2800 Ind. Eng. Chem. Res.

1993, 32, 2800-2811

Development of a Zero-Emissions Sulfur-Recovery Process. 1.

Thermochemistry and Reaction Kinetics of Mixtures of H2S and CO2 at
High Temperature
Gavin P. Towlert and Scott Lynn'
Department of Chemical Engineering, University of California at Berkeley, Berkeley, California 94720

When hydrogen sulfide is heated above 600 O C in the presence of carbon dioxide, the conversion
of H2S to elemental sulfur is greater than when hydrogen sulfide is heated alone. Formation of
elemental sulfur is favored by high temperature, low pressure, and low water content in the gas.
The rate-limiting step is the thermal dissociation of H2S. The hydrogen then equilibrates rapidly
with C02, forming CO and H2O via the water-gas-shift reaction. The equilibrium of H2S dissociation
is therefore shifted t o favor the formation of elemental sulfur. The main byproduct is COS, which
is formed by a reaction between C02 and H2S that is analogous to the water-gas-shift reaction. A
quench rate of 1000 "C/s or greater is sufficient to prevent loss of elemental sulfur by back-reaction
or reaction to COS during cooling. Formation of small amounts of SO2 and CS2 is thermodynamically
feasible but has not been observed. Molybdenum disulfide is the best catalyst for H2S dissociation
of those discussed in the literature. A process based on this chemistry has significant advantages
over the Claus process in that it need not produce any tail gas, it allows recovery of the chemical
(or fuel) value of the hydrogen from the H2S, and it requires much less stringent process control.

Introduction 99.8% (West, 1984). This technology allows economic

The recovery of sulfur from fossil fuels is of major
importance in the chemical and energy industries. Sulfur
must be removed from fuels in order to comply with
legislation designed to prevent environmental damage due
to acid precipitation. Sulfur must also be removed from
petrochemical feedstocks to prevent degradation of cat-
alysts used in downstream processing. If this sulfur can
be recovered in a usable form then its sale will partially
offset the cost of its removal from the fossil fuel. The
amount of sulfur recovered from fossil fuels accounted for
roughly 62 % of all sulfur consumed in the United States
in 1991 (Chem. Eng. News, 1992).
Most industrial sulfur recovery is carried out using
variants of the Claus process, which is based on the partial
oxidation of H2S by S02:
2H2S+ SO2 s 3 s + 2H20 (1)
To provide the SO2 for this reaction, a part of the H2S is
burned with added air, which leads to the problems
described below. The gas mixture then passes through
several stages of catalytic conversion, with condensation
and removal of product sulfur between stages. Because
of the introduction of air to the process, there is a con-
siderable amount of nitrogen flowing through the Claus
plant (>60% of the gas stream at any point downstream
of the combustor). This inert material must be removed
as tail gas; however, after three or four conversion stages
the tail gas still contains some sulfur-containing species,
typically 2000-3000 ppm of H S plus S02. The tail gas
must therefore be sent to a treatment plant to remove
these contaminants to an acceptable level. A number of
tail-gas processes are reviewed by West (1984). Of these,
the process most widely used industrially is the SCOT
process; however, a SCOT unit may cost as much as the
Claw plant itself (West, 1984). If a sulfur-removal process
is run in conjunction witha Claus plant and tail-gas cleanup
process, then overall recovery of sulfur may be as high as
+ Current address: Centre for ProcessIntegration, Department
of Chemical Engineering, U.M.I.S.T., P.O.Box 88, Manchester
M60 lQD, United Kingdom.
0888-5885/93/2632-2800$04.00/0
recovery of sulfur; however, it is very costly because of the
large number of processing steps needed to prevent sulfur
emissions, and it does not recover the chemical or fuel
value of the hydrogen from the H2S.
An alternative route for sulfur recovery suggested by
Raymont (1975) was to decompose H2S either thermally
or catalytically, and hence recover the hydrogen as well
as the sulfur:
H2S e H2 + (1/2)S2 (2)
This route received much attention in the 1970's and early
1980's, but proved uneconomic due to the high temper-
atures required to achieve significant conversion. At-
tempts to improve the conversion by continuous separation
of the products were attempted, but these also proved
uneconomic due to the high costs associated with sepa-
rating H2 from H2S at high temperatures (Fukuda et al.,
1978). Several processes were designed using reaction 2
(Banderman and Harder, 1982; Fukuda et al., 1978), but
none was developed commercially.
The chemistry which led to the present work was
observed experimentally while experiments on the de-
sulfurization of coal gas using limestone were carried out.
These experiments involved heating limestone in an
atmosphere containing 96 mol% C02, 4% H2, and 1%
H2S. The reaction-gas mixture entered the outer tube of
a reactor that extended into a furnace and was withdrawn
through a smaller, concentric inner tube. The difference
in diameters between these tubes was such that the
residence time in the inner tube was only one-thirtieth
the residence time in the outer tube. The gases exiting
the reactor were consequently quenched very rapidly by
countercurrent heat exchange with the cooler incoming
gases. More details of the experimental design are given
in Towler (1992). When these experiments were carried
out at a temperature of 800 OC, it was observed that a
yellow deposit, which was found to be elemental sulfur,
formed inside the inner tube in the region where the tubes
exited the furnace.
The reaction by which sulfur formation occurs was
initially postulated as
0 1993 American Chemical Society

