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Recovery of sulfur from sour acid gas: A

review of the technology
ARTICLE in ENVIRONMENTAL PROGRESS OCTOBER 2002
Impact Factor: 1.31 DOI: 10.1002/ep.670210312

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Recovery of Sulfwr from Sour Acid

Gas: A Review of the Technology
John S. Eow
Department of Chemical Engineering, University of Leeds, Leeds, LS2 9JT, United Kingdom

i%e modified Clausprocess is the major technologyfor the

recovery of elemental sulfurfrom H S and SO2 A number of
commercial technologiesfor the recovery of sulfurfrom acid
gases are also highlighted here. A Claus tail-gas clean-up
treatment is essential to give high sulfur recovery efficiency
from sour acid gases. Generally, the existing tail-gas clean-up
technologies can be classified into two groups: those that
attain 99%overall sulfur recovery efliciency, and those that
achieve 99.9%efficiency, including the sulfur recovered in
the Claus unit. Theseprocesses are the Amocos Cold Bed
Adsolption (CBA), the SNPMLurgi Sulfreen, the IF8 the SCOT,
the Beavon, and the Wellman-Lordprocesses. The SCOT
process is generally the most reliable and flexible technology.
Process comparisons are also summarized in terms of the sulfur recovey efficiency, hazards and disadvantages, reliability and advantages, plant capacity and ecological impacts.
Several changes and new trends are also highlighted here,
such as the introduction of non-permselectivecatalytic membrane reactorsfor the Claus reaction, and the in situ adsoption of water inside the Clam catalytic reactor. ?be successful
utilization of H S by converting it to sulfur and H 2 attains
the triple objectives of waste minimization, resource utilization, and environmentalpollution reduction. Photochemical
and plasmochemical methods are still in the development
stage. Application of electrochemical technology to H2S
requires further development. Research for an optimum
porous catalyst structure is ongoingfor obtaining a relation
of micropores and macropores which would provide effective
conversion of H S and SO2
INTRODUCTION

Sulfur is often considered one of the four basic raw

materials in the chemical industry. It can be produced
from various sources using many different methods,
such as conventional mining methods, o r it can be
recovered as a byproduct from sulfur removal and
recovery processes [ll.
However, changes worldwide have affected sulfur
sources and the amounts consumed in the last 30
years [ l l . Recovered sulfur production has become
more significant as sour feedstocks are increasingly utiEnvironmental Progress (V01.21, No.3)

lized, and environmental laws on emissions and waste

streams have continued to tighten worldwide [2, 31. For
example, voluntary sulfur from the Frasch mining
process supplied only 25% in 1995, compared to about
53% in 1980. Recovered sulfur increased from 5% of
the total production in 1950, to 67% in 1996 111. Discovery and development of large sour natural gas fields in
many countries have also been important factors in this
rapid growth. Increased processing of sour crude oil
and tighter pollution control has caused most refineries
to recover the sulfur content of its crude oil.
Historically, sulfur recovery processes focus on the
removal and conversion of hydrogen sulfide (H2S) and
sulfur dioxide (S02) to elemental sulfur [4, 51, as these
species represent the largest source of potential sulfur
emission [61. H2S occurs naturally in many natural gas
wells, and is produced in large quantities in the desulfurization of petroleum stocks [7-91. It has been considered a liability, which only occasionally can be an
asset, depending on the international sulfur price [51. It
has a high heating value, but its use as a fuel is not
possible because one of its combustion products is
S o l , which is not environmentally acceptable. Therefore, one of the immediate alternative routes for the
utilization of H2S is to break it down to its constituent
elements of hydrogen and sulfur [lo, 111.
Various processes for the removal of SO, in the
combustion gases have been reviewed [121. The majority of the processes are based on a throw-away process,
in which alkali or alkali earth metal reacts with SO, to
form metal sulfate 113-171. However, this approach
results in the disposal of large quantities of sulfate
waste materials. Direct catalytic oxidation of SO2 to
SOg, and subsequent absorption of SO3 in water to
produce sulfuric acid, is an alternative method [17, 181.
This approach applies to process or combustion gases
containing moderate to high concentrations of SO2.
Copper smelters are the primary example.

October 2002 143

Currently the modified Claus technology is widely

used, compared to other processes, to produce elemental sulfur from H2S present in gases from oil
refineries, natural gas, coal gasification an d other
industries [9, 19-23. It was developed by C.F. Claus, in
1883 1241 and was significantly modified in the late
1930s by I.G. Farbenindustrie AG [251. Major improvements were not made in the technology itself or its
application until such a process was required in the
United States in 1950s. This technology h as n o w
advanc e d t o a stage w h e r e overall recovery h a s
increased from 9042% to the level of 98-99% of inlet
sulfur [3, 23, 261.
STUDIES AND RESEARCH ON CIAUS PROCESS MECHANISMS AND TECHNOLOGY

Figure 1 shows a simplified process diagram of a

Claus plant. Acid gas contains HzS, C 0 2 and H 2 0 as
major components, an d N 2 a n d hydrocarbons a s
minor components. Ammonia (NH3) is also present in
sour water stripper gas [27, 281. The Claus furnace and
the waste heat boiler are normally treated as a single
unit [29, 301. Monnery, et al. [311 and Nasato, et al. [301
identified the reaction furnace as o n e of the most
important, yet least understood, parts of the modified
Claus process. The initial sulfur conversion occurs
there, the SO2 required by downstream catalytic reactors is produced there, and contaminant destruction is
supposed to take place there [22, 321. However, many
side reactions also occur, reducing sulfur recovery and
producing unwanted substances [201. According to
Nasato, et al. [301, Kaloidas and Papayannakos [331
and Dowling, et al. [34], the disassociation and re-formation of H2S in the furnace is important as it provides a portion of the sulfur and a majority of the H2
for other reactions and consumes H2S that could be
used in the Claus reactions. At temperatures below
1,000" C and residence times below 0.5 second, the
H2.S cracking rate is insignificant [321. Below 950" C,
the overall conversion of H2S is low even at a long
residence time. Therefore, the main purpose of the
reaction furnace is to provide optimum temperature
and residence time so that the exiting ratio of H2S to
SO2 is 2: 1, maximizing catalytic conversion downstream [221.
The waste heat boiler, usually a shell and tube heat
exchanger, cools the furnace exit gases from 1,188"C to
154" C in one or two tube passes, generating low-pressure steam [301. This is to condense the sulfur products
(mostly Sg and S6, and a small amount of S2>[4, 21, 221.
Moreover, at 154" C, the sulfur products are at their lowest viscosities [35, 361. Hence, the products would easily
flow through the pipes into the sulfur pit. To prevent
the pipes from becoming blocked, a low pressure jacketed steam generated in the waste heat boiler is introduced around the pipes. Two reactions are believed to
occur in the waste heat boiler tubes:

The principal reaction of the Claus process are as

follows [4, 9, 22, 37, 381:

