3.
Sulphur cycle
3.2.1 Introduction
The removal of sulphur components from liquid
and gas streams is required in many sectors of the
hydrocarbon processing industry. With more
stringent fuel regulations and increasing
environmental concerns, together with the need to
process sourer crude oils and natural gases,
sulphur recovery has become one of the leading
issues in emission reduction.
The term sulphur cycle (Fig. 1) designates a
large number of processes widely used in the
refining industry, for purposes ranging from the
transformation and/or capture of sulphur
compounds contained in the petroleum fractions
to their removal, generally as elemental sulphur.
The general idea of the sulphur cycle is to
eliminate sulphur compounds from various
petroleum fractions (Heinrich and Kasztelan, 2001).
This is realized via: a) isolation and concentration
of the undesired sulphur compounds; b) sulphur
species transformation mainly into hydrogen
sulphide (H2S) in HydroDeSulphurization (HDS)
units (HDS units included in a typical reforming
cycle are presented in Chapter 3.1) and in
hydrocracking or catalytic cracking units; c) capture
and enrichment of H2S via solvent washing (e.g.
amines units); d) conversion of H2S into elemental
sulphur in the Sulphur Recovery Unit (SRU): Claus
and/or other processes (see Sections 3.2.3-3.2.4).
Elemental sulphur is the ultimate state of
recovery of the sulphur species. In the past,
recovered elemental sulphur had considerable
value and was sold in the commercial
marketplace. However, as the hydrocarbon
extraction industry continually recovers more
sulphur, the supply far exceeds demand and prices
are driven down to levels where transportation is
VOLUME II / REFINING AND PETROCHEMICALS
no longer economically possible. This market is
now expected to exhibit a chronic oversupply. On
a worldwide basis, approximately 60 million
metric tons of sulphur were produced in the year
2000. It is generally assumed that the Claus
process had produced 85% of this sulphur, 90% of
which being used for sulphuric acid (H2SO4)
production (60% of H2SO4 is used for fertilizer
production).
The discussions below intend to give a general
idea of the capabilities of various sulphur
recovery processes, while taking into account the
nature of the stream. Compared to gas processing,
petroleum refining is a source of gas with low
carbon dioxide (CO2) content; nevertheless, if
there is a catalytic cracking unit in the refinery
scheme, the gas may contain some other
contaminants such as carbonyl sulphide (COS),
refinery gas
sweet/
fuel gas
acid gas
SWS gas, NH3
incineration
overall sulphur
recovery up to 99.9
sulphur incineration
Fig. 1. Typical sulphur cycle
in the refining industry.
137
PROCESSES RELATED TO ENVIRONMENTAL ISSUES
organic sulphur, cyanides, ammonia and organic
acids.
3.2.2 H2S recovery processes
Several factors must be considered when selecting
a gas treating process: processing temperature and
pressure, quality and quantity of sour gas to be
treated, product gas specifications and/or
subsequent processing requirements for the acid
gas as well as the produced gas. A few other
factors, such as capital investment, operating
costs, climatic conditions and operability, bear an
impact on the final choice. Acid gas requirements
are linked to its final processing. A wide range of
available processes dedicated to elemental sulphur
recovery from H2S is described in Section 3.2.3.
There are sweetening units in the refinery to
recover H2S from acid gas streams. A typical
refinery exhibits multiple absorbers and a
common regenerator, as there are several units
where H2S is produced. Among the products to be
sweetened, one can find the following: fuel gas,
Liquefied Petroleum Gas (LPG), hydrotreater
product and/or fuel gas and recycle gas,
hydrocracker product and/or fuel gas and recycle
gas, cracker gases, and the remaining gases
generally combined. The solvent is then
regenerated in a single stripper and the acid gas,
produced at low pressure, is sent to the Claus unit,
transforming H2S into sulphur, or to an equivalent
unit. Chemical, physical or hybrid solvents are
those typically encountered in the industry.
Chemical sweetening technology has been used
for over 70 years; alkanolamines are the most
widely used of the many available solvents for
removal of H2S and CO2 from refinery and
natural gas streams.
The traditional way of operating sweetening
units has been to remove CO2 along with H2S.
Unfortunately, this CO2 removal causes several
problems. More energy is needed at the amine
Fig. 2. Acid gas sour gas
enrichment schemes.
H2S, CO2
H2S to ClausTGT
138
regenerator or stripper, together with a larger
circulation rate of amine. On the one hand, a large
CO2 concentration dilutes the gas to be treated in
the Claus unit, sulphur recovery being optimal for
a concentrated H2S feed stream, typically more
than 50%. On the other hand, as more CO2 is
rejected, more H2S can be converted to elemental
sulphur in the Claus unit and, therefore, less
sulphur dioxide (SO2) will be vented or removed
by a tail gas scrubber. Moreover, if there is a loop
to recover H2S from TGT (Tail Gas Treating) and
it is sent to the Claus, then the minimum amount
of CO2 is essential to ensure amine and Claus
efficiencies. This loop generally utilizes a
reducing atmosphere to convert all of the
remaining sulphur species to H2S; the resulting
acid gas is amine washed and the H2S stream is
recycled to the Claus. These considerations
demonstrate the interest in selective absorption or
Acid Gas Enrichment scheme (AGE), combining
two amine units (Fig. 2), one being H2S selective
to provide highly H2S concentrated feed to the
Claus unit.
Amine process schemes
A very common amine design configuration
includes one single absorber, one single
regenerator and all related equipment such as
pumps, heat exchangers and filters. Fig. 3
illustrates a typical gas treating plant using
alkanolamine. After passing through an inlet
separator and/or a liquid-gas separator to remove
any entrained solids or liquids, the sour gas enters
the bottom of the absorber. Generally, trays (or
eventually packing) are used as internals for this
vessel, where the gas is contacted counter-currently
with the solvent. The acid gas is absorbed
in the solvent and reacts with the amine.
Depending on the application, the absorber may
have multiple amine feed entry points. Rich
amine solution leaving the absorber flows to the
flash tank, where the solution pressure is reduced
to flash the soluble hydrocarbons and to remove
sour gas
H2S
sweet gas to Claus
TGT
CO2 H2S, CO2
vent / incineration
incineration
sweet gas
ENCYCLOPAEDIA OF HYDROCARBONS