C02 + H2S CO + H20 + (1/2)S2 (3)
which can be seen to be the sum of reaction 2, Le., H2S
decompoeition, and the reverse of the water-gas-shift
reaction:
CO + H20 F=? CO, + H, (4)
Reaction 3 is similar in form to the Claus reaction in that
it achieves partial oxidation of H2S and could therefore
form the basis for a potential sulfur-recovery process.
Furthermore, the byproduct of reaction 3 is carbon
monoxide, which can be reacted with steam to generate
hydrogen, thereby effectively recovering the H2 from the
H2S. Initial stages in the development of such a process
are described below, and a full description of the process
is given in the second part of this paper (Towler and Lynn,
1993). However, we cannot claim to be the first to have
reported this reaction, as the same chemistry was patented
by Bowman (1991) and used as the basis for a process
which will be discussed below. We were unaware of
Bowman's patent until the work reported here was nearly
completed.
Previous Work
A great deal has been written on the oxidation of H2S
by SO2 as required in the Claus process. There has also
been much research into the thermal decomposition of
H2S as a source of hydrogen, including some efforts that
tried to react the H2S with CO to form COS and H2 (see
below). Very little research has been reported addressing
the partial oxidation of H2S with C02.
As was noted above, North American interest in the
thermal decomposition of H2S began with a paper by
Raymont (1975), although it had received some attention
in Japan prior to that date (Kotera, 1976). The main focus
of Raymont's work (and much of that which followed)was
on H2S decomposition as a source of hydrogen, rather than
as a means of S recovery. Raymont found the decom-
position of H2S (reaction 2) to be thermodynamically un-
favorable at temperatures below 1800 K. His kinetic
studies showed that the reaction proceeds rapidly to
equilibrium without requiring catalyst at temperatures
above 1250 K, though he did not state the residence time
of the reactor in which these experiments were carried
out. Below this temperature catalysis is required to achieve
a satisfactorily rapid rate; however, Raymont did not
identify a particular catalyst. Raymont also correctly
observed that the equilibrium conversion of H2S could be
enhanced by combining the decomposition reaction with
a more favorable reaction. Because of his emphasis on H2
recovery, he chose the reaction
2CO + s2 * 2cos (5)
giving the overall reaction
+
H2S CO * H2 + COS (6)
The COS could then be converted to S2 via
*
2 c 0 s + so2 2Co2 + (3/2)s2 (7)
the SO2 being produced in a manner similar to the Claus
process. He suggested that reaction 6 be carried out under
conditions that allow continuous separation of Ha from
COS, i e . , in a reactor with metal-alloy-membrane walls.
Since this technology was not available, attention shifted
to continuous removal of sulfur instead.
Roth et al. (1982)investigated the mechanism of thermal
decomposition of H2S a t low concentrations (<200 ppm)
and high temperatures (>1965 K) as part of an investi-
Ind. Eng. Chem. Res., Vol. 32, No. 11, 1993 2801
gation of sulfur conversion in flames and found the primary
mechanism to be second order. It should be noted,
however, that their experimental temperatures were
significantly higher than those of interest to this study.
Kaloidas and Papayannakos (1989) investigated the
noncatalytic thermal decomposition of H2S in the tem-
perature range 60+860 OC and pressure range 1.3-3.0 atm.
They developed a kinetic model based upon a free-radical
mechanism with the splitting of H2S into free-radical
intermediates as the rate-limiting step. The model gave
good agreement with their experimental results, and they
found the rate of decomposition to be given by
= kIPH2S (8)
where k l = 784.1 exp (-23600/T) (mol/(cm3.s-atm))and
PH~S is the partial pressure of H2S in atm. They dem-
onstrated clearly that the rate of thermal decomposition
was first-order in PH~S under the conditions observed and
cited numerous references confirming the presence of H',
HS', and S' radicals in gaseous systems containing H2S
at high temperatures (Bradley and Dobson, 1967a,b;Levy
and Merryman, 1965; Merryman and Levy, 1967, 1972;
Norrish and Zeelenberg,1957). They also determined that
alumina (A12031 does not catalyze the decomposition
reaction.
Several catalysts for H2S decomposition have been
described; in particular, molybdenum disulfide, MoS2, was
identified at an early stage (Katsumoto et al., 1973).
Fukuda et al. (1978) described the kinetics of H2S de-
composition over molybdenum disulfide and also deter-
mined that tungsten disulfide is a slightly less effective
catalyst than molybdenum disulfide, whereas NiS is much
less effective due to the formation of NiS2. Chivers et al.
(1980) performed similar testa and found that Cr2S3 gave
similar performance to WS2, while FeS, COS,and a range
of copper sulfides (CU~S, CugS5, and CuS) were not effective
as catalysts. Chivers et al. also found that MoS2 was the
most effective catalyst above 600 "C, but WS2 and Cr2S3
were more effective below 600 "C. Possible mechanisms
for H2S decomposition over MoS2 are described by Sugioka
and Aomura (1984) and Katsumoto et al. (1973).
Chivers and Lau (1985) reported catalytic activity for
Li2S but found that sodium and potassium sulfides (Na2S,
K2S) and polysulfides (Na2S2, K2S2, Nan&, K2S3, Na&,
and K2S4) were not catalytically active; however, these
sulfides react with the gas, forming amorphous mixed
polysulfideproducts. Chivers and Lau (1987)investigated
vanadium sulfide, v2s3, and mixed sulfide systems (v2s3/
FeS, V2S3/CugS5 and V2SdZnS) in both flow and thermal-
diffusion-column reactors a t temperatures between 400
and 800 OC. They suggested that v2s3 and V2S3/CugS6
both perform better than MoS2 in flow reactors, with v2s3/
CugS5 being particularly effective at high temperatures.
Kotera (1976) investigated the decomposition route via
reaction 6, but found this pathway to be complicated by
the reaction
2cos * CO, + CS, (9)
He therefore switched his attention to the thermal
decomposition route. Interest in the COS route has
recently been revived by Gangwal et al. (1991), who
proposed using coal gas to reduce SO2 to elemental sulfur
via
2co + so2F? 2CO2+ (l/n)S, (10)
and suggested that coal gas would also react with COS
and H2S to form elemental sulfur. The maximum tem-
2802 Ind. Eng. Chem. Res., Vol. 32, No. 11, 1993
perature they investigated was 650"C, and they suggested
a process pressure of 20 atm. Their experiments showed
that a high conversion of HzS to elemental sulfur could be
obtained in a system containing coal gas and SOz;however,
they were not aware that the H2S must be undergoing
oxidation by COZ as well as SO2 in this system. The
pressure selected was too high for formation of elemental
sulfur to be strongly favored.
Fellmuth et al. (1987) examined the reaction of H2S
and C02. They were, however, chiefly interested in zeolite
deactivation and did not extend their studies above 300
"C. The main reaction they observed was therefore
H2S + CO, * COS + H,O (11)
which they found to be catalyzed by basic zeolites. This
reaction can be seen to be analogous to the water-gas-shift
reaction and is important as a mechanism for COS
formation. The equilibriumconstant, KW,for this reaction
is fitted over the temperature range 450-1100 "C by the
expression
= 0.4347 exp(-2917/T)
KsBB (12)
The endothermic nature of the reaction and weak
temperature dependence of the equilibrium constant give
further evidence to support the comparison with the water-
gas-shift reaction, and we might therefore expect this
reaction to have equally rapid kinetics. Unfortunately
most of the research on this reaction has been related to
the development of catalytic processes for COS hydrolysis
prior to gas scrubbing and was thus carried out at low
temperatures, typically below 300 "C. Although there is
much discussion of the competitive absorption of different
species and the nature of the catalytic sites, only one paper
was found to give an activation energy for the reaction.
George (1974) found the activation energy to be 12 kcaU
mol for COS hydrolysis on cobalt molybdate at 230 "C.
The Arrhenius plot he presented showed, however, that
this energy was based on a line drawn through only four
data points. The line fitted the three points at lower
temperatures reasonably well, but substantially under-
predicted the point at the highest temperature. There is
therefore good reason to believe that George may have
overestimated the activation energy, especially when we
consider that we are operating several hundred degrees
above the temperatures used in his study. In any case,
the value 12 kcal/mol is low for an activation energy,
confirming the similarity between this and the water-gas-
shift reaction and giving us good reason to believe this to
be an important step in COS formation.
An alternative route by which COS may be formed in
the H2S/C02 system is reaction between CO and S2 via
reaction 5, which is the reverse of the thermal dissociation
of COS. The kinetics of COS decomposition was studied
by Schecker and Wagner (1969) in the temperature range
1500-3100 K. They found the rate to be second order and
given by
dCcos - 61000
dt --lo
14.2
(
exp -- RT )'btdccOs (13)
where CCOSis the concentration of COS (mol/cm3),Cbd
is the total concentration (ie., COS + inerts) (mol/cm3),
and R is the ideal gas constant (cal/(mol K)). The results
of Schecker and Wagner (1969) were subsequently con-
f i i e d by Chenery et al. (1983). Dokiyaet al. (1978)looked
at the reverse of COS decomposition, i.e., the formation
of COS from CO and elemental sulfur. They did not report
a kinetic expression; however, their data showed the
conversion attained to be strongly influenced by flow rate,
indicating that this reaction can be quenched.
It should be clear that for the HzS/COZsystem at high
temperatures we are concerned with the interplay between
a large number of possible gas-phasereactions. For process
design purposes we wish to be able to predict the reactor
size required to achieve a given conversion of H2S. We
must also understand the mechanism by which the main
byproduct, COS, is formed if we are to design a satisfactory
quench. Although most of the reactions in the H2S/C02
system have been analyzed in isolation there is little
information in the temperature range of interest, and no
report of the kinetics of H2S decomposition in the presence
of C02 was found in the literature.
Thermochemical Analysis
A series of calculations was performed to evaluate the
equilibrium properties of mixtures of carbon dioxide and
hydrogen sulfide at high temperatures. These calculations
were used to confirm the experimental findings described
above and to determine suitable operating conditions for
a sulfur-recovery process based on this chemistry.
The calculations were carried out using a modified
version of a computer simulation developed by Whitney
et al. (1987),whichcalculates the equilibrium composition
of a reaction mixture, given a feed stream cornposition,
together with a temperature and pressure. The calculation
is performed by first selecting a set of independent
chemical reactions, then determining material balances
for all elements present, and finally determining the
composition of the mixture having the minimum Gibbs
free energy by using a robust, multidimensional Newton-
Raphson iteration procedure. For the high temperatures
(>600 "C) and low pressures ( 4 0 bar) of interest to this
study, it was reasonableto assume that all gas-phase species
behave ideally; therefore fugacity corrections were not
made. Thermochemicaldata were taken from the JANAF
Thermochemical Tables (Chase et al., 1985).
Following the findings of Kaloidas and Papayannakos
(19871, S2 was assumed to be the only elemental sulfur
speciespresent. In actuality, small amounts of other sulfur
allotropes will also exist; therefore the calculations may
slightly underpredict the fraction of elemental sulfur in
the gas at equilibrium. This is a safe-side approximation
that considerably shortens calculation time and obviates
the selection of a thermodynamic database for the other
elemental sulfur species. The sensitivity of the results to
this assumption is discussed below.
In analyzing the results of these calculations the most
important informationis the distribution of sulfur between
the different sulfur-containing species. The results are
therefore presented as graphs showing the fractional
distribution of sulfur, i.e., the fraction of the total sulfur
present as each species on a molar basis. The sulfur-
containing species included in the calculations were H2S,
S2,SO2, CS2, COS, and SOS. Results for CS2 and SO8 are
not reported, however, as neither ever accounted for more
than 0.002 of the total sulfur present.
In discussing the results of the survey it is useful to note
that since we consider eight chemical compounds (Cop,
CO, Ha, H20, H2S, SZ,, 9 0 2 , and COS) containing four
elements (C, H, 0, and S), we require four reaction
equations to specify the equilibrium composition of the
gas phase. For the purposes of this discussion these will
be taken as being the water-gas-shift reaction,
CO + H20 Z= C02 + H, (4)
the H2S decomposition reaction,
 Ind. Eng. Chem. Res., Vol. 32, No. 11, 1993 2803
1.0, I 0.8 0.10