144 October 2002

2H,S

+ SO,

+ -3 S, + beat

& 2H20

(4)

where n is the average molecular species of the sulfur

vapor product, with n = 2 to 8 and possibly more. In
Reaction (3), about a third of the H2S is combusted in
the reaction furnace to form a stoichiometric amount
of S 0 2 , which is then reacted with the remaining H2S
in Reaction 4 to yield elemental sulfur and water [23,
391. Reaction 3 is carried out in the furnace at 1,188"C,
usually under partial oxidation [40, 411.
Reaction 4 is an equilibrium reaction favored at low
temperature in the presence of a catalyst [21, 37, 421. In
order to increase conversion, Bonsu and Meisen 1431
proposed using fluidized bed reactors, rather than conventional fixed-bed reactors, so that the last reactor
could be continuously operated below the sulfur dew
point. According to Puchyr, et al. [211 and Bonsu and
Meisen [431, if equilibrium conversion could be
achieved in each reactor, the use of fluidized-bed reactors could result in an overall H2S conversion of 99.5 Yo.
The most widely used Claus catalyst is non-promoted spherical activated alumina [23, 441. However, Paik
and Chung [17] reported that Co-Mo/AlzOg, which is
usually used for hydrodesulfurization of a petroleum
feed stock, can convert SO2 with H2S selectively to
elemental sulfur at lower temperature than that commonly used. However, the hydrogenation of SO2 to
H2S occurring o n metal sulfide sites was found to be
much slower than the Clam reaction on alumina 1181.
T h e active sites for t h e SO2 hydrogenation was
believed to be sulfur vacancies in metal sulfide, and
the most effective catalyst had an ability to form and
regenerate sulfur vacancies most easily.
In the Claus process, other sulfur compounds will
form, such as carbon disulfide (CS2) and carbon oxysulfide (COS), and these compounds can often contribute from 20 to 50% of the pollutants in the tail-gas
[44, 451. COS and CS2 are usually hydrolyzed in the
catalytic converter [21, 381, as shown below:

CS2 + 2H20 + 2H2S+ C02

(6)

Studies carried out by Laperdrix, et al. [461 also

reveal that the presence of 0 2 traces in the CSZ-H~O
mixture caused a decrease in the activity of alumina
and titania catalysts due to sulfate formation. IR studies show that sulfate species are reduced by H2S at
320 C on titania, in contrast to the sulfate species on
alumina, implying that titania is much more effective
than alumina when the CS2 iH 2 0 feed also contains
H2S and 0 2 traces [461.
The temperature of the first catalytic re a c to r is
maintained at about 350" C to hydrolyze COS a n d
CSz, while that of the subsequent r e a c t o r s is just
above the sulfur vapor d e w point [421. Transition
metal oxides can be used to modify gamma-alumina
Environmental Progress (V01.23, N0.3)

~~

Recycle from Tail-gas Unit

II

TOTail-gas Unit
~

Preheater

Preheater

I
I

feed
Steam

furnace

p,0

G-l

Reactor

Reactor

boiler

0
0
w
Condenser

Boilkr feed
water

Condenser

Sulphur Pit

Figure 1. Simplified two-stage Claus process flow diagram.

to form a catalyst that is effective at temperatures

higher than the dew point of sulfur [47-491. However,
thermodynamics provide a strong incentive to operate
the catalytic converters at low temperature [3, 501 as a
lower temperature should increase the exothermic
reaction efficiency. Under these conditions, the produced sulfur would be deposited, thus deactivating
the catalyst by fouling [3, 511 and/or decreasing the
specific surface area and pore volume [23, 52-541.
Uncondensed gas, mainly H2S, S02, COS, CS,, N2,
unburned hydrocarbon and NH3, are reacted in the
lower temperature catalytic reactors [381. Alvarez, et
al. [531 and Pineda and Palacios [541 showed that H2S
conversions higher than 90% can be achieved using
concentrations in the range of 1-5% with a relatively
slow catalyst deactivation, especially if the operation
conditions and catalyst properties are optimized.
The adverse effect of water on alumina catalyst,
especially at low temperatures, has been recognized
as being responsible for low activity in the COS
hydrolysis [55, 561 and a decrease in H2S conversion
[571. Conversion with low water content, such as 5%
water vapor, was found to be 2 to 2.5 times higher
than that obtained with 35% water content, apparently
due to a competition with SO2 and H2S for adsorption
sites. The results by Laperdrix, et al. [261 and Steijns
and Mars [571 also indicate that, in the presence of Sn
Environmental Progress (V01.21, No.3)

and H20, H2S and SO2 can be produced. However,

according to Ledoux, et al. [31, the use of a new type
of support, such as Sic, and a nickel-based active
phase provide an active, extremely selective and stable catalyst for the oxidation of H2S into elemental
sulfur by 0 2 at relatively low temperature. The catalyst exhibited a high and stable H2S conversion even
at a sulfur loading of more than 60%. While in the
feed without water, a rapid deactivation was
observed. Water assists in the mechanical removal and
transport of the sulfur formed by the particles of the
active phase on the hydrophilic part of the support
(i.e., oxycarbide or oxide of Si) to the hydrophobic
part (i.e., Sic), leaving free access to the active particles even at high sulfur loading [31.
From thermodynamic calculations, Laengrich and
Cameron [21, Ledoux, et al. [31, Anon [191, Opekar and
Goar 1271, Grancher 1581, and Pearson 1591 recommended three or four catalytic converters operating
under steady state conditions at low temperature.
Thermodynamic calculations indicate the possibility of
reaching efficiencies > 99% [501. Unfortunately, these
results cannot be obtained with current technology
due to reaction kinetic limitations and, particularly,
because of sulfur deposition in the catalyst pores [37,
52, 54, 601. As a catalyst is being covered by sulfur, a
change in the process kinetics should be expected,
October 2002 145

with activity declining. The life and performance of a

catalyst, such as Sepiolite with a structural formula
Si12Mg~030(OH)4(H20>4.8H20[51, 61, 62,1, are thus
closely related to its ability to preserve activity
through fouling. Dowling, et al. [341, Alvarez, et al.
[511Alvarez, et al. (531, Guijarro, et a1.[631, Steijns, et al.
[641, and Dudzik and George [651 suggested that the
sulfur radicals formed during the reaction also act as a
catalyst, yielding water and new sulfur radicals. As the
exposed surface decreases and sulfur radicals stabilize
and condense, depending on the temperature and the
vicinity of the chains, so does the accessible reactive
sulfur, and the reaction decays. Therefore, according
to Alvarez, et al. [511 and Pineda and Palacios [52, 541,
the deactivation process under the same reaction conditions and temperature should be strictly related to
the texture and macroporosity of the catalyst.
Under the reaction conditions, micropores in catalysts are useless as they are normally lost with the first
gram of sulfur produced [621. Mesopores and small
macropores, by contrast, are critical because the reactants can diffuse less and less towards the solid active
surface as sulfur deposits are produced in voids and
throats of the porous system, deactivating the catalysts
[23, 661. There seems to be no diffusional limitation to
the reactants in the macroporous system of the catalyst u p to the studied level of Guijarro, et al. [621.
The open structure should allow a better reactant flow
through the voids, which would result in greater activity and longer life of the catalyst [661. From the investigation of the performance of treated alumina as catalyst at low temperature, Pineda and Palacios [521 concluded that by applying either acidic or basic treatments to optimize the textural properties, the activity
of the catalyst was greatly enhanced.
So far not enough information is available on reaction kinetics in the presence of catalyst [23, 42, 59, 671.
In designing the reactors, the reaction rate expression
must be known. Factors possibly effecting the rate
expression are: (1) the so-called kinetics of the Claus
reactions and of the reverse reactions, (2) the influence
of the mass and heat transfer inside the catalyst, (3) the
effect of catalyst granulometry, (4) the effect of sulfur
deposition as a function of the operating conditions,
and (5) the influence of reversible and irreversible catalyst aging [23, 41, 60, 671. Reaction is limited by the rate
of internal diffusion through the porous particle [231. It
may also be limited by the rate of external mass transfer
if the linear velocity of the gases is too low. Consequently, it is preferable to use catalyst of small particle
size and large macroporosity.
To reach the highest possible conversion of COS and
CS2, the outlet temperature of the first converter must
exceed 350" C. Under this condition, H2S and SO2 conversion at equilibrium are lower [371. The Claus reaction
rate is reduced in the second and third catalytic converters because of lower temperatures imposed by thermodynamics, lower H2S and SO2 partial pressure, and in
order to maintain higher conversion of H2S [71. The second and third reactors operate at their lowest possible
temperature, which is the temperature of the sulfur dew
point. Sulfur formed in each stage is condensed and
recovered in the sulfur pit to achieve maximum conver146 October 2002

