1.05 1.60 0.75 0.41 0 <0.1 0 0.5 3.2 100
1255 2.0 5 2 0.80 1.53 0.94 0.47 0 <0.1 0 0.6 3.3 100
effect of residence time
1055 0.5 5 2 1.52 1.50 0.18 0.40 0.08 0.15 0 0.1 3.3 96.0
1055 1.0 5 2 1.38 1.58 0.40 0.35 0.05 0.10 0 0.2 3.2 97.5
1055 1.5 5 2 1.34 1.64 0.48 0.36 0 <0.1 0 0.3 3.2 100
effect of H2O/COS feed ratio
1055 2.0 20 2 1.00 1.52 0.75 0.48 0 0.18 0 0.4 18.2 100
1055 2.0 10 2 1.10 1.55 0.65 0.45 0 0.14 0 0.4 8.3 100
a Equilibrium calculations predict quantitative conversion of COS under all conditions investigated.

Table 10. Product Distribution from the Decomposition of COS

COS feed products (mol per 100 mol of reactant) % COS


T °C tr (s) (mol %) CO CO2 COS CS2 S2 conversion
effect of temperaturea
800 0.5 2 0 (1.5) 0 (0.13) 2.01 (0.27) trace (0.13) 0 (0.73) 0.0 (86.3)
900 0.5 2 0.23 (1.7) 0 (0.07) 1.77 (0.15) 0 (0.07) 0.1 (0.86) 11.5 (92.6)
1055 0.5 2 0.95 (1.9) 0 (0.03) 1.05 (0.06) 0 (0.03) 0.5 (0.94) 47.5 (97.0)
1155 0.5 2 1.82 (1.9) 0 (0.02) 0.17 (0.04) 0 (0.02) 0.9 (0.96) 91.5 (98.2)
1255 0.5 2 2.00 (2.0) 0 (0.01) 0 (0.02) 0 (0.01) 1.0 (0.98) 100 (98.9)
effect of residence time
1055 0.3 2 0.65 0 1.35 0 0.3 32.5
1055 0.4 2 0.81 trace 1.19 trace 0.4 40.5
1055 1.0 2 1.65 0.07 0.23 0.06 0.9 88.5
effect of COS concentration
1055 1.0 5 3.81 0.34 0.55 0.31 2.2 89.0
1055 1.0 10 8.39 0.36 0.93 0.33 4.5 90.7
1055 1.0 20 16.04 0.52 2.98 0.47 8.5 85.1
a Values in parentheses are calculated equilibrium.

Scheme 4. Pathways for Decompositions of COS Scheme 5. A Synopsis of CO2/H2S Chemistry in


the Claus Furnace and WHB

examined to provide comparative decomposition data in


the fully dense alumina reactor used for the bulk of this
study. Overall, the results in Table 10 and Figure 5
show that COS only readily underwent decomposition
in this reactor system at higher temperatures (>1155
°C) for a 0.5-s residence time. A comparison of data
obtained from the experiments carried out on the effect
of residence time at 1055 °C to equivalent data for
reaction of SO2 or H2O with COS (Tables 5 and 9) also
leads to the conclusion that these bimolecular reactions
are somewhat faster than COS decomposition. Perhaps
one of the more interesting features of this study was
the formation of CS2 and CO2 at the highest feed COS
concentrations. Although such high concentrations of
Summary and Concluding Comments
COS are not expected in the Claus furnace, it is of
intrinsic interest to observe CS2 formation, as it might Clearly, the H2S/CO2 system is a very complex one,
occur via a transition state of the type depicted in with product species being interconnected through
Scheme 4. Furthermore, because the products of COS multiple reactions, nearly all of which appear to be
decomposition include both S2 and CO2, at still higher readily reversible. An attempt has been made to pull
initial COS concentrations, the decomposition of COS all of the relevant chemistry together in Scheme 5,
at high temperatures could also include all of the although it is not comprehensive in terms of every
chemistry depicted in Scheme 1 arising from the inter- reaction discussed in the previous sections. It should
action of CO2 and S2. be noted that species from one side of some of the
Ind. Eng. Chem. Res., Vol. 40, No. 2, 2001 507