0.08

B
VI
0.06
5 0.6 - In
e

1
Q
VI I.
c 2
004 d"
v)
0.4 e
Q

002 89

". , 0.00
0 2 4 6 8 10 12

nn I
"." I
900 1000 1100 1200
Temperature (K)
Figure 1. Equilibrium distribution of sulfur-containing species aa
a function of temperature for H2S only (1atm).
- /
0.0
900 1000 1100 1200 1300
Temperature (K)
Figure 2. Effect of temperature on sulfur distribution for a feed
containing 50% HzS, 50% COZ at 1 atm.
H2S ~i H2 + (1/2)S,
the Claus reaction,
2H2S + SO, e (3/2)S2+ 2H20
and the formation of COS from CO and S2,
2co + s, Fi 2 c o s (5)
It should be noted that these reactions merely form an
independent set for equilibrium calculations and are not
necessarilyindicative of the reaction mechanism. Reaction
mechanism and kinetics are discussed below.
Effect of Temperature. Figure 1shows the equilib-
rium sulfur distribution given by the decomposition of
H2S as a function of temperature at 1atm in the absence
of C02. Figure 2 shows the distribution for an initial feed
of 50% H2S, 50% C02. Comparing the figures, it can be
seen that the fraction of S present as elemental sulfur at
equilibrium has been enhanced by a factor of roughly 2
a t all temperatures. This significant increase in conversion
suggests that a process based on this chemistry would be
more successfulthan a process based on the decomposition
of H2S in the absence of COa and demonstrates the
effectiveness of the water-gas-shift reaction for shifting
the equilibrium of H2S decomposition.
1300 1400
The equilibrium yield of S2 increases with increasing
temperature because of the endothermic nature of HzS
decomposition (reaction 2). Increasing H2S decomposition
causes an increase in the amount of HzO present in the
gas, which helps drive the reverse of the Claus reaction
(1);therefore the equilibrium fraction of SO2also increases
with temperature. This imposes an important limit on
the operating conditions for the sulfur-recovery process
as formation of SO2 is detrimental to process operation
and should be avoided whenever possible. The formation
of COS is favored by low temperatures, since reaction 5
is exothermic as written. An important consequence of
this thermal behavior is that if a mixture of C02 and H2S
is brought to equilibrium at high temperature and then
cooled slowly, the elemental sulfur is able to back-react
to H2S and COS, thereby losing part or all of the reaction
yield. This can be prevented by quenching, Le., cooling
0 00 the gas rapidly to a temperature a t which the sulfur-
1400
consuming reactions are very slow compared to processing
timescales. Quenchingto about 600"C a t a rate of roughly
lo00 K/s was found experimentally to be sufficient.
Effect of Pressure. The water-gas-shift reaction (4)
is equimolar, and therefore its equilibrium composition is
(2) independent of pressure. All of the elemental-sulfur-
forming reactions lead to a net increase in the number of
moles; consequently the amount of S present as elemental
(1) sulfur decreases with increasing pressure as can be seen
in Figure 3. An interesting, and perhaps unexpected, result
is that the equilibrium fraction of SO2 also decreases. If
we consider the ratio (number of moles of products)/
(number of moles of reagents) for the S2-formingreactions,
we find that for reactions 2 and 5 the ratio is 1.5, whereas
for the Claus reaction it is only 1.17. COS formation and
H2S decomposition are therefore much more sensitive to
pressure than the Claus reaction, and consequently when
the pressure is increased S2 is more likely to be converted
to H2S or COS via these routes than to SO2 via the Claw
reaction. Obviously this is somewhat dependent on the
initial composition of the gas (particularly the amount of
HzO present) since the water-gas-shift equilibrium is
pressure-independent.
Effect of the COdH2S Ratio in the Feed. Figure 4
shows the effect of increasing the initial mole fraction of
H B in C02 on the equilibrium distribution of sulfur
compounds. At very low H2S/C02 ratios, SO2 is the most
favored product; however, the fraction of the S present as
SO2 falls rapidly as the initial HzS concentration is
2804 Ind. Eng. Chem. Res., Vol. 32, No. 11, 1993
, 0.20

Feed sat w i t h H,O

a t 4OoC

i\\
0.15

Yield of S2 per mole of H,S

0 5 i i in Reactor Feed
0.10 04

0.3

0.05

0.2

0.0 n ""
"."I 0.1
0 10 20 30 40 50
Inltid X H,S In COz

Figure 4. Effect of the initial H&C02 ratio on the equilibrium 0.0 1

I , , 1 I / , I l
o io 20 30 40 so 60 70 a0 90 loo
distribution of sulfur-containing species at 1 atm, 900 OC.
Initial Z H,S in CO, (900°C, 1 bar)

Figure6. Yield of elemental sulfur as a function of feed concentration

,E
0
E
c 0.6
I
~ 10.06
(900 OC,1 bar).