Fig. 3. Amine unit, treated gas
simplified
flow diagram.
absorber
raw
gas
the condensed hydrocarbons. From the flash tank,
the rich amine passes trough a lean/rich cross
exchanger that ensures liquid preheating and
flows to the top of the regenerator. The heat
provided by the reboiler is necessary to raise the
rich amine to its boiling temperature, to break the
chemical bond between acid gas and amine, and
finally to produce enough steam, which reduces
the partial pressure and allows the acid gas to be
stripped from the solvent. The stripped acid gas,
whose pressure depends on SRU requirements,
then typically flows to a Claus plant for sulphur
recovery. The hot and lean amine is circulated
back from the reboiler to the absorber after
passing through the lean/rich exchanger, where it
is used to preheat the rich amine, and lean solution
cooler. Part of the solution is filtered to minimize
the quantity of potentially corrosive degradation
products and the quantity of anti-foaming agents
for better control of the absorber.
Other considerations may lead to more
complicated unit designs, including several flash
regeneration steps (especially for hybrid and
physical solvents), several absorbers in series,
several absorbers in parallel and split-flow
configurations. An example of split-flow
configuration is presented in Fig. 4, where a
semi-lean amine stream realizes the bulk
sweetening, while a small stream of lean amine
is used to reach the sweet gas specifications.
VOLUME II / REFINING AND PETROCHEMICALS
SULPHUR CYCLE
fuel gas acid gas
stripper
lean
amine
Many treating processes are available, though
no single process is ideal for all applications. The
initial selection must be based on required feed
specifications together with feed parameters
including the composition, pressure, temperature,
and nature of the impurities. A more detailed
approach follows, considering the percentage of
acid gas in the feed. CO2 concentration could
impose a selective removal of H2S to reduce the
regeneration duty of the amine unit. Finally, a
given process is selected according to economics,
reliability and versatility factors of the design,
while taking environmental constraints into
account. As a result, gas processing in the
refinery is growing more complex. In fact, the
challenge resides in choosing between various
solvents and process configurations. Hence, more
upstream and downstream gas processing steps
should be implemented, which results in a need
for more equipment.
Base for solvent selection
Feed gas composition should be evaluated
prior to entering the absorber section of a solvent
unit. Contaminated gas damages the solvent and
may cause corrosion, foaming, plugging, together
with products that do not meet specification
standards. The contaminants discussed include
solids or dust, elemental sulphur, COS,
mercaptans (RSH), carbon disulphide (CS2),
139
PROCESSES RELATED TO ENVIRONMENTAL ISSUES
Fig. 4. Amine unit,
split-flow
configuration.
treated gas
semi-lean
absorber
raw
gas
Benzene-Toluene-Xylenes (BTX), heavy
hydrocarbons and mercury.
The numerous possible processes available as
well as the amount of variables involved render
absolute determination impossible (Lallemand et
al., 2004). The feasibility and desirability of
sulphur recovery leads to limitations on the
selection of sweetening processes.
The quality of sulphur produced from a Claus
unit is quite sensitive to the presence of heavy
hydrocarbons in the acid gas. If the solvent absorbs
large quantities of heavy hydrocarbons, an
additional process may be required on the acid gas
leaving the unit or a high efficiency burner must be
installed in the Claus to destroy these components.
Chemical and physical solvents are used over a
wide variety of process conditions, ranging from
medium pressure to atmospheric pressure for
refinery off-gas and Claus tail gas treating. Solvents
for H2S selectivity are employed for refinery
applications with high CO2 slippage, tail gas
treating and LPG streams. The absorption of H2S
and the selectivity over CO2 could be controlled by
kinetics and contact time, and are enhanced when
operating at low temperature. Consequently, it is
desirable to lower the lean amine temperature and
to run the absorber at a low temperature.
140
acid gas
lean
amine
fuel gas
amine
stripper
Solvents overview
Generic and speciality solvents are generally
divided into three categories: chemical solvents,
physical solvents and hybrid (mixture of chemical
and physical) solvents. The removal of acid gases
by the chemical solvent is brought about through
a chemical reaction. Physical solvents remove
acid gases by absorption. Hybrid solvents utilize a
combination of absorption and chemical reaction.
Chemical solvents
Amine processes utilize an aqueous solvent
containing a chemical reactant: an alkanolamine.
On the one hand, hydrogen sulphide and carbon
dioxide are considered acid gases because they
dissociate to form weak acids in aqueous
solutions. On the other hand, alkanolamines are
weak bases and react with the acid gases in the
absorber to form soluble acid-base salts. These
soluble complexes are then reversed in the
regenerator at elevated temperature and low
pressure. Reduced pressure in the regenerator
allows acid gas release and regenerates the
solvent to be reused. Alkanolamines exhibit two
important chemical properties. The amino group
is responsible for weak reactivity of the base,
allowing heat regeneration of the salt; moreover,
ENCYCLOPAEDIA OF HYDROCARBONS
 SULPHUR CYCLE

physical 50°C
Table 1. Classification of alkanolamines
physical 80°C
acid gas/solvent
volume ratio

Primary Amines
chemical 50°C Monoethanolamine
HOCH2CH2NH2
(MEA)
Diglycolamine
HOCH2CH2OCH2CH2NH2
chemical 80°C (DGA agent)
Secondary Amines
acid gas partial pressure Diethanolamine
HOCH2CH2NHCH2CH2OH
(DEA)
Fig. 5. Acid gas recovery: Diisopropanolamine
chemical versus physical solvents. CH3CHOHCH2NHCH2CHOHCH3
(DIPA)
Tertiary Amines
Methyldiethanolamine
the OH group weakens the basicity, increases HOCH2CH2N(CH3)CH2CH2OH
(MDEA)
solubility in water and lowers vapour pressure
when compared to a single amine. Chemical Triethanolamine
N(CH2CH2OH)3
solvents are well suited for low operating (TEA)
pressure applications since the removal capacity
is high and relatively insensitive to partial reaction mechanisms can occur. The dissolved
pressure when compared to physical solvents CO2 in aqueous solution hydrolyses to carbonic
(Fig. 5). As a general rule, amine solution acid, which slowly dissociates to bicarbonate. The
concentration and loading (the ratio between the bicarbonate then forms a salt with the amine
number of moles of acid gas and the number of through an acid-base reaction. The various
moles of amine) are limited by equilibrium and reactions are summarised as follows:
corrosion issues. Nevertheless, amines are
characterized by a relatively high heat of [2] CO2H2O
H2CO3 (carbonic acid)



absorption and then require a substantial amount [3] H2CO3

HHCO3 (bicarbonate)



of heat for regeneration.

The alkanolamines are classified by the degree of [4] HR1R2R3N
R1R2R3NH 


substitution of the hydrogen atoms on the central [5] global reaction:

nitrogen (Table 1). Tertiary amines are fully CO2H2OR1R2R3N R1R2R3NHHCO3 


substituted on the nitrogen atom, while primary and

secondary amines keep two or one hydrogen atom on
nitrogen, respectively. These differences in
molecular structure clearly impact their acid gas
removal capabilities. Moreover, modern solvents
include hindered and formulated amines, which
influence some of the amine’s properties for specific
applications. When considering generic amines
(Table 2), there is a marked difference in solution
concentration due to the physical-chemical
properties and potential corrosion of the solution.
The carbonic acid dissociation to bicarbonate is
kinetically slow, causing the overall reaction to be
slow.
When the amine is of primary or secondary
type (i.e. exhibiting labile hydrogen), CO2 reacts
directly with the amine through intermediate
formation of a carbamate, which reacts with a
second molecule of alkanolamine to form an
amine salt or zwitterion.
[6] CO2R1R2NH
R1R2NHCOO 


The reaction between acid gases and

alkanolamine is exothermic and liberates a [7] R1R2NHCOOR1R2NH
R1R2NCOO 


substantial amount of heat. Reaction type differs for R1R2NH2

H2S and CO2. In the following reaction, where R1,
[8] global reaction:
R2 and R3 indicate hydrocarbon or alkanol parts of
CO22R1R2NH R1R2NH2
R1R2NCOO





the molecule, H2S reacts instantaneously with

alkanolamine: The kinetics of this reaction is faster than the
carbonic acid dissociation, though somewhat
[1] R1R2R3NH2S 

R1R2R3NHHS


slower than H2S absorption. This reaction requires

The reaction between alkanolamine and two alkanolamine molecules, which limits CO2
carbon dioxide is more complex, in that two maximum loading to 0.5; therefore, upper loading

VOLUME II / REFINING AND PETROCHEMICALS 141

PROCESSES RELATED TO ENVIRONMENTAL ISSUES
Table 2. Alkanolamines and their applications
Amine Solution Applications
(% weight)
MEA 15-20 CO2
DEA 25-40 Refinery
MDEA 25-50 Refinery and TGT
Formulated MDEA 40-50 H2S/CO2
DGA 50-60 Refinery
DIPA 25-55 Refinery
may result from carbamate hydrolysis to
bicarbonate. Unlike common amines, hindered
amines are based on a steric hindrance provided
by a bulky hydrocarbon-hydroxyl chain adjacent
to the amino atom. Consequently, the reaction of
CO2 with this amino group is no longer possible
and the H2S selectivity is thus amplified.
Physical solvents
Physical solvents are based on non-aqueous
solvent and physical absorption. They are
characterized by low volatility, low to moderate
viscosity, high boiling point, and exhibit excellent
thermal and chemical stability. The solubility of
H2S, CO2, RSH, CS2 and SO2 is higher in physical
solvents than hydrogen, methane, oxygen and
nitrogen. Nevertheless, heavy hydrocarbons are also
soluble in the physical solvents. Therefore, the flow
scheme takes this particularity into account with
multi-step flashing to lower the pressure, followed
by an inert stripping gas and/or a low energy
demand regeneration. This method is generally
more complex than that of basic amine, though
attractive from an economic standpoint since the
energy demand is low. The above is considered for
H2S selective recovery when the acid gas partial
pressure is greater than 4 bar and when the
hydrocarbon content, particularly BTX, is low in
feed gas.
Hybrid solvents
Hybrid solvents, or mixed solvents, are
designed to merge the effects of chemical and
physical solvents by mixing amine (40-60% by
weight), physical solvent (10-40% by weight) and
water (20-30% by weight). The process combines
the advantages of both solvents as it uses physical
solvent for acid gas bulk removal and chemical
solvent to achieve gas specifications. Heavy
hydrocarbon absorption remains one of the
disadvantages of the hybrid process. Their
142
Comments
Low pressure
Commonly used
Selective absorption
Displacing other amine types, low aromatic absorption
Absorbs all sulphur compounds and aromatics
Absorbs heavy HC and partially COS
application involves the removal of H2S, CO2 and
trace sulphur. The energy requirement and
circulation rate are relatively low (Lecomte et al.,
2003). In practice, process schemes combine flash
and thermal regenerations.
Another example of mixed solvents is
activated hot potassium carbonate (e.g. with
DEA). It is used for H2S and CO2 recovery. Since
the solvent is hot, which avoids any
crystallization and lowers the viscosity,
regeneration does not require a great amount of
energy and is performed through low pressure
flashing. Packing is preferred to trays for this
technology, which allows process optimizations.
The operating costs of this process are primarily
determined by the overall heat utilization in the
refinery.
Main solvents and their applications
An approach for initial solvent and process
selection should take into account several factors:
lean or rich gas, large or small flow, the amount
of sulphur, trace sulphur compounds,
contaminants, pressure and site factors.
Amine solvents
These include generic and hindered amines.
All are used, but DEA and MDEA have probably
been applied more in refinery and natural gas
sweetening industries in general. Up to now,
amine-based processes have dominated the gas
sweetening industry:
• MEA is used for low-pressure applications and
complete acid gas removal. It is a highly
reactive primary amine that exhibits low cost,
good thermal stability, partial removal of COS
and CS2. However, MEA presents a low
solvent vapour pressure, a highly corrosive
nature, high-energy demand for regeneration,
and the removal of acid gas is non-selective.
• DEA is a secondary amine and one of the most
ENCYCLOPAEDIA OF HYDROCARBONS