sion in the reactors. Unrecovered sulfur, in elemental or

combined form (HzS, COS, and CS2) is treated in the
amine system [5, 681.
There are two principal process variations [6, 21,
58, 691. The first is the straight-through process, in
which all of the air and the acid gas pass through the
combustion zone. In this process, the primary purpose of the reaction furnace and the waste heat boiler
is to oxidize approximately 1/3 of the H2S feed to
SO2 so that stoichiometric proportions of these two
main reactants are present for the reactors [211. The
second is the split-flow process, in which all the air
and at least 1/3 of the acid gas pass through the combustion zone, with the remaining acid gas sent to the
first catalytic reactor.
ALTERNATIVE TECHNOLOGIES FOR SULFUR RECOVERY

Beside the Claus technology, many commercial

processes based on adsorption, absorption, and wet
oxidation have been used for removing H2S from
gases [14,70, 711. Dry catalytic processes based on the
selective catalytic oxidation of H2S to elemental sulfur
have recently been developed 1721. Examples of commercial catalysts developed for the processes are the
titanium-based catalysts for the MODOP process [73,
741 and the iron-based catalysts for the Superclaus
process [75, 761. Titanium based catalysts require a
stoichiometric amount of 0 2 , but are easily poisoned
by water vapor, while iron-based catalysts are resistant
against water, but requires an excess amount of O2
[721. Vanadium oxide catalysts have also been reported to be active with a stoichiometric amount of O2
[77, 781. However, the catalysts have not yet been
widely used, due to uncertainty about water poisoning effect and long-term stability [721.
Paik and Chung [171 reported a new catalytic system, cobalt molybdenum on alumina, for the reduction
of SO2 with H2. The catalyst is active and selective for
the production of sulfur at significantly lower temperatures (around 300" C). When the feed ratio of H2 to
SO2 is optimized to 3.0, about 80% yield of sulfur
could be obtained. The selective reduction of SO2 to
elemental sulfur occurs in two reaction steps; SO2 is
first totally hydrogenated to H2S on the metal sulfide
phase, followed by the Claus reaction to produce elemental sulfur over acidic alumina support [171.
Many factors affect the selection of the gas-treating
process including the volume, temperature, and pressure of gas to be processed, the selectivity required,
the desirability of sulfur recovery, the types and concentrations of impurities present, air pollution laws
and specifications to be met, as well as capital and
operating costs [2, 281. Table 1 shows a comparison
among the major types of gas-treating processes,
which can generally be categorized as adsorption,
absorption, and conversion [681.
From Table 1, it is clear that, of the three process
types, the conversion process, such as the Claus process,
has the highest efficiency at 94% to 97%, as well as the
least number of hazards and disadvantages. Moreover, its
problems can be easily solved by using the correct stoichiometric amount of air, fuel gas, and acid feed gas [61.
The adsorption process is limited to a low volumetric
Environmental Progress (V01.21, No.3)