Table I. Effect of Including Sulfur Allotropes

v) fraction of fraction of
P 8 Sulfur-Containing Sulfur-Containing
Species Species
species S2only S2, ...,Se species S2only S2, ...,SS
S2 0.324 0.318 Se 0 O.ooOo24
ss 0 0.00649 H2S 0.614 0.613
s
4 0 0.000303 SO2 0.000811 0.000798
s5 0 O.ooOo5 COS 0.0607 0.0604
S6 0 0.000123 CS2 0.0000087 0.0000087

-
SI 0 0.000107

In particular, the equilibrium fraction of S2 decreases only

increased and the mixture becomes more reducing in
nature.
The fraction of sulfur present as S2 passes through a
maximum at around 6% H2S in C02, since increasing the
amount of H2S present not only makes the mixture less
oxidizing in nature, but also lowers the S2 fraction by
dilution with H2S. A similar effect is observed for COS.
It should be noted that the results for COS are plotted on
an expanded scale (4X magnification) and that the COS
fraction is therefore much less sensitive to the feed
composition than the S2 fraction.
Effect of H20. For processing reasons, it is likely that
any gas stream containing H2S and CO2 would also contain
a small amount of water vapor. (This arises from the use
of absorber/stripper loops for acid-gas cleaning-the acid
gas stream usually leaves the stripper saturated with water
at condenser temperature.) It is therefore important to
understand the effect of the initial HzO concentration on
the equilibrium distribution of sulfur-containing species.
Figure 5 shows this variation at 900 OC and 1atm, for a
feed containing 1:l C02 and HzS, as the water fraction is
increased from 0 to 109%. At l-atm pressure, 10% initial
water concentration corresponds to the feed gas being
saturated with water at 46 OC. Perhaps the most salient
feature of Figure 5 is that none of the species is strongly
affected by increasing the H2O fraction over this range.
from 0.32 to 0.29, a change of under 10%.
Increasing the water content helps drive the reverse
Clam reaction; thus the SO2 fraction increases, though
not strongly. The effect of increasing the feed H20 content
on the water-gas-shift reaction is to drive the reaction
toward C02 and H2, thereby tending to reduce H2S
decomposition. This also reduces the CO concentration
and hence favors the reverse of reaction 5, leading to COS
decomposition and causing the COS fraction to decrease
as the H2O fraction increases. The increased COS de-
composition to some extent counteracts the reduced H2S
decomposition, giving rise to the observed weak depen-
dence of S2 fraction on H20 content.
Allowance for Sulfur Allotropes. As was stated
above, elemental sulfur can exist as a number of allotropes
S2, ...,SSunder the conditions of this study. To confirm
the results of Kaloidas and Papayannakos (1987) cited
above, the base calculation (1 atm, 900 "C, 5050 H2S:
CO2) was repeated with the sulfur speciesS3,...,Sa included.
The results are shown in Table I. The fraction of S present
as elemental sulfur was 0.3240 in the case where only S2
was considered and 0.3256 in the case where all S allotropes
were allowed. This confirms that the effect of including
the compounds S3,..., Se is negligible.
Reactor Yield. In considering the design of a sulfur-
recovery process the optimum reactor feed is determined
by several factors, which are somewhat dependent upon
the process configuration, and will therefore be discussed
in greater detail in the second part of this paper (Towler
and Lynn, 1993). To a first approximation, however, we
can consider the best feed composition to be that which
maximizes the number of moles of elemental sulfur

I I
Pipellno
I v
I
11
SRI 8610 Gal Chromatoirsph
8
Sulfur
Condemer
Figure 7. Experimental apparatus.
Inner tube o.d, 0 3 m m
td 3.9 mm
C u Inlet
II II h
I
I
Outer Tuba 1.d. 21.8 mm
T
. I
cu
outlet
I . .
kction
Figure 8. Reactor dimensions.
produced per mole fed to the reactor, i.e., the yield per
reactor pass. We can determine the yield at chemical
equilibrium quite easily, by multiplying the fraction of S
present as elemental sulfur by the fraction of HzS in the
feed.
Figure 6 shows the reactor yield at 900 "C, 1 bar, as a
function of the concentration of HzS in the feed (drybasis).
The solid lines in Figure 6 are for a dry feed, in which case
the maximum yield is 0.167 at an initial concentration of
67% HzS in C02. This represents an improvement of 36%
over the yield in the absence of C02. This could raise the
question of whether the presence of C02 is really necessary
to the process; however, it must be remembered that the
water-gas-shift reaction (41, by significantly lowering the
hydrogen concentration, also minimizes back-reaction
during the quench. It is therefore much easier to maintain
a high yield in the presence of C02 than in its absence.
As noted above, the feed will normally contain some
H2O; therefore the calculations were repeated for a feed
saturated with water at 40 "C, 1 atm. The results are
shown as the dashed lines in Figure 6. In this case the
maximum yield of elemental sulfur per mole of feed gas
is 0.1452 a t a feed fraction 71% H2S in C02. This is
somewhat lower than the dry case, mainly due to dilution:
if we correct the results to a dry basis, the yield is 0.157,
Le., an improvementof 27.7% over the yield in the absence
Ind. Eng. Chem. Res., Vol. 32,No. 11,1993 2806
Vent
U U I
T
hookout
TUlk
-H N.08AbiorpUon
1 ScNbbclr
I I I I L
u u u u u
C02 NP E2S E2 CO
QwtrT b r m o w l l
a.d 7 mm
Cu Sampling/
smep G u Port
of C02. As noted above, the optimum reactor feed com-
position may depend upon other factors as well as reactor
yield, and this will be discussed in the second part of this
paper (Towler and Lynn, 1993). It is, however, important
to note that the maximum in the yield curve is in fact
rather broad and that high yield can therefore be achieved
over a wide range of feed compositions. This has some
important implications (discussed below) when a sulfur-
recovery process based on this chemistryis compared with
a process based on the Claus reaction.
Experimental Section
Experiments were carried out in the continuous-flow
apparatus shown in Figure 7. The C02 and H2S (industrial
grade, supplied by Mattheson Gas Products, Newark, CA)
were mixed at the desired flowrates using high-precision,
low-flow-rate rotameters (Omega Engineering Inc., Stam-
ford, CT), before being sent to the reactor. The reactor
consisted of two concentric quartz tubes mounted in a
high-temperaturefurnace. The gas entered the outer tube
of the reactor, where it was preheated by contact with the
exiting gas and by heating tape around the outside of the
reactor. The gas was then further heated in the furnace
section of the reactor before exiting through the inner
tube. The difference in the tube diameters caused the
2806 Ind. Eng. Chem. Res., Vol. 32, No. 11, 1993
900 1000

800 900

h
700 800
U
0- 0-
u

3e
0
2
600 e
D
700

c
i Inner tube entrance
located here
F
i
500 600

0 Thermowell temperature
400 V Inner tube temperature 500
0 Thermowell temperature
(repeat) /
300 , I f I , I , 400
-5 0 5 10 15 20 25 30 35 0 1 2 3 4 5 6 7 0
Distanoe Along Reactor Time (8)

Figure 9. Reactor temperature profile (T-t = 800 "C, flow rate = Figure 10. Typical Reactor Temperature-Time Ronie
2.935 mL/s). (T- = 900 T,F = 2.935 mlis)