equations are shared to simplify the scheme. Also, some (4) Hyne, J. B.; Goar, B. G. The Claus Revisited-Part 4.
reactions are repeated within the scheme to highlight Sulphur 1997, 248, 43-48.
the formation of certain species (CO, COS) by more than (5) Kerr, R. K.; Paskall, H. G.; Ballash, N. Claus Process:
Catalytic Kinetics: Part 1. Modified Claus Reaction. Energy
one pathway. Species highlighted in squares can be Process. Can. 1976, 5, 66-71.
considered to represent feed species in the Claus (6) Kerr, R. K. and Paskall, H. G. Claus Process: Catalytic
furnace, although SO2, of course, is derived from the Kinetics: Part 2. COS and CS2 Hydrolysis. Energy Process. Can.
primary reaction of H2S with O2. 1976, 6, 38-44.
One of the most interesting aspects of this chemistry (7) Paskall, H. G. Capability of the Modified Claus Process. A
is the high reactivity of SO2 in COS, CS2, and CO Final Report to the Department of Energy and Natural Resources
of the Province of Alberta; Western Research and Development:
formation and destruction. Indeed, SO2 can actually be Calgary, Alberta, Canada, 1979; Chapter IV.
formed by reaction of CO2 with S2 although this reaction (8) Paskall, H. G. Reaction Furnace Chemistry and Operational
would only proceed quickly in the flame zone. Also, it Modes. Sulphur Recovery; Western Research: Calgary, Alberta,
is evident that the amount of hydrocarbon impurity 1981 (republished 1990).
being fed with the acid gas will have a marked influence (9) Sames, S. A.; Paskall, H. G. So You Don’t Have a COS/CS2
on the CO, COS, and CS2 levels of the furnace/WHB Problem, Eh?. Sulphur Recovery; Western Research: Calgary,
Alberta, 1984 (republished 1990).
process gas as these species derive directly from hydro-
(10) Monnery, W. D.; Svrcek, W. Y.; Behie, L. A. Modeling of
carbon reactions and the myriad of CS2 conversion the Modified Claus Process Reaction Furnace and the Implications
pathways. It should be noted, however, that hydrocar- on Plant Design and Recovery. Can. J. Chem. Eng. 1993, 71, 711.
bons entering the furnace could undergo the desired (11) Karan, K.; Mehrotra, A. K.; Behie, L. A. COS-Forming
oxidation to CO2, although partial oxidation or steam Reaction Between CO and Sulfur: A High-Temperature Intrinsic
reforming would lead to CO, among other products (see Kinetics Study. Ind. Eng. Chem. Res. 1998, 37, 4609.
ref 21 for further discussion of these points). As can be (12) Karan, K.; Mehrotra, A. K.; Behie, L. A. Use of New
Kinetics for COS Formation to Achieve Reduced Sulfur Emissions
noted from Scheme 5, multiple pathways give rise to from Claus Plants. Can. J. Chem. Eng. 1999, 77, 392.
CO. Thus, all of these reactions will affect the CO/S2/ (13) Sames, J. A.; Paskall. H. G.; Brown, D. M.; Chen, M. S.
COS chemistry in the WHB by virtue of controlling the K.; Sulkowski, D. Field Measurements of Hydrogen Production
CO concentration entering that unit. in an Oxygen-Enriched Claus Furnace. Proceedings of the Sulfur
Overall, it would appear that a vast amount of kinetic 1990 International Conference, Cancun, Mexico, 1990; pp 89-105.
data on individual reactions would be needed to model (14) Towler, G. P.; Lynn. S. Development of a Zero-Emissions
Sulfur Recovery Process: 1. Thermochemistry and Reaction Kinet-
CO and COS species within the furnace/WHB system. ics of Mixtures of H2S and CO2 at High Temperature. Ind. Eng.
Although this task is not impossible, we are taking the Chem. Res. 1993, 32, 2800.
more direct approach of producing data sets under (15) Faraji, F.; Safarik, I.; Strausz, O. P.; Torres, M. E.;
relevant combustion conditions with the goal of produc- Yildirim, E. CO-Catalyzed Conversion of H2S to H2S + S. 1.
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(16) Dowling, N. I.; Clark, P. D. Kinetic Modeling of the
Acknowledgment Reaction Between Hydrogen and Sulfur and Opposing H2S De-
composition at High Temperatures. Ind. Eng. Chem. Res. 1999,
We thank the member companies of Alberta Sulphur 38, 1369.
Research Ltd. for supporting these studies: AEC West; (17) Graven, W. M.; Long, F. J. Kinetics and Mechanisms of
Agrium Inc.; Air Liquide Canada Inc.; Air Products & the Two Opposing Reactions of the Equilibrium CO + H2O f CO2
Chemicals Inc.; ALCOA Industrial Chemicals; Ametek + H2. J. Am. Chem. Soc. 1954, 76, 2602.
Process & Analytical Instruments Division; Amoco (18) Sames, J. A.; Paskall, H. G. So You Don't Have a COS/
CS2 Problem, Eh?. Sulphur 1984, 172, 47-50.
Canada Petroleum Company Ltd.; Apollo Environmen- (19) Svrcek, W. Y. Kinetic Modeling of the Modified Claus
tal Systems Corp.; Bechtel Corporation; BG Technology; Process Reaction Furnace; Contract #509-4913-2795; Progress
Black & Veatch Pritchard Inc.; BOC Group; Brimstone Report, July-December 1998; Gas Research Institute: Chicago,
Engineering Services Inc.; Burlington Resources; Ca- IL, 1998.
nadian 88 Energy Corporation; Canwell Enviro-Indus- (20) Clark, P. D.; Dowling, N. I.; Huang, M. Mechanisms of CS2
tries Ltd.; Chevron Canada Resources; Crescent Tech- Formation in the Claus Front End Reaction Furnace. Proceedings
of the 47th Annual Laurance Reid Gas Conditioning Conference;
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