~~

~~

~~~~

Table 1. Comparison of the alternative processes for sulfur recovery. Part one of two.

Absorption Process

Adsorption Process

Conversion Process
94 % to 97 Yo

- Overtime, all of the iron

Other components in the

oxide becomes sulphided
feed gas may react with
and degrade the amine
and its adsorptive capacity
becomes exhausted.
solution.
The zinc sulphide formed
Solution must be purged
cannot be oxidised back to
and fiesh amine added
zinc oxide.
periodically.
MEA process require
The sulphur removed via
higher solvent circulation
this process is usually not
recovered. The sulphur
rates and higher
and sorbent both undergo
regeneration energy.
disposal.
MEA process has shown a
higher tendency towards
Limited capacity of
sorbent bed.
corrosion and foaming.
Limited to gas streams of
Safety is most important as
limited volumetric rate
H2S is extremely toxic.
having low concentration
of H2S.
Safety is most important
because H2S is extremely
toxic and quickly paralyses
the sense of smell.
Molecular sieves
Solvent can be regenerated
developed to extend the
for reuse.
Many absorption processes
operating range.
Molecular sieves can be
also removed COzand to a
controlled to target the
lesser extent COS, So2 and
removal of certain
mercaptans.
components selectively.
MEA removes both H2S
Molecular sieves can be
and COznonselectively.
regenerated.
MEA lowest solvent cost
The advancementof
and lowest hydrocarbon cointegrated gasification
absorption relative to other
combined cycle (IGCC)
mine process.
power plants developsthe
fluidised bed adsorption
bed processes which are
able to withstand severe
operating condition.

- Processing streams
having lesser amounts
of H2S may result in
combustion flame
instability.
The kinetics are
incompletely
understood.
Fog formation during
sulphur vapour
condensation.
- Water vapour a f f e c t
adversely the
equilibrium of the
reaction of H2S and
SO2 over the catalyst.
Safety is most
importaut as H2S is
extremely toxic.

- The most widely used

-

- The sorbent bed has a

limited capacity.
- Limited volumetric rate
having low concentration
of H2S.

Environmental Progress (Vo1.21,No.3)

- Amine absorption

processes can be applied

when H2S Concentration is
relatively low (e.g. <5-25
mol %).
Can achieved high purity
in treated gas.

to convert H2S to
sulphur.
Operate at nearly
atmospheric pressure.
0 2 enrichment of
the combustion air can
be used to increase the
processing capacity of
an existing unit and to
extend operation to low
concentrationH2S feed.
0 2 enrichment
improves sulphur
recovery, increase
contaminant destruction
and more reliable
operation.
The Claus process has
proven very reliable
and is considered a
mature technology.
H2S concentration can
be reduced fiom 0.85%
in Claus off-gas to
4Oppm in incinerated
SCOT Off-gS.
SO2 concentration can
be reduced fiom 0.42Yo
in Claus off-gas to
0.02% in incinerated
SCOT Off-gas.
October 2002 147

Table 1. Comparison of the alternative processes for sulfur recovery. Part two of two.

of feed gas with high

Ecological
Impact

costs

- The sulphur removed is

- Chemical and physical

generally not recovered,

therefore it affects the
environment.
- The disposal of sorbent
material also affects the
environment.
- High operating costs due to
sorbent materials disposal.
- 2 adsorption towers.

solvents leakage can affect

the surrounding ecology.
- Also affect workers'
health.

- High solvent costs.

- 1 absorber, 1 regenerator, 1
cooler, 1 heat exchanger, 1
reboiler, 1 condenser

ecological impact with

a tail-gas treatment.
- Suitable to employ
various Claus tail-gas
treatment processes.

- Consists of 1
combustion furnace, 1
waste heat boiler, 1
condenser and a series
of catalytic stages, each
employing 1 reheat, 1
catalyst bed and 1
sulphur condenser.

I
feed rate containing low concentrations of H2S. The
Claus process has also proven to be very reliable and
mature [691. Only the Claus process, among the three,
can treat large amounts of feed gas with high H2S concentration, and produce minimum ecological impact
with a tail-gas treatment unit [40, 501. At the same time
that the capabilities of the conversion process have dramatically improved, innovations and process optimization have reduced its capital and operating costs [ll.
CLAUS TAIL-GAS TREATMENT TECHNOLOGIES

In the early Claus sulfur recovery plants, the tailgases were usually exhausted to atmosphere through a
stack without any treatment. Sometimes the gases were
incinerated after leaving the last converter, and the SO2containing tail-gas was passed through a tall stack [581.
As the need to reduce SO2 emissions receives greater
emphasis, Claus technology has to be improved to
obtain higher recovery rates. At the present time, most
Claus plants are unable to meet existing or proposed air
pollution regulations in developed countries without
additional methods of reducing or eliminating the sulfur
content of the exhaust gas [5, 661. Adding a tail-gas
cleanup process should be the last resort, as it is expensive in terms of investment and energy consumption,
depending on the process selected [51.
Several processes have been studied for application
as a Claus plant tail-gas cleanup service [2, 791. Many
commercial processes are based on low temperature
Claus reactions or on the removal of H S from tailgases by absorption and adsorption 16 I. However,
these processes require batch or periodic operation,
and, sometimes, heavy installation costs [91. A Claus
tail-gas desulfurization process should preferably be:
(1) easy to operate and flexible; (2) based on familiar
technology and easily adapt to existing Claus units;
(3) generate no secondary air/water pollution or
waste; and (4) deliver a high degree of desulfurization
over a wide range of operating conditions.

148 October 2002

Generally, there are two broad classes of tail-gas

cleanup treatment [21, as illustrated in Figure 2. The former consists of processes which allow the Claus reactions to take place under more favorable conditions.
These processes claim an overall sulfur-recovery efficiency of approximately 93%, including sulfur recovered
in the Claus main unit. Three processes under this
group are Amoco's Cold Bed Adsorption (CBA), the
SNPMLurgi Sulfreen, and the IFP processes [71].
In the adsorption process, gas from the main Claus
plant last condenser is fed to an adsorption reactor,
operating between 130" C and 150" C, and containing
conventional Claus catalyst. The low temperature
favors equilibrium conversion. Sulfur vapor condenses
on the bed and is removed, shifting the equilibrium
towards higher conversion. Gas from the reactor is
then incinerated. While one reactor is on adsorption
cycle, a second reactor is being regenerated. However, regeneration for removing sulfur deposit from catalyst surface leads to a decrease in sulfur storage
capacity and in initial desulfurization activity [31. Hot
gas from the first Claus reactor vaporizes the condensed sulfur and reactivates the catalyst. The gas is
then cooled and the sulfur vapor condenses. Gas is
returned to the Claus cycle just downstream of the
first Claus sulfur condenser.
The Sulfreen process, developed by the Societe
Nationale des Petroles d'Aquitaine (SNPA) and Lurgi
Gesellschaft GmbH, uses a vapor-phase extended Claw
reaction carried out below the sulfur dew point. The
process operates in the same temperature range as the
CBA method, with the produced sulfur being deposited
on a alumina catalyst bed. In the two-reactor case, one
reactor is in service while the other is being regenerated.
The Sulfreen design uses a closed regeneration loop containing a sulfur condenser and a regeneration gas heater,
usually an indirect-fred unit with stainless steel tubes.
The Institute Francais de Petrole (IFP) developed a
treating process used for Claus plant tail-gas cleanup,
Environmental Progress (V01.21, No.3)

rn
Tail-gas Cleanup Treatment

99% sulfur

recovery efficiency

(1) Shell Claus Off-GasTreating

(SCOT) Process
(2) Beavon Process
(3) Wellman-Lord Process

(1) Amocos Cold Bed Adsorption

(CBA) Process
(2) SNPALurgi Sulfreen Process
(3) IFP Process
Figure 2. Major tail-gas cleanup treatment processes.

Stack
Reducing
gas steam

Sorbent Bed A
(Sorption)
sulfur

-)+.+

*,orbent
Regeneration off-gas

Bed B*
(Regeneration)

Figure 3. Simplified MOST process flow diagram [391.