Figure 10. %icd reactor temperaturetime profiie (T,t = 900 "c,

residence time in the inner tube to be roughly 4% of that flow rate = 2.935 mL/s).
in the outer tube, which, together with the temperature
profile obtained in the reactor and judicious selection of Table 11. Exwrimental Conditions and Results
flow rates, ensured that the gas spent long enough at high outlet
temperature to guarantee significant conversion of H2S, temp flowrate feedconcn conv COSmole
before being cooled rapidly as it left the furnace. The (OC) (d/s) ( % HzS in COz) (%) fraction x 103
physical dimensions of the reactor are given in Figure 8. 950 2.935 5 34.4 4.05
These dimensions are of great importance in the modeling 950 2.935 5 35.2 4.43
of the reactor; each dimension is the average of several 950 2.935 10 34.0 2.82
950 2.935 10 34.4 3.99
measurements (taken at different points of the reactor 950 1.468 5 54.3 3.57
where possible). 950 1.468 5 53.1 4.15
The gas leaving the reactor passed through a condenser 950 1.468 10 43.8 4.79
that collected more than 99% of the elemental sulfur 950 1.468 10 44.3 5.16
900 2.935 5 21.5 3.86
formed during the reaction. The gas was then sampled 900 2.935 10 20.0 3.36
using an SRI 8610 Gas Chromatograph (SRI Instruments, 900 2.935 10 22.2 2.99
Torrance, CA), which was used to detect for C02, CO, 900 1.468 5 36.1 3.32
COS, H2S, and S02. This, together with knowledge of the
feed rates, allowed the composition of the gas leaving the Rasults
reactor to be determined.
Because we are concerned with t L e interp.dy between
The temperature profile of the reactor was measured several reactions over a wide range of temperature and
for different heater set-points and gas flow rates. The composition,where substantial changes in the equilibrium
profile was found to vary slightly with flow rate; therefore behavior of the system can occur, the results are best
three standard flow rates were selected and the temper- presented in tabular, rather than graphical, form. The
ature profile was measured for each. A typical temperature conversion of HzS achieved for various experimental
profile for the reactor is shown in Figure 9. The tem- conditions is given in Table 11.
perature profile in the inner tube was found by removing Comparingthe experiments at high flow rate (where we
the condenser and inserting a thermocoupleinto the tube. are furthest from equilibrium conversion),we can see that
The temperature in the outer tube was measured by a the fractional conversion obtained with a feed of 10% H2S
thermocouple in the reactor thermowell and a slight in C02 is roughly the same as that obtained with 5% H2S
correction was made to allow for radiative effects. The in C02. This behavior would be expected if the rate-
uncertainty in the temperatures measured was roughly 3 limiting step were the first-order thermal decomposition
OC. of HzS. At low H2S feed concentrations the water-gas-
Knowledge of the temperature-distance profile and the shift reaction lowers the hydrogen concentration to such
gas flow rate allows calculation of the reactor temperature an extent that back-reactionby recombination of hydrogen
time profile, i.e., the temperature history experienced by and elemental sulfur is negligible. The overall reaction
the gas as it passed through the reador. We can also would thus behave as a first-order irreversible reaction,
calculate the quench rate from the highest temperature for which the conversion in a plug-flow reactor is inde-
attained to any lower temperature. Such calculations were pendent of the feed concentration. We see that this limit
incorporated into the kinetic models described below. A is obtained at both set-point temperatures (but note, how-
typical temperature-time profile is shown in Figure 10. ever, that the gas does not experience a single temperature,
To investigate the effect of quench rate, some experi- but a range or profile, as indicated in Figure 9). Obviously
ments were run with a 3.06-mm quartz rod inserted into as the conversion approaches its equilibrium value this
the inner tube. This reduced the flow area and increased approximation can no longer be true, and we see that the
the gas velocity by a factor of roughly 2.6, allowing the experimentsrun at high temperature and low flow rate do
quench rate to be increased by roughly the same factor. not satisfy this condition as equilibrium effects are more

Table 111. Outlet Compositions Measured for Quenched
and Nonquenched Experiments.
feed outlet composition
H2S quench Hz
fraction rate and
(%) (K/d C02 H2S CO H2O COS S2
5 990 0.928 0.0218 0.00973 0.0260-000357 0.0112
5 2560 0.930 0.0218 0.00884 0.0248 0.00415 0.0103
10 1040 0.873 0.0524 0.0108 0.0408 0.00479 0.0180
10 2700 0.872 0.0519 0.0113 0.0412 0.00516 0.0180
In all cases the flow rate was 1.468 mL/s and the maximum
(I
temperature in the profile was 950 "C.
important for these runs. The error in the reported
conversions can be assessed from the difference between
repeated runs and is typically of the order of 3% ,though
it may be as high as 11%for the experiments with the
lowest conversion.
The outlet compositions found for the high-quench
experiments (in which a quartz rod was inserted into the
reactor exit tube) and experiments run under the same
conditions with lower quench rates are shown in Table
111. Table I11 shows that the outlet compositions for the
high-quench experiments are practically identical to those
for the corresponding low-quench experiments; i.e., the
increase in quench rate gives no added conversion. (The
apparent slight increase in COS formation for both
quenched experiments is negligible compared with the
error in the COS measurements, but see below.) This
confirms that the quench rates used in the bulk of the
experiments (>lo00 "C/s) were high enough to quench
completely both the H2S decomposition back-reaction and
the COS-forming reactions. These results are also useful
in analyzing the formation of COS, as discussed below.
Kinetic Model
In developing a model for the kinetic behavior of the
H2S/C02 system at high temperature, our main goal is to
be able to predict the conversion of H2S to elemental sulfur,
i.e.,to identify the rate-limiting step(s) in H2S conversion.
A secondary goal is to predict the formation of carbonyl
sulfide, so that reactor conditions can be arranged to
minimize formation of this byproduct. Several models
were tried; however, in the interest of brevity we shall
concentrate upon the model that gave the best agreement
with the data.
The reactor is assumed to be in plug flow and is divided
into sections corresponding to the interkls at which the
temperature was measured. For each interval the average
temperature can be found, and hence, knowing the feed
flow rate and pressure, the time the gas spends in the
interval may be calculated (the flow rate can also be
corrected to allow for the increase in molar flow rate that
occurs on reaction). Given the residence time and tem-
perature for each interval we can use a suitable algorithm
to find the concentration of each species a t the end of the
interval. By treating the intervals as a set of plug-flow
reactors in series, we eventually obtain a prediction of the
final outlet concentration.
The pseudo-first-order-irreversible behavior observed
a t high flow rates suggested that the rate-limiting step of
H2S conversion is the thermal decomposition of H2S, with
the hydrogen thereby produced reacting with C02 via the
water-gas-shift reaction. The water-gas-shift reaction is
known to equilibrate very rapidly at temperatures above
600 "C and may therefore be assumed to be always a t
equilibrium.
Ind. Eng. Chem. Res., Vol. 32,No. 11,1993 2807
If this is the mechanism of H2S conversion, then the
rate of change of the H2S partial pressure is given by
d@H2S)/dt = -klPH# + k&-@S:'2 (14)
where kl should be the first-order rate constant as found
by Kaloidas and Papayannakos (1989) and other symbols
are as defined in the Nomenclature section.
If we use suitable average values for the quantities in
the second term on the right-hand side of eq 14 and
integrate, we obtain a "partially integrated" algorithm:
PH2S,n
-- PH,S,n-l exp(-kl,nAtn) +
which may be used to update the H2S partial pressure
from one interval to the next. The first term in this
equation allows for decomposition with no reverse reaction,
and the second term is a correction to allow for the reverse
reaction. It can be seen that in the limit as n and At,, tend
to infinity at a constant temperature, the first term goes
to zero while the second term approaches the equilibrium
concentration.
Having found the number of moles of H2 formed from
the H2S decomposition and knowing the number of moles
of CO2 fed, the concentrations of Con, CO, H2, and H2O
are then found by solving the water-gas-shift reaction
equilibrium equation and three mass balances (C, H, and
01,and the concentration of elemental sulfur is found
from a sulfur mass balance.
This basic model gave good agreement with the exper-
imental data using the published kinetic parameters of
Kaloidas and Papayannakos (1989);however, it is unsat-
isfactory in that it does not describe the formation of the
byproducts COS and SO2. Sulfur dioxide formation was
accounted for by assuming that the Claus reaction was
always at equilibrium. This is a reasonable approximation
above 700 "C, but in practice this did not significantly
alter the predictions of the model as SO2 was formed at
very low levels under the conditions studied. Sulfur
dioxide was not detected in any of the noncatalytic
experiments; therefore the validity of this assumption
could not be tested and remains a subject for future
investigation.
The formation of COS is not so simple to describe. There
are two likely mechanisms for COS formation, namely
reactions 5 and 11. The kinetics of these reactions was
described above, though it should be noted that the work
of George (1974) was carried out under conditions some-
what removed from those of this study.
Since most of the formation of CO and S2 occurs a t the
highest temperatures in the profile, we would expect
reaction 5 to be significant as a COS-forming mechanism
only at the highest temperatures or during cooling, whereas
reaction 11 would be a reasonable mechanism at lower
temperatures when substantial amounts of CO and S2 have
not yet formed. (Indeed, reaction 11plus the reverse of
reaction 5 would be a second-order alternative mechanism
for H2S conversion.) In practice, both reactions are
important, as will be shown by considering the experi-
mental results.
The COS concentrations detected were greater than the
concentrations that would have been found if COS had
been in equilibrium with the other species at the maximum
temperature in the profile. As was shown above, COS
formation is favored by lower temperatures. These high
COS concentrations must therefore have been formed
either as the gas entered the reactor or else as it cooled
2808 Ind. Eng. Chem. Res., Vol. 32, No. 11, 1993