widely employed for gas containing H2S, CO2,
COS and CS2, due to an overall balance
between reactivity and corrosion. It is less
reactive, has lower solvent vapour pressure
and lower corrosion potential than MEA,
coupled with a lower solvent cost. DEA is
non-selective and requires higher circulation
rates in the sweetening unit.
• DIPA is primarily used in European refineries
at 40-50% weight concentrations. Its steric
hindrance provides a moderate selectivity for
H2S over CO2, which can be a disadvantage
for Claus off-gas treatment applications. It
exhibits a partial removal of COS, though
hydrocarbon solubility takes place to some
extent. Its cost is comparable to that of generic
MDEA.
• DGA, like DGA agent, allows high solvent
concentration. This highly reactive primary
amine removes COS, CS2 and (partially)
mercaptans. It shows excellent thermal
stability and requires low circulation rates.
However, DGA absorbs aromatics and is more
expensive than both MEA and DEA, which
must be considered for the sulphur recovery
design.
• MDEA is among the most recent amines and
is now displacing the other alkanolamines. In
highly concentrated solution, this tertiary
amine is selective to H2S. It exhibits low
vapour pressure, high resistance to
degradation, low corrosiveness and low energy
demand for regeneration. However, its
reactivity is low and solvents price higher
when compared to the above. In addition, the
removal of COS and CS2 is low. Formulated or
activated MDEA with primary or secondary
amines allow CO2 absorption and are now
displacing primary and secondary amines in
refinery applications. Among the advantages,
MDEA absorbs the lowest amount of BTX,
compared to DEA and MEA.
• Hindered amines are used as an attractive
approach for low-pressure acid gas
enrichment. One disadvantage of this
technology is the solvent cost of theses
proprietary amines, when compared to classic
acid gas enrichment based on selective
MDEA.
Application of physical solvents
Physical solvents are used with various
process schemes.
• DiMethyl ethers of PolyEthylene Glycol
(DMPEG) are contacted with dehydrated sour
VOLUME II / REFINING AND PETROCHEMICALS
SULPHUR CYCLE
gas to absorb the acid gas constituents. Some
selectivity for H2S may be designed in the
absorber with a much lower energy cost than
amine processes, since regeneration is mainly
obtained through flashing and power recovery
turbines. Hydrocarbon co-absorption,
especially for aromatics and olefins, is
characteristic of physical solvents.
• Methanol processes use a refrigerated (20°C
or lower) mixture of methanol and water. A
small amount of methanol is injected in the
sour gas to prevent hydrate formation. Being
that methanol has high solubility for
hydrocarbons, special attention is paid in the
Ifpexol process to recover them in a three-
phase drum.
• N-Methyl-2-Pyrrolidone (NMP) exhibits some
selectivity of H2S over CO2. The same can be
said of methanol, concerning hydrocarbon co-
absorption.
• Morpholine process uses a mixture containing
n-formyl morpholine and n-acetyl morpholine.
This new process is of interest for bulk
removal or for sulphur trace removal.
Application of hybrid solvents
The solvent combination of both chemical and
physical solvent results in a wide range of
applicability in terms of pressure and acid gas
content:
• Mixture of sulpholane (tetramethylene
sulphone), DIPA and water and mixture of
sulfolane, MDEA and water allow a high
degree of removal, not only of H2S and CO2,
but also of trace sulphur compounds such as
RSH, COS, CS2. Disadvantages of this process
include high hydrocarbon co-absorption and
sometimes a large solvent flow to obtain the
sweet gas specification.
• Mixture of methanol, amine and water exhibits
a high recovery for acid gas including trace
sulphur compounds, such as mercaptans.
Process design and simulation
The solvent behaviour results from the
operating conditions and must be monitored.
Process design is based on the equilibrium
between the dissolved gas and the solvent. The
loading varies with the solvent concentration in
active species for a given H2S partial pressure. To
achieve a treated gas specification at the unit
outlet, it is necessary for the solvent entering the
absorber to exhibit an H2S concentration lower
than that in the solvent in equilibrium with the
exhaust gas leaving the absorber. Moreover, it is
143
PROCESSES RELATED TO ENVIRONMENTAL ISSUES
known that H2S reacts with aqueous alkanolamine
at a faster rate than CO2, providing selectivity
when used with special designs. The absorber
internal efficiency must be incorporated to take
into account the selectivity in amine unit models.
This efficiency is then a function of the kinetic
rate constants for the reactions between each acid
gas and the amine, the physico-chemical
properties of the solvent, the pressure, the
temperature and the internal design variables. For
trays, these variables include diameter, weir
length, weir height and the number of trays.
Absorption and desorption of H2S (and CO2)
involve a heat effect in amine solutions as a
chemical reaction takes place, and are a function
of amine type, concentration and loading. This
leads to water evaporation and condensation in
the absorber and in the regenerator; thus the water
content of the feed gas must be considered when
predicting the temperature profile.
Commercial simulation software generally
made use of thermodynamic models, such
as the one developed in 1976 by R.L. Kent and
B. Einsenberg, which are fitted using sets of
proprietary data.
Operating problems
The operating problems encountered in such
units are usually linked to design; trouble free
operation results from unit control and, in
particular, solution control. The parts of the unit
that must be carefully checked will follow.
Inlet scrubbing. The type and design of inlet
separation must be carefully considered, as they
are critical for trouble-free operation of the
solvent unit. They can vary from slug catchers,
removing condensed water and hydrocarbons, to
reverse flow filter or coalescers when sub-micron
range aerosols are expected.
Absorber. The diameter is determined by the
feed gas flow rate and the solution circulation rate
by the type, concentration and equilibrium
loading of the amine. Trays are the most common
internals, but random and structured packing can
be found.
Flash tank and lean/rich exchanger. Low
pressure at the flash tank (3-6 bar) helps to
remove hydrocarbons, which reduces the amine
foaming potential. Exchanger corrosion must be
avoided in the rich amine line due to flashing acid
gases at the outlet. Stainless steel metallurgy
should be considered for low solvent
concentration and high amine loading.
Regenerator. The purpose is to strip the acid
gas from the rich amine using steam generated by
144
the reboiler. Steam or hot oil provides heat to the
reboiler; a 3.5 bar saturated steam is
recommended to avoid solvent degradation and
corrosion. The reflux ratio, ranging from 1 to 3, is
linked to the lean solvent specification.
Filter. The solvent should be kept clean by
using adequate mechanical filtration (5 or 10 mm)
and carbon filtration. The removal of FeS and
FeS-hydrocarbon materials from this equipment
avoids problems. A minimum 10-20% slipstream
of the circulation unit should be submitted to
filtration. The filtration media is to be changed
when the solvent colour varies and heat stable
salts should be prevented from building up.
Activated carbon filtration can reduce the need
for antifoam.
Amine solution control system. Solution
control leads to more reliable and trouble-free
operation. It is important to test the amine
behaviour with appropriate analytical techniques.
The operator should have the procedures, the
equipment as well as the expertise to perform the
tests defined by the process or amine vendor.
Foaming, corrosion, solvent degradation and the
resulting unit loss in capacity may be the result of
inappropriate analytical tests or evaluation time-
schedule. General analysis includes amine tests
(alkalinity titration, chromatographic spectrum),
acid gas loading, water content, solids and ash
content, heat stable salt content and anion
analysis (ion chromatography). Moreover, a
specific test for foaming ability could be of great
interest to monitor the unit.
Process variables
As the unit is properly designed, the main
variables in solvent processes include the
following.
Quality of the feed. The unit is generally
designed for a specific feed or a range of H2S
concentration. Since sweet gas quality depends on
the feed characteristics, specifications could
eventually not be reached for some feed streams
even using a higher flow rate or a more
regenerated solvent.
Absorber and regenerator pressures. Absorber
pressure generally results from the pressure of gas
at the exhaust of the previous refinery unit. A
change in the regenerator pressure may be the
result of a revamp of the SRU, when, for example,
a higher sulphur recovery is required.
Absorber temperature. Solvent temperature
must be higher than feed gas temperature,
typically 5-8°C, to prevent condensation and
foaming.
ENCYCLOPAEDIA OF HYDROCARBONS