in which the tail-gas from the Claus unit is contacted

by an IFP solvent, a high boiling point glycol. Both
HZS and SO2 are thus absorbed. The Claus reaction
then converts these compounds to sulfur. This entire
process occurs above the sulfur melting point. As sulfur has low solubility in the IFP solvent, liquid sulfur
accumulates at the bottom of a packed contacter and
is withdrawn. Treated gas leaves the top of the tower
and is incinerated. Solvent is circulated back to the
Environmental Progress (V01.21, No.3)

top of the tower. In normal operation, no fuel or

steam is required except the condensate for make-up.
The Mobil Oil SO, Treatment (MOST) process consists of combusting the Claus tail-gas with air, converting all sulfur species to SOz/SOg [801. The SOx is then
sorbed onto a solid sorbent, and the sulfur is reductively desorbed as a concentrated stream of mainly
SO2 and HlS, which can then be recycled to the Claus
plant for further processing. Catalyst screening for this
October 2002 149

Table 2. Comparison among three-stage Claus, 1 CBA, and 2 CBA processes for Claus plant. Part one of two.

3-Stage Claus with

Tail-Gas
Cleanup Unit indirect reheat
Conversion
efficiency
(Overall
recovery
capacity)

Hazards &
Disadvantages

95 % 97.8 %

2-Stage Claus (96%

recovery) with 1 CBA
stage in tail gas
cleanup unit

2-Stage Claus (96%

recovery) with 2 CBA
stages in tail gas
cleanup unit

Up to approximately 99 %

Up to approximately
99.5%

- The kinetics of the Claus - Mechanical and

maintenance problems
process are incompletely
associated with the gas
understood.
switching valves and the
- Water vapour affect
regeneration gas blower
adversely the equilibrium
of the reaction of HIS and and heater.
- Requires good control of
SOz over the catalyst.
stoichiometric HzS/SOZ
- Fog formation can also
ratio.
be a problem during
Catalyst activity
condensation of the
gradually declines as
sulphur vapour.
sulphur condenses on the
- HzS gas extremely toxic
bed.
and quickly paralyzes the
- The process requires
sense of smell.
- One major problem can multiple reactors.
occur with the operation
of the main burner (on
reaction furnace).

application focuses on examining alumina and magnesium aluminates, with oxidation promoters such as
ceria, vanadia, and platinum, where effective SO2 oxidation promoters are required. The materials with the
highest SOx uptake are a commercial FCC SOx transfer additive, and a vanadia/ceria-promoted, magnesium aluminate (V/Ce/Mg2A1205) spinel, with 54%
and 46% SO, uptake, respectively. During most of the
adsorption period, the SO2 level in the effluent from
the sorbent bed is below 1 ppmV [801.
According to Stern, et al. [391, the MOST process,
which can combust sulfur containing species and
selectively capture SO2 produced, offers operational
advantages over other wet scrubbing processes. A
simplified process flow diagram of the MOST
process is shown in Figure 3. The tail-gas is sent to a
burner which oxidizes the remaining H2S to SO2
and SO3. The burner effluent, which contains 1 to
4% 0 2 , goes to sorbent Bed A, where adsorption of
the SOx takes place. The tail-gas is then sent to the
stack. Reducing gas flows through Bed B to desorb
the sulfur as a concentrated stream of H2S and S 0 2 ,
which is then diverted to the Claus unit. At the end
of the cycle, Bed A is loaded with sulfur, while Bed
B had its sulfur removed. At this moment, the valve
positions are changed, causing the regeneration gas
to flow through Bed A a n d the tail-gas to flow
through Bed B. The process is described in detail by
Stern, et al. [391.
150

October 2002

- Mechanical and
maintenance problems
associated with the gasswitching valves and the
regeneration gas blower
and heater.
- Requires good control of
stoichiometric H 2 S / S 0 2
ratio.
- Catalyst activity
gradually declines as
sulphur condenses on the
bed.
The process requires
multiple reactor.

The second class includes processes capable of

achieving overall sulfur recoveries in the range of
99.5% to 99.9%. This level corresponds to about 300
ppmV or less total sulfur in the exhaust gas. Three
commercial processes of this type are the Shell Claus
Off-Gas Treating (SCOT), the Beavon, and the Wellman-Lord processes. The SCOT process consists of a
reduction stage, followed by a concentration stage
that provides a H2S-rich stream to be recycled to the
Claus plant. A simplified flow diagram of the process
is shown in Figure 4. The concentration process is
similar to the amine gas sweetening process commonly used in gas processing. In the reduction section, all
sulfur compounds and any free sulfur in the Claus tailgas are completely converted into H2S with H2 or a
mixture of Ha and CO over a cobalt/molybdenum on
alumina catalyst at a temperature of about 300" C [44,
811. The tail-gas contains some H2 and CO. The hot
gas is then cooled, and water is condensed in a cooling tower. The cooled gas, which normally contains
up to 3 vol. % H2S and 20 vol. % C 0 2 , is then countercurrently scrubbed by an alkanolamine solution in
an absorption column [51. A conventional stripper can
be used to strip the acid gases from the solvent. These
gases are recycled to the Claus plant inlet. The
remaining tail-gas, normally containing 200 to 300
ppmV HzS, is then incinerated. The SCOT process has
been designed for minimum pressure drop so that it
can be easily added to an existing Claus unit.
Environmental Progress (V01.21, No.3)

Table 2. Comparison among three-stage Claus, 1 CBA, and 2 CBA processes for Claus plant. Part two of two.
~

Reliability &
Advantages

Plant capacities

Ecological
impact

- Has proven very reliable - Low energy

- 260F to 300F for
and is considered as
consumption.
operation; favours
mature technology.
- 260F to 300F for
equilibrium conversion.
- Use of modem, highoperation; favours
- Low energy
intensity, efficient mixing equilibrium conversion.
consumption.
main burners can result in - Can reduce SO2content - Can reduce SO2content

a more stable flame,

especially with leaner
feeds.
Much better contaminant
destruction for
compounds such as
hydrocarbons, NH3,
mercaptons, etc.
- Reduced or nil oxygen
breakthrough.
- Improved Claus thermal
conversion, and much
wider turndown or turnup
operations.
- Improvements are being
made in better Claus
catalysts and improved
process control.
In most U.S. states, a
sulphur recovery unit of
20 Itd or larger will
require some form of tail
gas cleanup.
- In Canada, Sulphur
recovery units of 50 ltd or
larger normally require a
tail gas cleanup unit.
- Safety is very important
in plants handling and
processing hydrogen
sulphide gas.
Poisoning by H2S.
Nowadays, units without
tail gas treatment cannot
meet the regulations.

to about 1500 ppmv.

- Uses the same

construction and
materials proven in the
Claus plant.
- Requires little plot space
and only minor
modification to an
existing plant.

- Example, Amoco

costs

~~

- Has the lowest cost

because no tail-gas
treatment unit. However
it is the least efficient and
unable to meet the
specifications.

Environmental Progress (V01.21, No.3)

built a 1500 ltd sulphur

plant with CBA near
Calgary.
Requires 2 reactors, 1
condenser and 1 blower
for addition.

to less than 1000 ppmv.

- Uses the same

constructionand
materials proven in the
Claus plant.

- Produce more but need

more equipment and
energy.
- More efficient at higher
costs.
4 reactors, 2 condensers,
2 blowers.

- Level of COS and CS2is - Levels of COS and CS2

not reduced, therefore

affecting the surrounding
air quality.
Problems have occurred
with H2S spikes during
the regeneration
procedure which have
resulted in occasional
environment violations.
. A new sulphur recovery
costs 1.5 times more than
a standard 3-stage Claus
unit.
- Capital cost to convert is
about % that of the Claus
plant.

are not reduced very

much.

- Two new sulphur

recovery units cost 3
times more than a
standard 3-stage Claus
unit.
- Capital cost to convert is
about that of the Claus
Dlant.

October 2002 151

Fuel

Air

Recycle to front end

Claus Unit

Emuent

Furnace

e
l

~~

Fuel

Air

Absorber

Uni

Regenerator

Reactor

Reactor Effluent

Air

SWS Stripper

Figure 4. Simplified process flow diagram of the SCOT process.

The Beavon process, developed by Ralph M. Parsons Company and Union Oil of California, has been
used in several Claus tail-gas cleanup units [821. The