Table IV. Comparison of Experiments and Model

Predictions of the Conversion of HsS CO and S2 in Equilibrium
-
Dredictions of model with various assumptions
E,& from 5% variation 5% variation
-2
4
exptl published of E& for of E.& for -4 -
conv data reaction 1 reactions 1 and 8 Scheckcr and Wagner
34.4 35.1 34.6 34.2 -6 -
35.2 35.4 34.8 34.5
34.0 34.3 33.8 33.5
34.4 34.3 33.8 33.5
54.3 58.6 57.9 57.5 Entrance t o Quench
53.1 58.8 58.1 57.7 -a
-10 -- Tube
43.8 55.2 54.6 54.3
44.3 55.2 54.6 54.3
21.5 19.6 19.8 20.0 -12 -
20.0 19.0 19.2 19.2 0 Measured
22.2 19.0 19.3 19.3 -14 - Concentration
36.1 36.9 37.3 37.4
-16 1
upon leaving. If COS were formed during cooling (via 0 10 20 30 40 50
reaction 5), then the outlet concentration would show a Distance From Reactor Entry (cm)
dependence upon the quench rate, i.e.,the residence time Figure 11. Variation of COS concentration withd i c e into reactor
for cooling. It can be seen from Table I11that this is clearly (maximum temperature 950 "C, flow rate 1.468 mL/s, 5% H2S in
not the case; in fact, the COS outlet concentrations may Cod.
even be higher at higher quench rates. Alternatively, COS
may be formed via reaction (11)when the gas first enters of Schecker and Wagner (1969). Clearly neither of these
the furnace. As the gas flows to regions of higher gives an adequate description of COS formation.
temperature, a point would be reached a t which the COS We can improve the model predictions somewhat if we
concentration is greater than its equilibrium value, at which allow constrained variation of the activation energies for
point COS would begin to dissociate via the reverse of reactions 2 and 11. For HzS decomposition this is not
reaction 5 (thoughnot necessarilyvia the reverse of reaction unreasonable, since the experiments of Kaloidas and
11 since COZ and HzS could still be present at greater- Papayannakos (1989) were performed outside our tem-
than-equilibrium concentrations). By this hypothesis the perature range and must necessarily contain some exper-
outlet COS fraction would not be greatly affected by the imental error; furthermore, Fukuda et al. (1978) found an
quench rate (as long as this is rapid enough to prevent activation energy of 42 kcal/mol, which is somewhat lower
significant reaction when the gas reaches lower temper- than the 43.7 kcal/mol found by Kaloidas and Papayan-
atures) and might even increase at higher quench rates as nakos. If we use an activation energy 5 % lower than that
the time for COS decomposition a t high temperature is of Kaloidas and Papayannakos (41.5 kcal/mol), we obtain
reduced. the third column of Table IV. The preexponential constant
This mechanism not only gives a better explanation of in this case is 2.4 X 10 s-l. The root-mean-square error
the data, but is also more physically reasonable. We know is reduced to 11.3%,which is of the order of experimental
that reaction 11 is somewhat similar to the water-gas- error. The COS concentration predictions are not affected
shift reaction, (4), (see above), and, given that it has such by this change, as COS formation occurs in the low-
alow activation energy,it would be unreasonable to neglect temperature region of the entry tube, Le., before the HzS
its effect at temperatures above 800 "C. Both reactions conversion is significant. We can, however, improve the
5 and 11were therefore incorporated into the model, again prediction of COS concentration somewhat by allowing
using published kinetic parameters, and using an algorithm similar variation of the activation energy of reaction 11.
similar to eq 15 to upgrade the COS concentration from Again this is not unreasonable, due to the rather dubious
one interval to the next. Equation 15 was also modified nature of the graph presented by George (1974). We should
to account for the presence of reaction 11. Mathematical also note that although George was studying the reaction
details of the algorithm used are given in Towler (1992). in the presence of catalyst, his experiments were carried
Table IV shows the experimental results and model out 600 "C below ours, so extrapolation may not be
predictions obtained using the published values of the justified. If the activation energy for COS hydrolysis is
activation energies (Kaloidas and Papayannakos (1989) taken as 8 kcal/mol, we obtain the results of the fourth
for HzS decomposition, and George (1974) for reaction column of Table IV, which predict both conversion and
11). The preexponential constants used were adjusted to COS formation to within experimental error (for details
fit the data over the temperature range observed and were of the COS predictions see Towler (1992)). Obviously the
6.0 X lo6 s-1 for HzS decomposition and 2.4 X lo6 cm3 model predictions could be further improved by including
mole-1 s-l for reaction 11. The root-mean-square error more reactions in the model; however, this merely increases
between the experimental conversions and those predicted the number of adjustable parameters available and is
by the model is about 12%, and the error between the therefore rejected. The model thus obtained gives an
predicted and observed COS concentrations is roughly adequate description of the experimental data over the
the same as the error in the COS measurements. range of conditions studied and can be used for reactor
The predicted COS concentration for a typical exper- design. Some limitations of this model will be discussed
iment is plotted against temperature in Figure 11, from below.
which we see that the model gives the right qualitative
behavior. Figure 11also shows the concentration of COS Effect of Catalysis
that would be found if COS and SZwere in equilibrium
and the concentration that would be present if COS were Having identified the rate-limiting reaction for the HzSl
only formed from CO and SZas predicted by the kinetics COZsystem to be the thermal dissociationof HzS, it follows