Space velocity. Absorption is affected by
hydrodynamics. It is especially important to
control space velocity when slow kinetic for CO2
is opposed to equilibrium absorption of H2S in a
selective removal.
When all of these items are well established,
changes in operating conditions may lead to the
following problems:
Amines losses. They could be either
physical-mechanical or chemical based. Excessive
solution losses are generally linked to solution
foaming.
Foaming. Foaming will not occur if no
extra-unit contaminant is present in the streams.
Classical contaminants include corrosion
inhibitors, additives, liquids or solids entering the
unit and dissolved degradation products (FeS).
The above leads to decreased efficiency,
unattainable specification and solvent losses.
Some additives (silicon-based) are used to lower
the surface tension of liquids, and thus reduce
foaming. Use of an antifoam agent should be
considered a short-term measure.
Corrosion. Corrosion in amine units requires
very special attention. Amine and degradation
products may cause severe corrosion to the
equipment. Industry experience has pointed out
three key corrosion issues: exceedingly high flow
velocities, air entries leading to corrosive
degradation products and excessive reboiler
temperatures. These issues are resolved through
proper design and operating practices (Bonis et
al., 2004) for units working with high amine
concentrations (up to 40% weight for DEA). As
long as amine degradation products are identified
as key factors, MDEA is expected to be
significantly less corrosive than DEA, due to a
higher stability coupled with a lower degradation
product concentration.
Impact of feed gas composition on sulphur
removal unit efficiency. The composition of the
acid gas leaving the acid gas removal unit has an
impact on sulphur recovery efficiency.
If the H2S content is low, acid gas enrichment
is recommended. Basically, H2S, hydrocarbons and
ammonia contents would establish the criteria for
sulphur recovery efficiency and designs. The
conventional sulphur plant could then be converted
to oxygen enrichment so as to process more sour
gas and destroy the remaining impurities.
Nevertheless, if the solvent has been changed
either to process more acid gas or for economic
reasons, the downstream sulphur recovery units
generally need some equipment modifications for
capacity expansion.
VOLUME II / REFINING AND PETROCHEMICALS
SULPHUR CYCLE
3.2.3 The Claus process
The objective of the Claus process is to recover
elemental sulphur (Sx, with x between 2-8
depending on the temperature) from gas streams
containing hydrogen sulphide (H2S) stripped from
gas sweetening solvents (see Section 3.2.2). The
Claus process produces elemental sulphur by the
partial oxidation of H2S:
[9] H2S1/2 O2 1/8 S8H2Oheat (209 kJ)

The Claus plant effluent gases are either sent to
an incinerator or to a TGT unit (see Section
3.2.4), depending on the local air pollution
control regulations. The final effluent gas, which
cannot be valorized, is incinerated to convert all
of the sulphur compounds to sulphur dioxide
(SO2) in a thermal or catalytic incinerator. Being
of very good quality, the elemental sulphur
produced in the SRU, Claus or Claus plus TGT, is
used as a basic chemical in the industry. The
properties of elemental sulphur are well described
in various literature (Meyer, 1976; Shuai and
Meisen, 1995).
In the original Claus process, reaction [9] was
carried out in a single step over a catalyst. Since
the heat of the reaction was dissipated only by
radiation, high sulphur recovery was very difficult
to obtain. A very important modification to the
Claus process was made in 1940, which allowed
energy recovery, increased process capacity and
eliminated the issue of maintaining, in the
catalytic reactor, the low temperature favouring
high sulphur recoveries. In this modified-Claus
process (Fig. 6), reaction [9] is carried out in two
stages.
In the first stage, the thermal section, one-
third of the H2S is oxidized to SO2 with air or
oxygen enriched air at high temperature
(generally 925-1,200°C):
[10] H2S3/2O2 SO2H2Oheat (518 kJ)

This reaction is highly exothermic and is not
limited by equilibrium. The unburned H2S in the
acid gas reacts with the SO2 (obtained through
reaction [10], to yield the stoichiometric H2S/SO2
ratio of 2:1) to form elemental sulphur vapour:
[11] 2H2SSO2
3/2S22H2O


This reaction is endothermic and is limited by
equilibrium. About 60-70% of the conversion of
H2S to elemental sulphur occurs in the thermal
stage. An important function of the thermal
section is also to destroy the impurities that may
be present in the feed acid gas stream, such as
145
PROCESSES RELATED TO ENVIRONMENTAL ISSUES
thermal stage
HP or MP
air steam
H2S
burner
muffle furnace
re-heater
waste heat boiler LP
steam
S S
Fig. 6. Typical Claus process scheme (straight-through design).
ammonia (NH3), hydrocarbons, etc. During the
thermal stage, side reactions also occur in the
presence of CO2 or hydrocarbons, which produce
COS and CS2.
In the second stage (i.e. catalytic section), the
overall conversion of H2S to elemental sulphur is
increased in a series of catalytic reactors (1 to 3)
by reaction of the generated SO2 and the
unreacted H2S over fixed beds of Claus catalysts
at much lower temperatures (190-360°C):
[12] 2H2SSO2
3/8 S82H2Oheat (108 kJ)


Reaction [12] is called the Claus reaction. The
use of appropriate catalysts at selected
temperatures optimizes the Claus reaction yield
and also allows COS and CS2 produced in the
thermal stage to be eliminated. High-Pressure
(HP) steam is generated in the Waste Heat Boiler
(WHB), in which the gases are cooled from the
high flame temperature to the lower catalytic
reactor (converter) temperature (see again Fig. 6).
Sulphur condensers are provided to condense and
separate the elemental sulphur formed after the
thermal stage and after each catalytic reactor. The
heat released by the Claus reaction is recovered as
Low-Pressure (LP) steam in each sulphur
condenser. Product removal, lower catalytic
converter temperatures and an increased number
of catalytic converters enhance sulphur recovery.
Table 3 presents the typical, total sulphur recovery
of the modified-Claus process depending on the
number of catalytic reactors used.
Nowadays, sulphur recovery plants are based
on the modified-Claus process, although the
146
catalytic stage
optional 3rdd catalytic stage
catalytic catalytic
reactor reactor
or direct
erator
re-heater
re-heater
0-150°C
LP LP
steam steam
S
original Claus process is still implemented to treat
very low H2S concentrations gases, though in this
case, it is referred to as direct oxidation process.
There are a number of different process
configurations for the modified-Claus process,
depending mainly on the H2S concentration in the
Claus feed gas.
Chemistry and thermodynamics of the Claus
process
In principle, ideal performance is achieved
when all stoichiometric requirements for the basic
process reactions are satisfied under the most
favourable thermodynamic conditions, and
equilibrium is reached at all points in the process.
While thermodynamic favourability determines
ideal performance, the practicable capability is
dictated by the kinetic limitations imposed by the
operating conditions and plant equipment.
Thermodynamics
The basic design of a typical modified-Claus
plant can be best understood by looking at the
thermodynamic equilibrium curves calculated for
the reaction of pure hydrogen sulphide (H2S) with
air (Fig. 7):
[13] H2S1/2 O2
1/xSxH2O


Calculations are based on the principle of
minimization of the Gibbs free energy. All three
curves were calculated without sulphur removal
from the system. The difference between the
upper and lower curves (see again Fig. 7) results
from the sulphur vapour species under
ENCYCLOPAEDIA OF HYDROCARBONS
 SULPHUR CYCLE