first industrial unit, at Wintershall AG, Linden, Germany, started in January 1978, a n d has performed
very satisfactorily, aimed at 98.5 to 99.5%overall sulfur recovery. In this process, tail-gas from the Claus
unit is first treated by a reducing gas over a cobaltmolybdenum catalyst to convert all sulfur-containing
species to H2S. The Claus. gas usually contains a significant portion of the required reducing agents. Additional reducing gas is supplied by an auxiliary burner,
which is also used to maintain a temperature between
315" C and 370" C [821.
Residual concentrations of COS, CS2 and CH SH
for the reactor are low. The reduced gases are t e n
cooled in a condenser to about 150' C to 190" C, and
contacted by a sodium carbonate-bicarbonate solution
at a pH > 7 to scrub o u t any SO2 that might have
passed t h r o u g h t h e catalyst bed without being
reduced. The cooled gas then goes t o a Stretford
absorber where it is contacted by a sodium carbonatesodium bicarbonate solution containing sodium vanadate, and an oxidation catalyst, where the H2S in the
feed gas is absorbed and oxidized to sulfur. Additional
holding time for this reaction is provided by a reaction
tank. Air is then used to oxidize the vanadium back to
the pentavalent state. The recovered sulfur forms a

152 October 2002

froth at the top of the oxidizer which is skimmed off,

filtered, washed and dried, and melted [821. The Beavon/Stretford process can reduce sulfur emissions to
several p p m , but is less effective than the SCOT
process in removing CS2 or COS, or mitigating any
CO which may pass through the Claus plant [391.
In the Wellman-Lord process, the Claus tail-gas is
incinerated, then cooled to about boo C and fed to an
absorber, where it is contacted by a sodium sulfide
solution. The solution reacts with SO2 to form bisulfide. Steam is used to drive off the SO2 and much of
the aqueous solution in the evaporator/crystallizer
(831. Sodium sulfide crystals precipitate here, forming
a slurry. Gas from the evaporator/crystallizer is cooled
to recover most of the vaporized water, which is used
to dissolve the crystals. The SO2 gas is recycled to the
front end of the Claus unit. To complete the regeneration process, the solvent is also treated with sodium
hydroxide, reacting with any remaining bisulfide to
form sodium sulfide and water. The H2S/S02 ratio
control is not critical, as the Wellman-Lord process
removes sulfur after the tail-gas is incinerated. Tankage can be added to allow operation for u p to three
days while the regeneration cycle is down.
Table 2 provides a comparison among a three-stage
Claus with indirect reheat unit, a two-stage Claus with
o n e CBA unit and a two-stage Claus with two CBA
units. Comparison among the Sulfreen, the IFP, and
Environmental Progress (V01.21, No.3)

~~

Table 3. Comparison among Sulfreen, IFP, and SCOT processes for Claus plant. Part one of two

Tail-Gas
2-Stage Claus (95.5%
Cleanup Unit recovery) with
Sulfieen process tail
gas cleanup unit
Conversion
efficiency
(Overall
recovery
capacity)

2-Stage Claus (95%

recovery) with IFP
process tail gas
cleanup unit
98.1 %to 99.4 %

Upt to approximately99%

- Mechanical and

- Air control needed for

maintenance problems
associated with the gasswitching valves and the
regeneration gas blower
and heater.
- Limited by equilibrium
conversion and sulphur
vapour pressure losses.
- Require careful operation
of the parent sulphur
plant to achieve
maximum recovery.
- More complicated
than CBA process.
- Not very energy efficient.
operating temperature is
quite low at 2609: to
300OF.
- Facility is compact.
- Some H2S is oxidised by
injection of a small
quantity of air, monitored
by an analyser, in order to
provide an optimal
H2S/S02ratio at the
Sulfieen reactor inlet.
- The simplicity of
operation makes operator
familiarisation more
simple.

correct H2S/S02ratio.
Proper operation of the
Claus plant is required to
miniiise COS, CS2 in
the Claus tail gas for
optimum performance.
- Operation of an IFF'
installation is quite
different fiom the parent
Claw unit, presenting a
new set of operating
problems.
- Some difficulties present
in the CBA and Sulhen
processes.
IFP solvent has good
thermal and chemical
stability, and low
volatility reducing
solvent losses.
- Recovered sulphur is
high quality.
No fuel or steam is
required other than
condensate for makeup.
Low operating
ternperatwe at 125OC.
Retrofit is not
complicated as
installation requires little
plot space and does not
recycle any gas to the
Claus feed.

Clam plant (94%

recovery) with SCOT
process tail gas
cleanup unit
99.9 + %

- High temperature needed

for catalyst at 575F.

- Not a good selection for

- The concentration

direct treating of the tail

gas from Claus plant that
processes a feed gas with
a high C02, low H2S
content.

process is similar to the

mine gas-sweetening
processes, making SCOT
process easier to operate.
- Flexibility and overall
process reliability are
good.

- Catalyst life is good.

- Presulphiding of the

catalyst is not critical.

- Controlled bum-off

followed by resulphidmg
is said to restore catalyst
to its original activity.
- The reduction step
converts essentially all
sulphur-containiig
compoundsto H2S.
- Absorption column is
aimed at achieving
essentially complete
removal of H2S while
coabsorbing only a
fraction of the C02
present.
Can be designed to
operate from 20% of
design fedrate up to full
rate.
- Changes in the feed have
only a small effect on

Environmental Progress (V01.21, N0.3)

October 2002 153

Table 3. Comparison among Sulfreen, IFP, and SCOT processes for Claw plant. Part two of two.

overall sulphur recovery.

- Reduces the sensitivity of

the overall sulphur
recovery facility to
variations in the air
supply rate.
Can be designed for
minimum pressure drop
to make it more suitable
for add-on installation.
Proven and familiar
equipment is used in each
step of this process.
Produces no secondary
waste streams.
2 reactors using
Capable of reducing the
From 10 todstream day
conventional Claus
SO2content of the
(sulphur intake) to 2100
catalyst beds, 1
incineratedtail gas to as
todstream day equivalent
condenser, 1 regeneration
low as 1000 ppmV.
Claus capacity.
gas heater.
- Require only a contactor, - With an excess of H2,
1 pump, 1 solvent heater
40 Sulfreen units in
virtually complete
operation (in 1992)after
for start up.
conversion of elemental
Claus units &om about 50
Sulphur and SO2 into H2S
to 2200 tpd of sulphur
is obtained (i.e. residual
and 5 presently under
S02contents-= 10 ppm).
construction.
Most widely used.
130 units (in 1992) are
committed, with capacity
from 3 to 2100 tpd of
fresh sulphur feed.
Proper operation of the
Tail gas contains some
The tail gas contains
H2 and CO which is toxic
Claus plant to minimise
some H2 and CO. CO in
significant quantity can
COS and CS2in the Claus in significant quantity.
- Does not affect CS2and cause health problems.
tail gas. COS and CS2
cos.
can cause air pollution.
The IFP solvent is
Capital costs equal to the
Sulfreen investment
relatively inexpensive,
costs of the Claus plant.
amounts to 30% to 45%
- For a new facility with
keeping initial and
of the Claus unit cost for
operatingcosts down.
SCOT design optimised
the conventionalversion
for the best possible fit,
and 40% to 55% for the
the cost can be as low as
improved version.
Utility requirements per
75-85% of the Claus unit.
ton of sulphur: electricity
300kW,catalyst about 4
lb for conventional
version and 5 Ib for the
improved version.
Operating costs are much
lower than solvent-based
Drocesses.

154 October 2002

Environmental Progress (V01.21, No.3)

Table 4. Comparison between Beavon and Wellman-Lord processes for a Claus plant.

Claus plant with Beavon process

Tail-GS
Cleanup Unit tail-gas cleanup unit
Conversion
effciency
(Overall
recovery
capacity)
Hazards&
Disadvantages

99.4 Yo

- At high temperature around 600 to

Claus plant with Wellman Lord

process tail-gas cleanup unit
99.9 + Yo

- Process chemistry and equipment are

not familiar to many plant personnel,
thus compounding operating and
training difficulties.

700F.

- Big space is needed.

- Absorber has to be clean-out about
every 6 months.

- Absorber plugging.
- Plugging in the sulphur fioath lines.
- The reducing catalyst life is only about
2 years.
- Concerns over vanadium used in the
process have limited its application.

Reliability &