that one would improve the overall reactor performance
by supplying a catalyst for this reaction. This is of great
importance in the development of a process based on this
chemistry, as use of catalysis considerably reduces the
reactor volume required. Even with catalysis the reactor
is likely to be the most expensivecapital item in the process
designed (Towler, 1992). Catalysts for the thermal de-
composition of H2S were discussed above; in particular,
molybdenum disulfide (MoS2) is well-known as a catalyst
for H2S decompositionat high temperatures. A short series
of experiments was therefore performed to demonstrate
that MoSz would act as a catalyst for the H2S/C02 system.
It should be stressed that this was only a preliminary
investigation to demonstrate feasibility and that a full
analysis of the catalysis of this system would be a major
piece of work in its own right and was beyond the scope
of this study.
The apparatus described above was modified by packing
the reactor with MoS2 catalyst supported on quartz wool.
Initially, experiments were performed with the reactor
packed with quartz wool in the absence of catalyst; the
quartz wool alone was determined to have a negligible
effect on reaction kinetics. The experiments were then
repeated with the same mass of quartz wool onto which
MoS2 powder had been loaded. The conversion increased
significantly at all temperatures studied (up to 900 "C),
and no evidence of catalyst deactivation was observed over
52 h of operation. This does not eliminate the possibility
that catalyst deactivation is occurring;however, it suggests
that if it occurs at all then it is a rather slow process. In
several cases the distribution of sulfur-containing species
was close to that expected for chemical equilibrium at the
highest temperature in the profile, with the exception that
the fraction of SO2 was lower than expected. It is not
clear whether SO2 was not formed at high temperature or
whether it was lost by back-reaction during cooling.
The experimental conditions were not sufficiently well
defied to allow detailed modeling of the experiments with
catalyst (Towler, 1992). It would be possible to extend
the model described above by using the kinetic expression
developed for H2S thermal decomposition over MoS2 by
Fukuda et al. (19781,but this would not account for the
effect of catalysison reaction 11 and hence COS formation.
Since the catalytic mechanism is known to involve
formation of H*, HS*, and S* free radicals (Katsumoto
et al., 1973),it is unreasonable to expect the catalyst to
affect only the H2S-decomposition reaction. We may
however, use the kinetics of Fukuda et al. (1978)as a first-
order approximation for process design if we assume the
gas reaches the equilibrium concentration (a reasonable
assumption in the light of the experimental results) and
the catalyst loading is the same as that used experimentally
by Fukuda et al. For a fundamental understanding of the
catalytic behavior a more complete analysis is necessary,
which should include not only the effect of the catalyst on
the other reactions in the system, but also the preparation
of catalysts and optimization of properties such as surface
loading, etc. This was beyond the scope of this work;
however, the beneficial effects of catalysis on the H2S/
COz system were clearly demonstrated. More details of
this work are given in Towler (1992).
Discussion
The goal of this study was to develop an understanding
of the kinetics that could be used to design a reactor for
the Zero-Emissions Sulfur Process discussed in part 2 of
this series (Towler and Lynn, 1993). For this purpose the
model developed above is adequate, since it describes both
Ind. Eng. Chem. Res., Vol. 32, No. 11,1993 2809
H2S conversion and the formation of the main reaction
byproduct, COS. On a more fundamental level, however,
the model is somewhat less satisfactory.
Firstly, undoubtedly the greatest source of error in the
model is also, unfortunately, the hardest to quantify. The
model assumed the reactor to consist of two plug-flow
reactors in series, each with a different residence time,
corresponding to the inner and outer flow volumes. In
practice the Reynolds numbers used experimentally were
2 or 4 for the outer tube and 48 or 96 for the inner tube,
so the flow was laminar in all cases. For a first-order
isothermal reaction the conversion in a laminar-flow
tubular reactor is somewhat less than that in a plug-flow
reactor, mainly due to bypassing by material that flows
through the reactor at velocities faster than the average
velocity. If the velocity profile is known (e.g., for a simple
tube), the conversion can be found mathematically (this
involves use of the exponential integral function for a first-
order isothermal reaction). In our case, however, the outer
tube contains two nonconcentric,nonparallelsmaller tubes
(the inner tube and thermowell) and has a marked
longitudinal (and possibly also a slight radial) temperature
gradient,all of which make evaluation of the velocity profile
a complex computational problem in fluid dynamics.
Furthermore, the high molecular diffusivities at the high
temperatures obtaining in the reactor cause some radial
mixing and tend to offset the dispersion of residence times
caused by the velocity profile. Exact characterization of
the laminar-flowreactor is therefore difficult and the plug-
flow assumption was thus necessary, but this may impose
a large error on the model predictions. Experiments that
were run with the outer tube entirely packed with quartz
wool (as preparation for the catalysis experiments) gave
somewhat higher conversionsthan experiments performed
in the absence of this packing. It was not clear, however,
whether the quartz wool was promoting radial mixing and
thus bringing the reactor closer to plug flow or whether
channelingeffects (the quartz wool could not be distributed
evenly) were causing changes in the temperature profile
experienced by the gas.
Secondly, at the high temperatures in question it is not
reasonable to suppose that the net rate of reaction is
affected only by the collisions of molecular species. In
practice there are likely to be many short-lived free radical
species present at low concentrations (for example, H*,
HS*, S*,OH*, SO*, etc.) which probably play an integral
part in the reaction mechanism(s)via a series of initiation,
chain propagation, and termination reactions, much the
same as is found in the analysis of combustion systems.
The presence of these species was referred to by Kaloidas
and Papayannakos (1989)and earlier workers, as noted
above. The success of the experiments with a catalyst
that is known to promote the formation of HS* radicals
is also good evidence of free-radical initiation as the rate-
limiting step; however, HO* radicals are also known to be
of great importance in the water-gas-shiftreaction kinetics
and we did not feel confident enough in the experimental
resulta (for reasons discussed above) to extend our analysis
to proposing a free-radical mechanism. Our analysis was
thus limited to molecular species. A more complete
analysis of the kinetics would take account of free-radical
effects, and also of other minor reactions and byproducts.
This would require rather more accurate data than are
presented here, in particular, the flow pattern in the reactor
would have to be more accurately described. Such an
analysis must therefore be the subject of future work, and
a suitable concluding note is that the engineering model
2810 Ind. Eng. Chem. Res., Vol. 32, No. 11, 1993
developed above will be useful not only in process design,
but also in designingan apparatus for more detailed kinetic
studies.
Process Synthesis
One can easily envisiona processbased on this chemistry,
in which a stream containing H2S and C02 in the correct
proportions is produced by absorbing these species from
a suitable sour gas. This mixture is sent to a furnace,
where it reacts forming S2, CO, HzO, H2, and small amounts
of COS, SOZ,and CS2. The sulfur is condensed and the
remaining acid gases are absorbed in a second absorber,
leaving a product gas consisting chiefly of Hz and CO. The
acid gases can than be stripped from the solvent in a
stripper and recycled to the reactor.
A detailed description of the process, operating con-
ditions, and flowsheet will be presented in part 2 (Towler
and Lynn, 1993). There are, however, some advantages
to a process based on this chemistry that were apparent
from an early stage, including some that arise from the
thermochemical considerations discussedabove. The most
important advantage is that by using CO2 instead of air
as oxidant the tail gas problem is eliminated. The
concentration of sulfur-containing species in the gas
streams leaving the process (the sweetened gas and the
product gas) is therefore determined by the operating
conditions of the two absorber/stripper loops, and may be
controlled to a very low value (a few ppm) depending on
how lean the solvent is stripped in each stripper. Note
that the process is strictly "zero-emissions" in the sense
that there is no tail gas. Effluent streams of course have
some sulfur content, but this may be controlled to as low
a level as can be achieved using absorber/stripper tech-
nology.
Secondly, the product gas leavingthe process is a mixture
of CO and HZsaturated with water vapor a t the absorber
temperature. This gas may be used as fuel or synthesis
gas; in the latter case it may be mixed with steam and sent
to a shift reactor for conversion to hydrogen. The choice
between these uses depends on economic considerations
that may be expected to vary from site to site; however,
the value of the hydrogen from the H2S is recovered in all
cases.
Further advantages arise from the breadth of the
maximum in the yield curve (Figure 6). The Claus process
requiresvery tight control of the air-to-HzS ratio to achieve
an exact stoichiometric ratio of 2 H2S to 1 SO2 in the
reactor sequence. If this ratio is upset slightly, then the
unconverted HzS or SO2 is passed on to the tail-gas unit,
creating considerable difficulties. For a process based on
the interaction between COZ and H2S, the COz-to-HaS
ratio is not critical owing to the rather broad maximum
in the reactor yield. The Zero-Emissions Sulfur Process
is therefore much more robust and requires much less
sophisticated control. A similar problem is caused for the
Claus process if the incoming H2S stream is contaminated
by hydrocarbon material. This is often the case if low-
temperature, high-pressure absorption is used, and is
caused by condensation of organicsin the absorber solution
and subsequent vaporization in the stripper. If hydro-
carbon material is present in the Claus process feed, it
consumes some of the oxygen from the air feed, making
control of the H2S-to402 ratio more difficult. Fluctua-
tions in the amount of hydrocarbon material present
obviously exacerbate this problem. For the Zero-Emissions
Sulfur Process any organic material sent to the furnace
will react with COz, forming carbon monoxide and
hydrogen, and will end up as part of the product gas. This
does not significantly affect the Zero-Emissions Sulfur
Process (except to slightly improve the quality of the
product gas). Other advantages of the new technology
compared to the Claus process will be discussed in part
2 (Towler and Lynn, 1993).
Acknowledgment
This research was funded by the Morgantown Energy
TechnologyCenter through the U.S.Department of Energy
under Contract DE-AC03-76SF00098.
Nomenclature
Ci = concentration of species i (mol/cm3)
Cbd = total concentration of the gas phase (mol/cm3)
Eact= activation energy (cal/(mol-K))
kl = first-order, noncatalytic, H2S thermal decomposition
rate constant (mol/(cm3.s.atm))
kz = rate constant for noncatalytic thermal-recombination
reaction between Hz and S2 (moF5 ~ m - ls-1 . ~atm-1)
KWs = equilibrium constant for the "sulfur-gas-shift"reaction,
reaction 8
n = (subscript) property evaluated under the conditions of
the nth interval
P = total pressure (atm)
Pi = partial pressure of species i (atm)
r = rate of H2S thermal decomposition (mol/(cm3-s))
R = ideal gas constant (cal/(mol.K))
t = time (a)
At = residence time (s)
T = temperature (K)
Tset= furnace set-point temperature ("C)
AT = temperature difference (K)
* = denotes that the species is a free radical
Literature Cited
Bandermann, F.; Harder, K. B. Production of Hz via Thermal
Decomposition of H2S and Separationof Hz and H2S by Pressure-
Swing Adsorption.Znt. J. Hydrogen Energy 1982,7 (6), 471-475.
Bowman, M. G. Thermochemical Cycle for Splitting Hydrogen
Sulfide. U.S. Patent 4,999,178, March 12, 1991.
Bradley,J. N.;Dobson, D. C. Oxidationof Hydrogen Sulfidein Shock
Waves, I. Absorption Studies of OH and SO2 in H&S-02-Ar
Mixtures. J . Chem. Phys. 1967a, 46 (8), 2865.
Bradley, J. N.;Dobson, D. C. Oxidationof Hydrogen Sulfidein Shock
Waves, 11. The Effect of Added Hydrogen on the Absorption of
OH and SOz. J. Chem. Phys. 1967b, 46 (8), 2872.
Chem. Eng. News 1992, June 29, 37.
Chase, M. W., Jr.; Davies, C. A.; Downey, J. R., Jr.; Frurip, D. J.;
McDonald,R. A,;Syvemd,A. N. JAIVAF Thermochemical Tables,
3rd Ed.;National Bureau of Standards: Washington, DC, 1985;
Vol. 14.
Chenery,J. A.;Fakhr, A.; Wood,M. I.; Simpson,C. J. S. M. Vibrational
Analysisof the Products fromthe ThermalDecompositionof OCS
and COz. Chem. Phys. Lett. 1983, 96(2), 143-147.
Chivers,T.;Lau, C. TheThermalDecompositionof HydrogenSulfide
Over Alkali Metal Sulfides and Polysulfides. Znt. J . Hydrogen
Energy 1986, 10 (l),21-25.
Chivers,T.;Lau, C. The Thermal Decompositionof HydrogenSulfide
Over Vanadium and Molybdenum Sulfides and Mixed-Sulfide
Catalyst in Quartz and Thermal-DiffusionColumn Reactors.Znt.
J. Hydrogen Energy 1987,12 (4), 235-243.
Chivers, T.; Hyne, J. B.; Lau, C. The Thermal Decomposition of
HydrogenSulfide Over TransitionMetal Sulfides.Int. J. Hydrogen
Energy 1980,5 (5), 499-506.
Dokiya, M.; Fukuda, K.; Yokokawa, H.; Kameyama, T. The Study
of Thermochemical Hydrogen Preparation. VI. A Hydrogen-
evolving Step through the H2S-CO Cycle. Bull. Chem. SOC.Jpn.
1978,51 (l), 150-153.
Fellmuth,P.;Lutz, W.;Biilow, M. Influenceof Weakly Co-ordinated
Cations and Basic Sites Upon the Reaction of H2S and COZon
Zeolites. Zeofites 1987, 7 (4), 367-371.