Table 3. Total sulphur recovery 100

of the modified-Claus process over the number
of catalytic reactors used 90
S2
Total sulphur recovery 80
Number of catalytic of a modified-Claus S3
reactors plant (%) S4
S5
1 75-90 70
S6
2 94-96 S7

composition (mole %)
3 95-98 60 S8

50
consideration and the differences in
below 540°F, vapour saturated
thermodynamic data. The shape of the curves in above 540°F, vapour insaturated
40
Fig. 7 is a direct result of the temperature
dependency of the sulphur vapour composition
30
shown in Fig. 8. High molecular weight species
dominate at lower temperatures, and vice versa.
Thus, for a fixed number of sulphur atoms, fewer 20
moles of sulphur vapour are formed at lower
temperatures. This decreases the sulphur vapour 10
partial pressure and tends to shift the equilibrium
of reaction [13] to the right as well as increase the 0
0 500 1,000 1,500 2,000 2,500
conversion. The opposite is true at higher
temperatures. The same phenomenon causes the temperature (°F)
conversion to increase at low temperatures and Fig. 8. Equilibrium composition
of sulphur vapour from reaction of H2S
with stoichiometric quantity of air with
100 S8
a total system pressure
3.2ofBallaguet
1.0 atm (Paskall, 1979).
fig 08
S2
S2, S8
S2, S6, S8 decrease at high temperatures, as the total system
90 Sx (S1, S2, S3, S4, S5, S6, S7, S8) pressure is increased. The theoretical degree of
conversion is high at low temperature, falls off
rapidly and passes through a minimum at 560°C
(1,040°F), and then increases more slowly at
conversion (%)

80
higher temperatures. In the thermal stage region,
it is not possible to reach sulphur recoveries of
over 70%. Moreover, care must be taken to
70 quench the reaction mixture rapidly in order to
avoid reverse reaction. To convert more gases to
sulphur, thermodynamics suggests lower
60 temperatures in the catalytic region. Before
entering catalytic converters, elemental sulphur
must be condensed from the gas stream to prevent
sulphur condensation on the catalytic bed and
50 improve thermodynamic equilibrium yields. For
45 thermodynamic reasons, the catalytic unit should
0 500 1,000 1,500 2,000 2,500 be operated at as low a temperature as possible
temperature (°F) above the sulphur dewpoint, provided that the rate
of the reaction is fast enough. In practice, sulphur
Fig. 7. Equilibrium conversion of H2S
to elemental sulphur (Paskall, 1979): recovery is maximized by using two or more
effect of restricting the number of sulphur catalytic converters with sulphur removal between
vapour species (pure H2S with air, 1.0 atm, each converter, and by decreasing temperature in
no sulphur removal). successive converters.

VOLUME II / REFINING AND PETROCHEMICALS 147

PROCESSES RELATED TO ENVIRONMENTAL ISSUES

Chemistry in the thermal stage with the sulphur rich environment:

Combustion processes occurring in the Claus
[14] CH4 C2H2

reaction furnace are complicated (Connock, 1999
b). The presence of CO2 and small quantities of [15] CH2O COH2 

hydrocarbons in the feed acid gas must be taken

into account to ensure that gases leaving the [16] COH2O CO2H2 

WHB have the desired 2:1 H2S/SO2 ratio. CO2 is [17] CH42S2 CS22H2S 

particularly important as it becomes involved in a

multitude of processes leading to CO and COS, [18] CS2 CS2 

as well as affecting the amount of hydrogen

finally appearing in the product gas. Fig. 9
provides a simplistic overview of Claus furnace
chemistry showing what are considered the more
important reactions that occur in the furnace in
the absence of hydrocarbon contaminants, but in
the presence of CO2. Chemistry occurring in the
Claus reaction furnace may be split into two
types: combustion reactions occurring in the
oxygen-rich region; reactions proceeding in the
oxygen-free (anoxic) region driven
by the high temperature resulting from
combustion reactions.
The carryover of hydrocarbons with the acid
gas into the Claus reaction furnace further
complicates the reactions. The hydrocarbon
impurities may range from complex alkanes to
BTX. Although thermodynamic considerations
suggest that these hydrocarbons should fully
combust to CO2 and H2O, the rate at which they
COS and CS2 lower the Claus sulphur
recovery, unless their conversion to H2S is
achieved by hydrolysis at the relatively high
temperatures found in the first catalytic converter.
It has been well established that the design and
mode of operation of the furnace can significantly
influence the degree to which hydrocarbons are
converted to COS and CS2.
Ammonia (NH3) destruction is also a problem
when treating refinery Sour Water Stripper (SWS)
off-gas.
Chemistry in catalytic stages
Sulphur recovery in catalytic stages is
governed by two main catalytic reactions: the
Claus reaction [12] and the hydrolysis of COS
and CS2 (according to reactions [19] and [20],
respectively).
[19] COSH2O
CO2H2S 


do so is questionable since the CH bond is

generally stronger than the SH bond. Thus, [20] CS22H2O
CO22H2S 


kinetic factors will affect the fate of the

hydrocarbons in the reaction furnace, since they
will be in competition with H2S for a restricted
oxygen supply. In the event that hydrocarbons are
not fully combusted, it is expected that they will
produce CO, C, COS and CS2 through reactions
In terms of contribution to sulphur recovery,
the Claus reaction is by far the most important.
However, the efficiency of the COS and CS2
hydrolysis becomes increasingly important and
even limiting when recovery targets of more than

1,200°C 1,000°C 600°C

waste heat boiler

(heat removal
equilibria readjustment)

burner reaction furnace

SO2, 2H2S,
H2O, [S2]
H2S O2 SO2, H2S, SO2, H2S, CO2, N2,
H2S/CO2 [HC] S2, CO2, [CO, H2, COS, CS2]
SO2 [H2, CO,
N2, CO, H2,
CO2 N2 COS, CS2 COS, CS2]
minor products
O2-rich anoxic anoxic region
region region
water high temperature
steam

Fig. 9. Expanded overview of Claus reaction furnace and waste heat boiler (Connock, 1999b).

148 ENCYCLOPAEDIA OF HYDROCARBONS


97.5% are required. The proper selection of
catalysts is an essential part of modified-Claus
plant optimization to achieve maximum sulphur
recovery efficiencies. A wide range of industrial
catalysts is now available (Table 4). There are
basically five types of industrial Claus catalysts
(Sulphur […] 1995; Chasing […] 1997).
Activated alumina catalysts generally
demonstrate high activity toward the Claus
reaction in the first reactor, fair activity toward
COS hydrolysis in the first reactor and toward the
Claus reaction in the second reactor. They do not
have adequate activity for CS2 hydrolysis.
Activated aluminas are manufactured by
granulation of flash-dried alumina hydroxides
(hydrated alumina that has had its water thermally
removed to produce a transitional phase alumina).
Alumina-based catalysts are subject to various
deactivation mechanisms:
• A combination of temperature and water
content reduces the effective surface area of
the catalyst due to thermal and hydrothermal
ageing. This effect is irreversible, though
proper design, operation and maintenance of
the plant can limit it.
• Fouling by condensation of sulphur or by
deposition of carbon or ammonium salts
impairs catalyst activity by plugging the pores.
Sulphur deposition is reversible, the catalyst
being regenerated by heat soaking with no
adverse effect. Carbon and ammonium salts
deactivation is essentially irreversible. It is
best avoided by reducing contamination of the
feed gas (BTX, high molecular weight
hydrocarbons, ammonia compounds and
amines).
• All alumina-based sulphur recovery catalysts
are prone to sulphation if exposed to sulphur
and/or SO2 and traces of oxygen. Sulphation
is most likely to occur during start-up,
shutdown or periods of malfunction when the
feed gas/oxygen balance is disturbed.
Sulphation is partly reversible by heat soaking
under an H2S/SO2 ratio above 2:1. However,
activity improvement is temporary and
repeated rejuvenations result in irreversible
damage to the catalyst, shortening its
lifespan. It is best avoided by proper oxygen
control. However, a study (Clark et al., 2002)
has shown that the formation of sulphate on
alumina is directly related to the oxidizing
properties of the solid and the chemistry of
H2S/SO2 conversion over this material.
Indeed, although sulphate is formed by
oxygen ingress into a converter, it will also be
VOLUME II / REFINING AND PETROCHEMICALS
SULPHUR CYCLE
present on any Claus catalyst as a result of the
chemistry of H2S/SO2 conversion, even in the
absence of oxygen.
Titanium dioxide-based catalysts
(TiO2-based catalysts) have a higher activity than
activated alumina towards carbon sulphide
hydrolysis in the first reactor and towards the
Claus reaction in all stages. Appreciable carbon
sulphide conversion can also be attained at second
converter conditions. The Claus reaction
is driven virtually to thermodynamic
equilibrium. TiO2-based catalysts are much less
susceptible than alumina to ageing and remain
virtually unaffected by sulphation. Sulphate is
also formed on TiO2, though it appears to have no
influence on CS2 conversion at temperatures
exceeding 320°C. Moreover, they have
a virtually unlimited lifespan under
normal conditions.
Various promoted activated alumina catalysts
are also available. Alumina may be promoted by
alkaline earth oxides (calcium or magnesium
oxides), TiO2 or sodium monoxide (Na2O).
The alkaline earth promoted catalysts were
designed to improve the resistance of activated
alumina Claus catalysts to sulphation.
TiO2-promoted alumina catalysts have higher
activity than ordinary activated alumina for both
the Claus reaction and carbon
sulphide hydrolysis.
Protective catalysts (iron- and nickel-promoted
alumina) are used as a guard bed to protect standard
alumina catalysts in Claus reactors against sulphation
by reducing the oxygen content of the stream gas. It is
especially advantageous to use protective catalysts in
Claus plants when direct reheating is considered. They
are also active for the Claus reaction and hydrolysis
reactions. In fact, a bed of activated alumina catalyst
topped by a layer of protective catalyst is often more
reactive for all reactions than a single layer of
activated alumina. The use of these oxygen-scavenging
catalysts in the Claus unit also provides protection for
subdewpoint tail gas treatment units downstream. With
streams containing BTX, it is also possible to use a
protective catalyst layer, generally a selective
hydrogenation catalyst, in order to prevent carbon
fouling by avoiding BTX cracking
and polymerization.
Claus productivity can also be boosted if the bed
support material, used at the top and bottom of
Claus reactors, also acts as a catalyst. These active
bed support aluminas are used to replace inert balls
providing higher overall activity. These products are
especially useful when severe operating conditions
require an exceptionally strong material.
149
PROCESSES RELATED TO ENVIRONMENTAL ISSUES