Advantages

- Residual concentration of COSYCSz

and CH3SHfiom the reactor are low.
- Some sections of the unit are coated

with plastic to avoid corrosion by

deposited sulphur.
- A reaction tank can provide additional
holding time for reaction.
- No tail gas incinerator is required
during nonnal operations.
- Suitable for add-on installations to any
type of sulphur recovery plant if
adequate plot space is needed.
All pressures are near atmospheric.
To be able to achieve 100 ppmV or
Plant capacities
less total sulphur in tail gas.
- The clean tail gas containing less
10 ppm HzS when using the newer
solvents, which are highly selective
mine type solvents.
There are more than 15 Beavon MDEA
plants in the U.S.and Japan. 2 BeavonSelectox plants are in the U.S.and
Germany.
- After cooling in the reactor, HzS,CSZ,
Ecological
COS gases are treated by the Stretford
impact
process. The exit gas is discharged
with no further processing.
Total investment is approximately
costs
equal to that of the parent Claw plant.
High operating costs for sour gas
disposal during absorber clean outs
every 6 months, reduction of catalyst
changeouts and any mechanical failure.

- HzS/SOzratio control is not critical to

design tail gas treating.
- Tankage can also be designed into the

facility to allow design operation for up

to 3 days while the regeneration cycle is
down.
This process is well-suited for high COz
streams as it does not recycle C02with
the SO2.

- To achieve SOt emission level at 200

ppmV or less.

Environmental Progress (V01.21, N0.3)

- A bleed stream must be treated to take

out sodium sulphate.

- High capital cost because it requires

exotic metallurgy.

- Capital cost about 130-150%of the

parent Claus unit for a 100 ltd unit.

October 2002 155

b.. :c:ata&st.3:
. . . . . . . .wat<r:
. . . . .sprbept.(zpt)l&+)
.......... :

.........................

the SCOT processes are given in Table 3, while Table

4 illustrates the comparison between the Beavon and
the Wellman-Lord processes for a Claus plant. By considering the advantages and disadvantages of all the
six methods in Tables 2 to 4 , it is clear that the SCOT
process is generally the most suitable for a tail-gas
treatment unit. A Claus plant with a SCOT unit can
achieve conversion of 99.9% or more. If the feed gas
to the Claus plant contain a low CO2 concentration
and a high H2S content, then the SCOT process is a
good selection for direct treating of the tail-gas. Moreover, the amine system in the SCOT process is much
easier to operate compared to other processes. The
SCOT process, with good catalysts, is very reliable
and flexible to disturbances.
One of the most important features of the SCOT
process is that it can operate from 20% of design feed
rate to full rate. Therefore, its ability to cope with
changes in the feed conditions minimizes any effect on
overall sulfur recovery. The SCOT process can also be
designed for minimum pressure drop, thus making it
more suitable for add-on installations. It is also quite
environmentally-friendly since it produces no secondary
waste streams. Using excessive H2, the SCOT process
can achieve a residual SO2 contents of less than 10
ppm. The capital cost can be as low as 75% to 85% of
the main Claus unit if the design is optimized [441.
MODOP and Superclaus processes seem to be very
attractive as they can convert H2S directly to elemental sulfur by selective catalytic oxidation and do not
require periodic operation [91. Superclaus seems to be
superior to MODOP since the catalyst for the former
can tolerate the presence of water. However, Superclaus uses ten times more 0 2 than the stoichiometric
amount for converting H2S to sulfur, and cannot be
applied to treat H2S higher than 5%. Recently, it is
claimed that Fe-Cr/Si02 catalyst can give sulfur yields
of more than 90% at the Superclaus condition [841.
The catalyst is known to show little decrease in the
sulfur yield, even in the presence of 30 vol. % water
vapor in the feed. Vanadium/silica (V/SiO2) catalyst
shows a decrease in the yield when excess water is
introduced in the feed. The use of a stoichiometric
amount of 0 2 with V/SiO2 is possible to treat highly
concentrated H2S I31, whereas the Superclaus catalyst
is limited to H2S concentration of less than 5 vol. Yo.
The following is a simplified guide for selecting a
sulfur-recovery process configuration: (1) try a best
156 October 2002

Sulphur-

current technology Claus sulfur unit first; and (2)

consider a Claus sulfur-recovery unit plus a tail-gas
unit as a last resort. Tables 1 to 4 summarize the
recovery capability of several sulfur recovery systems,
ranging from the simple to the complex. This should
help in a preliminary determination of the system for
a particular requirement.
POSSIBLE IMPROVEMENTS IN TAIL-GAS TREATMENT PROCESSES

Claus sulfur recovery units at existing installations

will need to process significantly more sour acid gas
in the future. Therefore, current technology might not
be able to cope with increasing capacity and concentration of H2S in the acid gas. Several changes and
new trends are currently being studied, and other
technologies are under further development. Moreover, the more stringent environmental regulations in
the future might force some plants to shut down.
Conventional technology for carrying out the Claus
reaction involves a series of fixed bed catalytic reactors, with interstage removal of sulfur by condensing
the product vapor stream, as shown in Figure 1. An
alternative strategy that is much more thermodynamically efficient is the in situ adsorption of water inside
the reactor using a packed bed with a mixture of catalyst and zeolite adsorbent [85l, as illustrated in Figure
5. This allows high conversions in a single-stage Claus
process. The sulfur formed can be separated from the
almost completely converted gas emerging from the
adsorptive reactor in a single stage of condensation.
The sulfur-free gas can then be reheated and used for
the regeneration of the second adsorptive reactor [851.
Several companies are investing large amounts of
money to improve the sulfur recovery process. Several
new technologies are being studied or developed. For
example, BOC is investing in a development facility to
improve the SURE oxygen-based Claus sulfur recovery
process at Courtaulds Chemicals carbon disulfide production plant at Stretford, Manchester, UK. The Claus
system can be made more efficient by enriching o r
replacing the combustion air with 0 2 . The development unit at Courtaulds is part of BOC Gases program to develop the next generation of oxygen-based
Claus processes and burners.
Courtaulds already has a large Claus unit at its carbon disulfide plant. Part of the feed stream to this unit
is diverted to the development unit, and recovered
sulfur plus the residual gas stream are both returned
Environmental Progress (v01.21,No.3)

4SO2 + S +

H20

Figure 6. A non-permselective ceramic catalytic membrane reactor for the Claus reaction [861.
to the main Courtaulds plant. The composition of the
feed to the BOC development facility can be modified
to represent virtually any commercial installation. The

research program will also develop computational

fluid dynamics models for detailed kinetic studies of
the Claus process.
In another development, Kenneth Klabunde and
Shawn Decker, both of Kansas State University, are
developing a sulfur content removal technique. They
have produced calcium oxide crystals coated with
iron oxide, offering a greater surface area and a coating that helps increase the reactivity of calcium oxide
with the acid gases. The 7 nm crystals are twice as
efficient at removing SO2 as the current method.
Klabunde also perceives many other possible applications for his research, including an alternative to incineration of industrial waste, protection of soldiers from
chemical agents, and the removal of chlorinated compounds.
RESEARCH ON NEW CONCEPTS FOR REMOVAL OF H2S FROM TAIL-GASES

Thermal cracking of H2S at temperatures between

1,370" C and 1,650" C is being studied by the Alberta
Sulfur Research Laboratory (ASRL), Calgary. ASRL has
built a semi-works unit and installed it at Petro-Canada's

Wildcat Hills plant (near Cochrane, Alberta). The company plans to use a special ceramic membrane to separate the produced H2 from the elemental sulfur. The
laboratory is also working on a further development