Fukuda, K.; Dokiya, M.; Kameyama, T.; Kotera, Y. Catalytic
Decomposition of Hydrogen Sulfide. Znd. Eng. Chem. Fundam.
1978,17(4),243-248.
Gangwal, S.K.;McMichael, W. J.;Dorchak, T. P. The Direct Sulfur-
Recovery Process. Environ. h o g . 1991,lO (3,186-191.
George, Z.M. Kinetics of Cobalt-Molybdate-Catalyzed Reactions of
SO2 with H2S and COS and the Hydrolysis of COS. J . Catal. 1974,
32,261-271.
Kaloidas, V.; Papayannakos, N. Hydrogen Production from the
Decomposition of Hydrogen Sulfide. Equilibrium Studies on the
System HzS/H2/Si (i = 1,...,8)in the Gas Phase. Znt. J. Hydrogen
Energy 1987,12(6),403-409.
Kaloidas, V.;Papayannakos, N. Kinetics of Thermal, Non-catalytic
Decomposition of Hydrogen Sulfide. Chem. Eng. Sci. 1989, 44
(ll), 2493-2500.
Katsumoto, M.; Fueki, K.; Mukaibo, T. An Investigation of the Gas-
Solid Interface Reaction. Bull. Chem. SOC.Jpn. 1973,46,3641-
3644.
Kotera, Y. The Thermochemical Hydrogen Program at N.C.L.I. Znt.
J. Hydrogen Energy 1976,1,219-220.
Levy, A.; Merryman, E. L. The Microstructure of Hydrogen Sulfide
Flames. Combust. Flame 1965,9,229.
Merryman, E. L.; Levy, A. Kinetics of Sulfur Oxide Formation in
Flames: I1Low Pressure HzS Flames. J. Air Pollut. Control 1967,
17,800.
Merryman, E. L.; Levy, A. Disulfur and the Lower Oxides of Sulfur
in Hydrogen Sulfide Flames. J. Phys. Chem. 1972,76(14),1925.
Norrish, R. G. W.; Zeelenberg, A. P. The Combustion of Hydrogen
Sulfide Studied by Flash Photolysis and Kinetic Spectroscopy.
R o c . R. SOC.Ser. A 1957,240,293.
Ind. Eng. Chem. Res., Vol. 32, No.11,1993 2811
Raymont, M. E. D. Make Hydrogen from Hydrogen Sulfide.
Hydrocarbon Process. 1975,54 (7), 139-142.
Roth,P.; L&r, R.; Barner, V. Thermal Decomposition of Hydrogen
Sulfide at Low Concentrations. Combust. Flame 1982,45(31,273-
286.
Schecker, H. G.; Wagner, H. G. On the Thermal Decomposition of
COS. Int. J. Chem. Kinet. 1969,1, 541-549.
Sugioka, M.; Aomura, K. A Possible Mechanism for Catalytic
Decomposition of Hydrogen Sulfide over Molybdenum DisuKde.
Znt. J . Hydrogen Energy 1984,9(111, 891-894.
Towler, G. P. Synthesis and Development of Processes for the
Recoveryof Sulfur From Acid Gases.Ph.D. Dissertation, University
of California, Berkeley, 1992.
Towler, G. P.; Lynn, S. Development of a Zero-Emissions Sulfur-
Recovery Process. 2. A Sulfur-Recovery Process Based on the
Reactions of HzS and COz at High Temperature. Znd. Eng. Chem.
Res. 1993,following paper in this issue.
West, J. R. Sulfur Recovery. In Kirk-Othmer Encyclopedia of
Chemical Technology; Grayson, M., Ed.; Wiley: New York, 19W,
Vol. 22,pp 267-297.
Whitney, G. M.; Bang, Y.; Denn, M. M.; Petersen, E. E. Sulfur
Capture During Partial Coal Combustion. Chem. Eng. Commun.
1987,55(1-6),83-93.
Received for review January 11, 1993
Revised manuscript received June 8, 1993
Accepted June 24, 1993.
Abstract published in Advance ACS Abstracts, September
1, 1993.