Table 4. Commercial SRU catalysts from Axens (former Procatalyse) and Almatis (former Alcoa),
the world's leading suppliers

Name Company Type Activity

DR Axens Activated alumina Active bed support and Claus reaction

SRU Almatis/
Activated alumina Active bed support and Claus reaction
ABS Engelhard
CR Macroporous activated alumina Claus reaction for Claus and subdewpoint TGT
Axens
CR 3S Ultra-macroporous activated alumina (Sulfreen, CBA and MCRC)
DD-431
Almatis/ Activated alumina Claus reaction for Claus and subdewpoint TGT
S-400
Engelhard with tailored pore size distribution (Sulfreen, CBA and MCRC)
S-100

AA 2-5 Axens Microporous activated alumina Claus reaction for subdewpoint TGT (Sulfreen)

AM Axens Promoted activated alumina Oxygen scavenger and Claus reactions

AM S 31 Axens Promoted activated alumina Oxygen scavenger, Claus and CS2 reactions

Almatis/
S-100 SR Promoted activated alumina Oxygen scavenger
Engelhard
Selective hydrogenation catalyst used as a protective layer
CSM 31 Axens Proprietary promoter
with streams containing aromatics
Almatis/ Claus reaction and Resistance to deactivation
DD-831 Promoted activated alumina
Engelhard from sulphation
Almatis/ TiO promoted activated alumina Claus reaction, COS, CS2
DD-931 2
Engelhard

CRS 31 Axens TiO2 Claus reaction, COS, CS2, HCN*

TG 103 Axens CoMo / alumina Hydrogenation reactions for SCOT-type TGT

TG 107 Low temperature hydrogenation reactions

Axens CoMo / alumina
TG 136 for SCOT-type TGT
TGS 294 Adsorbent catalyst for direct oxidation of H2S to S
Axens Proprietary / alumina
TG 732 for subdewpoint TGT (Doxosulfreen)

* also for IGCC cogeneration plants

The industrial Claus processes and their evolution
The Claus is the technology of choice for
gases containing high concentrations of H2S
and/or large quantities of sulphur. Nevertheless,
when H2S content is lower than 30% and/or the
amount of sulphur is less than 10-20 tons of
sulphur per day (t S/d), some other processes are
often more economical.
furnace. According to the Claus reaction, the air needed
for combustion is one-third of that required for the
complete combustion of H2S. Consequently, the Claus
furnace operates far away from complete combustion in
the straight-through design. A minimum temperature of
925°C is generally considered to sustain a stable flame.
A higher flame temperature is often required to destroy
contaminants when present.

Rich acid gases (H2 S50%)
The H2S content of the Claus acid gas feed
encountered in most refineries is around 80%. It is
treated in the simplest, straight-through Claus process
where all of the acid gas is processed in the reaction
Medium acid gases (10%H2 S50%)
When H2S concentration is low, the stability of
the flame cannot be reached and the straight-
through design is no longer a good choice. The
following possibilities must therefore be chosen.

150 ENCYCLOPAEDIA OF HYDROCARBONS


Acid gas bypass. When part of the feed gas is
bypassed, the furnace operates nearer to complete
combustion, if one considers the same quantity of
air entering the Claus unit as in the straight-
through design. This results in an increased flame
temperature. The design is referred to as the split-
flow design. The upper limit for acid gas bypass is
two-thirds of feed gas, as the furnace must be
operated under reducing conditions. However, if
contaminants are present in the feed, they will
remain in part and enter directly into the catalytic
section of the Claus. Troubleshooting and/or
instability of the sulphur plant may then occur,
since these contaminants highly contribute to
deactivation and plugging of the catalytic
converters. Nevertheless, when this solution is
applicable, it is the simplest and most economical
way to treat medium acid gas composition.
Feed preheat. In order to maintain or raise the
flame temperature, combustion air preheating and
acid gas preheating must be examined. Acid gas
preheating is more difficult to apply when the
acid gas is recovered from the amine regenerator
at low pressure. Moreover, corrosion must be
properly checked as thermal cracking of the acid
gas constituents may occur. When considering a
revamp of an existing straight-through unit,
specific attention must be paid to the design of
the burner in order to avoid corrosion and to
enable the use of high temperature gas.
Oxygen enrichment. Oxygen enrichment raises
the flame temperature by limiting the nitrogen
effect of air. Moreover, this results in reductions
of the equipment size and investment cost, since
the global flow processed in the sulphur plant is
lower (Lee and Moore, 1997). Nevertheless, in
order to be applied, this technology requires an
available and economical source of oxygen. For
the time being, only low-level enrichments (i.e. up
to 28%) are addressed, since they lead to minor
changes at the Claus unit and provide up to a 25%
increase in capacity.
Fuel gas addition. Fuel gas can be added to
ensure a high flame temperature, though this can
bring about some disadvantages. Firstly, this will
enlarge the size of the sulphur plant and lower the
total sulphur recovery efficiency. Moreover, it
could provoke catalyst deactivation or converter
plugging, thus the consequences of fuel gas
addition on the sulphur recovery unit must be
carefully examined.
Lean acid gas (5%H2 S30%)
For this kind of gas, the Claus process is less
competitive because it is difficult to ensure a stable
VOLUME II / REFINING AND PETROCHEMICALS
SULPHUR CYCLE
flame at a low operating cost; consequently, some
other technologies are of interest. One method is to
replace the thermal section of the modified-Claus
process by a catalytic section. Over the catalyst, air
oxidizes H2S to SO2, which reacts with additional
H2S to produce elemental sulphur.
Extra-lean acid gases (H2 S5%)
Several technologies are proposed depending on
the H2S content and the sulphur tonnage to be
recovered. A way to treat extra-lean acid gas is
through direct oxidation. In this case, the higher the
H2S content, the lower the selectivity of the
reaction, though the upper limit is around 1.5%
H2S. Other processes, including redox processes
(wet oxidation, see Section 3.2.4) or non-
regenerative processes, achieve very high recovery
efficiency of nearly 100%. Among the redox, some
utilize vanadium complex, as does the Stretford
process. Others are based on iron chelates: Lo-Cat,
Sulferox or Sulfint HP processes. The chemical
consumption cost limits their application to low
sulphur tonnage (10 t S/d). When the quantity of
sulphur to be removed is very low (0.1 t S/d)
scavengers may be used. These liquid or solid
chemicals selectively react with H2S. Iron-sponge
and Sulfatreat caustic scrubbing are part of these
processes. They are based on non-regenerative
chemicals such as activated carbon, iron oxide,
caustic solution or regenerative chemicals (e.g.
triazine). The disposal cost for the used chemicals
should be accurately considered in the global
evaluation of the process.
Claus operating variables
The overall sulphur recovery efficiency of a
modified-Claus unit is greatly dependent on the
design, maintenance and operation of the unit.
The most important control variable in the
operation of Claus plants is the ratio of H2S to
SO2 in the gases entering the catalytic converters.
Maximum conversion requires that this ratio is
maintained constant at the stoichiometric
proportion of 2 moles of H2S to 1 mole of SO2.
Appreciable deviation from the stoichiometric
ratio leads to a drastic reduction in conversion
efficiency. Several methods, based on controlling
the air flow by continuous analysis of the ratio of
H2S to SO2 in the plant tail gas, have been
developed and are used ever more frequently.
Several analytical instruments based on vapour
chromatography and ultraviolet absorption are
available commercially.
In addition, it is very important to operate the
different catalytic converters at the right
151
PROCESSES RELATED TO ENVIRONMENTAL ISSUES
temperature (Bohme and Sames, 1999). For
example, the condensation of elemental sulphur
on the catalytic converters can be avoided by
maintaining their temperature above the sulphur
dewpoint of the gas mixture.
When the feed gas contains contaminants, a
higher flame temperature is often required to
destroy them. Ammonia, heavy hydrocarbons,
BTX, mercaptans and cyanides are among the
contaminants most often encountered.
As regards ammonia, it is typically provided
by the off-gas of the SWS of the refinery. The
Claus unit is considered the best place to destroy
this off-gas, which also contains H2S, thanks to
its high furnace temperature. NH3 must be
destroyed in the reaction furnace, otherwise
sulphur trioxide (SO3) can form due to the
following reactions:
[21] 2NH35/2O2 2NO3H2O