stage of the thermal cracker in which the ceramic material will also serve as a semipermeable membrane to
allow the removal of H2 formed in the cracker.
A new configuration of catalytic membrane reactor,
introduced by Sloot, et al. B61, consists of two chambers separated by a non-permselective ceramic membrane, as shown in Figure 6. The active components
of the catalyst can be easily incorporated within the
membrane. The membrane functions as a physical
barrier between the reactants which are fed to the
Environmental Progress (V01.21, No.3)

opposite sides of the membrane. Figure 6 also shows

the arrangement of the ceramic membrane reactor for
carrying out the Claus reaction 1861. This reactor type
has specific advantages for reactions requiring strict
stoichiometric feed of reactants. Any variation in the
molar fluxes of the reactants will result in a shift of the
reaction zone without affecting the reaction stoichiometry [861. This allows greater flexibility of the
reactor to feed rates of H2S and S 0 2 . It is also often
desired that all the products of a reaction be directed
to one side of the membrane. In this case, the produced sulfur should be directed to the SO2 side [871.
This can be achieved by applying an overpressure at
one side of the membrane to generate the combined
effect of convective and diffusive flows [87-891. Furthermore, a homogeneously active membrane can be produced by using sintered stainless steel as the membrane
for the concept of separated feed of reactants [891.
Veldsink, et al. I901 suggest that the membrane
reactor shown in Figure 6 can be used for kinetically
fast exothermic heterogeneous reactions. By feeding
the reactants on both sides of the membrane, premixing of the reactants is avoided. Therefore, thermal
problems, such as the formation of explosive mixtures
and the occurrence of thermal runaways, will not take
place "90, 911. However, accurate controlling of heat
balances of the membrane reactor will be a major task
for any large-scale industrial unit. Therefore, efficient
means to supply or remove heat from any large-scale
membrane reactor will have to be developed. According to Adris and Grace [921 and Mlezko, et al. 1931, the
combination of membranes and fluidized-bed reactors
are advantageous because fluidized beds provide
good temperature control.
Much attention is paid to the search for an optimum porous catalyst structure, i.e., the relationship
between micropores and macropores, which would
provide effective conversion of H2S and SO2 during
the entire period of adsorption until the reactor
October 2002 157

switches into the catalyst regeneration mode [661. The

larger the volume of micropores, and the smaller their
size, the greater the amount of sulfur that can be
extracted by the catalyst, and the smaller the sulfur
losses in the vapor phase. The catalyst efficiency in
tail-gas treatment processes is determined not only by
the relation of micropore and macropore volume, but
also by the number of micropores that the reactant
molecules must go through to get from one macropore to the next [661.
Raymont [LO, 111 came up with an alternative route
for the utilization of H2S by breaking it down to its
constituents. The interest in utilization of H2S as a
source of H2 and sulfur has intensified in recent years
due to: (1) global prospect for hydrogen energy and
waste minimization; (2) the unavoidable production
of H2S from gas plants, refineries and metallurgical
processes; and (3) the cost of a tail-gas clean-up
process for Claus plants that can exceed the value of
the recovered sulfur if the environmental regulations
are made more stringent [81. A suitable technology for
the production of H2 and sulfur must meet the triple
objectives of waste minimization, resource utilization,
and environmental pollution reduction.
Photochemical 194-971and plasmochemical [98-1031
technologies are still in the development stages and
are not mature enough to be applied to large-scale
chemical processing. Electrochemical technology [1041101 is established in certain areas, such as biochemical and biomedical separation processes, but its application to H2S requires further development in the area
of storage and disposal techniques, proper equipment
materials, and knowledge of possible side reactions.
In addition, it is unlikely that electrochemical processes can be competitive at today's electricity costs. Of
the thermal methods, membrane, thermal diffusion,
and solar technologies have not yet developed very
far [81. In fact, membrane technology, which appears
very attractive, is essentially a technology for the
future. For chemicals as difficult as H2S, the application has to wait until the technology matures to less
demanding processes.
As an alternative to the physico-chemical processes,
Basu, et al. [201 demonstrated that the anaerobic, photosynthetic bacterium, Chlorobium thiosulfatophilum,
could convert H2S to elemental sulfur in a single step at
atmospheric conditions. The autotrophic bacterium utilizes C 0 2 as carbon source, while energy for cell metabolism is provided by incandescent light and H2S oxidation [201. Almost all the H2S could be converted in a residence time of a few minutes. Moreover, high concentrations of H2S or organics did not seem to affect the
conversion efficiency.

environmental regulations in developed countries, a

Claus tail-gas cleanup treatment is essential to achieve
very high sulfur recovery efficiency. Established tailgas cleanup processes are Amoco's Cold Bed Adsorption, the Sulfreen, the IFP, the SCOT, the Beavon, and
the Wellman-Lord processes. The SCOT process is the
most reliable and flexible to disturbances.
Several changes and new trends in the conversion of
H2S and SO2 to elemental sulfur have also been highlighted in this review paper. Two examples of the recent
improvement in the Claus tail-gas treatment process are
the introduction of the non-permselective catalytic membrane reactors and in situ water separation by zeolite
adsorbent. The success in the utilization of H2S by breaking it down to elemental sulfur will signlfy the attainment
of the three objectives of waste minimization, resource utilization,and environmental pollution reduction.
Based on the considerations in this review, the following two processes for the conversion of H2S
and/or SO2 merit further analysis to act as the basis
for a prospective commercial technology: (1) catalytic
thermal decomposition at reduced pressure between
1,000" C and 1,200" C in a fixed bed reactor; and (2)
two-step sulfide processes in the temperature range of
500" C to 650" C in fluidized bed reactors as reactorregenerator systems. However, there may, in fact, not
be a universal approach for the selection of a desulfurization process. The economics of a process may be
influenced by diverse factors, making different
processes desirable based on plant size, the source,
temperature and concentration of H2S, the local energy situation and/or the environmental regulations.
Therefore, it is important to explore new ways of H2S
and SO2 elimination which will lead to high conversions at minimum cost, to increase sulfur recovery.
Photochemical and plasmochemical methods are still
in the development stage, while the electrochemical
technology is established in certain areas, but its application to H2S requires further development. Research
for an optimum porous catalyst structure is ongoing in
order to obtain a relation of micropores and macropores
which would provide effective conversion of H2S and
SO2 during the entire period of adsorption.

CONCLUSIONS

LITERATURE CITED

The modified Claus process is the major technology currently used to recover elemental sulfur from
H2S and SO2. Studies and research o n the Claus
process mechanisms and technology have been
described. A number of current commercial technologies for the recovery of sulfur from sour acid gas have
also been described and compared. Under modern
158 October 2002

ACKNOWLEDGMENTS

The author would like to acknowledge the assistance given by Mohd. Rusydan Abdul Naim and
Ikhsan Masadi, currently with the National Petroleum
Company of Malaysia (Petronas). Appreciation is also
due to Yasser Hussain, Ron Towers and Dr. John
Lamb of University of Surrey for their helpful comments and suggestions. Special appreciation is due to
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