[22] 2NOO2 2NO2 
[NO2]
[23] SO2
 SO3
SO3 causes severe downstream problems like
corrosion, catalyst deactivation and salt formation.
Two methods are available to successfully destroy
NH3 using the following reaction:
[24] 2NH33/2O2 N23H2O

The first method involves a split-flow reaction
furnace design; the second requires a high-
intensity reaction furnace burner. It is essential
for NH3 to be almost completely destroyed, being
that ammonia concentrations even as low as
500-1,000 ppm by volume (ppmv) can cause
problems.
As for BTX and heavy hydrocarbons, acid gas
may contain these compounds since solvent units
are able to co-absorb them together with H2S.
Feed stream must be analysed and the necessary
measures must be taken to keep them from
entering the Claus catalytic section, as they may
cause catalyst deactivation, plugging and off-
specification sulphur for market purposes (e.g.
green sulphur compared to bright yellow sulphur).
When acid gases of high H2S content are
processed, the temperature in the reaction furnace
is usually high enough to result in the complete
combustion of all hydrocarbons to CO2 and water,
and no carbonaceous material deposition is
experienced. However, at the low combustion
temperature occurring in straight-through plants,
processing gases with less than approximately
40-50% H2S, cracking and partial combustion of
152
hydrocarbons produce complex carbonaceous
materials that are carried into the catalytic
reactors, gradually deteriorating catalyst
performance. In addition, hydrocarbons can be
fed directly to the first catalytic converter without
being burned when a split-flow design is utilized.
These hydrocarbons can also cause catalyst
deterioration.
Regarding mercaptans and cyanides, the same
general considerations must be applied for the
Claus unit. For other processes, such as redox or
scavenger processes, problems connected to
chemical odours and disposal must be carefully
considered.
3.2.4 Tail gas treatment
The modified-Claus process has continually
improved since 1940. However, this process can
generally achieve only up to 98% sulphur
recovery for a three-stage configuration. With
new environmental requirements, sulphur
recovery efficiencies of 98.5-99.95% are now
required. Regulations differ from country to
country and may even vary between different
regions within the same country:
• In Canada, plants with a capacity of 50 t S/d
should achieve a total sulphur recovery of
98.5%, increasing to 99% for plants with a
capacity of 2,000 t S/d.
• In Europe, the 1998 ‘bubble concept’ for SO2
emissions is often applied, whereby all SO2
emission sources in one refinery can be
pooled and the total SO2 emission limit of
1,700 mg/Nm3 should be met in the flue gas.
This emission limit will be reduced in the
coming decades. In Germany, strict
regulations (TA-Luft) are in place and require
sulphur recoveries of 99.8% for plants with a
capacity of 20-50 t S/d and 99.5% for plants
with capacities over 50 t S/d.
• Japan requires recoveries over 99.8% and
Taiwan demands levels as high as 99.95%.
• In the United States, it depends on the
individual state. For example, in Texas
refineries, for new facilities, the recovery must
be between 96 and 99.8%, depending on the
sulphur production capacity. However, it
seems that 99.9% recovery efficiency is
becoming a regulatory standard for sulphur
recovery plants with a capacity of 20 t S/d or
greater.
Thus, the modified-Claus process has to be
supplemented with another process designed to
ENCYCLOPAEDIA OF HYDROCARBONS
 SULPHUR CYCLE

remove residual sulphur compounds from the
Claus plant tail gas. Processes of this sort are
usually called Tail Gas Cleanup (TGC) or Tail Gas
Treating (TGT) processes. The TGT processes,
which have achieved commercial status
(Connock, 1998, 2003; Keeping […] 1994), can
be categorized into six groups (Table 5). The most
important TGT processes are described as
follows.
Wet subdewpoint processes: Clauspol processes
The Clauspol process was one of the first
TGT processes to be developed. More than 40
Clauspol units, ranging from 25-700 t S/d
(single train), have been licensed worldwide
since 1971. The Clauspol process (Fig. 10) is
based on the continuation of the Claus reaction
[12] between the residual H2S and SO2 present
in Claus tail gas, in a non-volatile liquid organic
solvent containing a proprietary catalyst
(Barrère-Tricca et al., 2000). The reaction is
performed at a temperature slightly above the
sulphur melting point (120-130°C). The
produced sulphur (99.9% pure bright yellow) is
only slightly miscible with the solvent and, due
to its higher density, is recovered as a separate
liquid phase from the bottom of the reactor,
shifting the Claus reaction equilibrium very
favourably. There are other sulphur components
that are advantageously removed from Claus tail

Table 5. Main tail gas treatment (TGT) processes

Sulphur
Category Process name Licensor
recovery (%)
Wet subdewpoint Clauspol II 99.0-99.8 Prosernat, France
Clauspol Booster 99,9 99.9 Prosernat, France
Dry subdewpoint Sulfreen 99.0-99.5 Total, France / Lurgi, Italy / Prosernat, France
Hydrosulfreen 99.7 Total, France / Lurgi, Italy / Prosernat, France
Doxosulfreen 99.8-99.9 Total, France / Lurgi, Italy / Prosernat, France
CBA 99.3-99.4 BP Amoco, USA
MCRC 99.0 Delta Hudson Engineering, Canada
Clinsulf-SDP 99.4 Linde, Germany
Reduction to H2S
 H2S scrubbing SCOT 99.9 Shell Global Solutions, Netherlands
Super SCOT 99.95 Shell Global Solutions, Netherlands
LS-SCOT 99.95 Shell Global Solutions, Netherlands
Sultimate 99.95 Prosernat, France
BSR/MDEA 99.9 Parsons Energy & Chemicals Group Inc., USA
Sulften 99.9 FB&D Tech, USA / Union Carbide Corporation, USA
Resulf 99.9 TPA, USA
Resulf-10 99.95 TPA, USA
RAR 99.9 Technip KTI SpA, Italy
‘Flexorb SE Plus’ amine 99.9 Exxon Mobil, USA
HCR 99.95 Siirtec Nigi, Italy
BSR/Selectox 99.5 Parsons Energy & Chemicals Group, USA
 direct oxidation MODOP 99.3-99.5 Exxon Mobil, USA
BSR/Hi-Activity 99.5 Parsons Energy & Chemicals Group, USA
Ultra 99.7 BP Amoco Corporation, USA
 subdewpoint BSR/Stretford 99.9 Parsons Energy & Chemicals Group, USA
 wet oxidation BSR/Unisulf 99.9 Parsons Energy & Chemicals Group, USA
Dry oxidation to S Superclaus 99.0-99.5 Jacobs Engineering, Netherlands
Wet oxidation to S Sulfint/Sulfint HP 99.99 Prosernat, France / Le Gaz Intégral (LGI), France
LO-CAT/LO-CAT II 99.99 GasTechnologyProducts-Merichem, USA
Sulferox 99.99 Shell Global Solutions, Netherlands / LGI, France
Crystasulf 99.99 CrystaTech, USA
Thiopaq 99.99 Paques BV, Netherlands / Shell Global Solutions,
Netherlands
Oxidation to SO2  Wellman Lord 99.9 Kvaerner Process Technology, UK
SO2 scrubbing Clintox 99.9 Linde, Germany
Elsorb/Labsorb 99.9 Belco Technologies, USA

VOLUME II / REFINING AND PETROCHEMICALS 153

PROCESSES RELATED TO ENVIRONMENTAL ISSUES
gas in the Clauspol unit (e.g. entrained liquid
sulphur, sulphur vapour, COS and CS2,
which are partially hydrolysed). The basic
Clauspol II process allows sulphur recoveries up
to 99.8%, provided that COS and CS2
have been hydrolysed down to 300 ppmv of
sulphur or less in the catalytic stages of the
Claus plant, by using a TiO2-based catalyst. The
Clauspol process is a very simple and
continuous process. It requires neither hydrogen
nor blower and there is no recycling of H2S back
to the Claus unit. Investment and operating costs
are low, making the Clauspol II process the
cheapest TGT technology available on the
market from 99.4-99.8% sulphur recoveries.
Under normal conditions, the carbon steel
corrosion rate in Clauspol units is avoided by
applying simple rules regarding the design,
construction and operation of the unit (Barrère-
Tricca et al., 2000).
The latest main developments of the Clauspol
process are described below.
• The Clauspol II process circulates a sulphur-
saturated solvent that contains small amounts
of liquid sulphur. The liquid sulphur vapour
pressure, though low, contributes to sulphur
losses in the effluent from 350 ppmv With its
desaturation loop, the Clauspol Booster 99.9
process eliminates the liquid sulphur phase in
the solvent and circulates an unsaturated
solvent. This allows sulphur recoveries of over
99.9%.
• The desalter has been recently developed to
prevent the accumulation of solid salts on the
reactor packing.
The desaturation loop and the desalter treat
only a fraction of the solvent from the
recirculation loop. They are small, simple, easy to
install on existing units and easy to operate. They
can be shut down without shutting down the basic
Clauspol II section.
Dry subdewpoint processes: Sulfreen processes
The Sulfreen process (Willing and Linder,
1994) was developed in the early 1970s. There are
more than 50 references worldwide ranging from
10-2,200 t S/d (single train). The Sulfreen process
(Fig. 11) is based on the continuation of the Claus
reaction [12], between the residual H2S and SO2
present in Claus tail gas, on a dry catalytic bed at
low temperature (120-150°C). Activated alumina
is used as the catalyst. The Sulfreen process
produces 99.9% pure bright yellow sulphur. The
Claus reaction is extended and the sulphur
recovery enhanced. This occurs, firstly, because
154
gas to incinerator
120-130°C
gas/liquid
contactor
solvent
temperature
control
Claus
tail gas
catalyst
make-up
liquid sulphur
Fig. 10. Clauspol II process scheme.
the equilibrium is thermodynamically favoured at
low temperature and, secondly, since the sulphur
is adsorbed on the catalyst. The Sulfreen process
basically consists of two (occasionally three for
large capacities) Sulfreen reactors in series with
the Claus reactors. As the sulphur accumulates on
the catalyst, its activity decreases and the catalyst
beds have to be regenerated thermally at
250-300°C. During the regeneration step, sulphur
is desorbed and the catalyst is restored to full
activity by part of the preheated TGT gas. Once
regeneration is achieved, the catalyst bed is
cooled to the operating temperature. Sulphur from
the hot regeneration stream is then condensed.
Typical overall sulphur recoveries are in the
98.5-99.5% range, depending on the Claus unit
arrangement. COS and CS2 are not hydrolysed.
Two enhanced versions of the Sulfreen process
are also available and enable higher sulphur
recoveries to be reached.
The Hydrosulfreen process is based on the
pre-treatment of the Claus tail gas by hydrolysis
of COS and CS2 to H2S and direct oxidation of
H2S into elemental sulphur.
These reactions are performed by contacting the
Claus tail gas with a TiO2-based catalyst at about
300°C. This pre-treatment is followed by a basic
Sulfreen reactor. A Claus plant with two catalytic
stages and a Hydrosulfreen unit can achieve an
overall sulphur recovery efficiency
of over 99.5%.
The Doxosulfreen process is based on a
post-treatment after a Sulfreen unit or an
ENCYCLOPAEDIA OF HYDROCARBONS

Fig. 11. Sulfreen
process scheme. heater
Regeneration step:
S is removed
by vaporization
in hot tail gas.
Reaction step:
H2S and SO2 react on the
250-300 °C
Sulfreen alumina catalyst,
produced S is adsorbed. fuel air
gas
Claus tail
gas
blower
Hydrosulfreen unit. The upstream units are
operated to get a slight excess of H2S in order to
reach a nearly total SO2 conversion on the
Sulfreen reactor. Therefore, the remaining H2S at
the outlet of the Sulfreen reactor is oxidized with
air to elemental sulphur at a low temperature
(100-130°C). Both Sulfreen and oxidation
reactors are regenerated through a common
regeneration loop. The oxidation catalyst is based
on copper and optimized special alumina.
The Doxosulfreen process is capable
of reaching an overall sulphur recovery
of up to 99.9%.
Reduction to H2S plus H2S scrubbing
An entire family of TGT processes exists
based on the reduction of sulphur compounds to
H2S, followed by H2S scrubbing, and recycling of
the H2S stream to the Claus unit. The SCOT
process was the first to be developed and is the
most widespread, with more than 200 units
constructed all over the world since 1973, and
with single train capacities of up to 2,500 t S/d.
The other TGT processes of this family
(Sultimate, BSR/Amine, Resulf, RAR, ARCO,
HCR, etc.) are more or less designed and operated
in accordance with the SCOT concept (van den
Brand and Roos, 2002). The Claus tail gas is
heated to about 300°C using a heat exchanger or
in-line burner (Fig. 12). The heated gas is mixed
with a reducing gas containing hydrogen and
passes through a fixed bed of CoMo/alumina
catalyst or NiMo/alumina catalyst, where all
sulphur components are converted into H2S. Two
types of reactions occur: hydrolysis and
hydrogenation. The tail gas leaves the
VOLUME II / REFINING AND PETROCHEMICALS
SULPHUR CYCLE
Sulfreen reactors
to incinerator
- 0°C
120-1
- 50°
0 C
condenser
sulphur
hydrogenation reactor at a temperature of
approximately 320-340°C and is cooled in two
stages. The hot gases are cooled to about
160-200°C by passing through the tube-side of a
shell-and-tube heat exchanger or waste heat
boiler. The gas is then further cooled to 40°C by
direct contact with circulating water in a quench
tower. During gas cooling, most of the water
vapour contained in gas is condensed and mixed
with the circulating water. Since the circulating
water is in a closed loop system, the condensed
water must be removed from the system to
maintain a constant water level in the tower. The
water leaving the system contains a few ppm of
H2S and is typically recycled to the SWS unit for
H2S recovery. The cooled gas leaves the top of the
quench tower and is sent to the absorber, where it
is washed counter-currently with a lean H2S
solvent. Various types of solvent can be employed,
but a selective amine is normally used (e.g.
MDEA). The choice of the solvent depends on the
tail gas composition (see Section 3.2.2). The
downward flowing solvent contacts the upward
flowing gas and absorbs nearly all of the H2S and
some CO2 when present. The absorber off-gas
typically contains 150 ppmv of H2S or less and is
sent to the Claus incinerator. The rich solvent
leaving the absorber bottom is pumped through a
lean/rich solvent regenerator, where the H2S (and
eventually CO2) are removed by steam stripping.
Acid gas from the regenerator is recycled to the
Claus thermal stage. Lean solvent from the
regenerator is returned to the absorber.
The aims of developments in recent years were
to lower the total sulphur content of the emissions
to less than 50 ppmv (comparable to 99.95% total
155
PROCESSES RELATED TO ENVIRONMENTAL ISSUES
Fig. 12. Sultimate
process scheme. to Claus thermal stage
and cooling
air
heater
natural
gas
Claus
tail gas
reduction
reactor
steam
cooler
sulphur recovery) and to significantly reduce
investment and operating costs.
In order to reduce capital costs, it is possible
to use a common amine regeneration section for
the TGT unit as well as for the existing amine
desulphurization unit. To reduce operating costs,
it is also possible to use the solvent in cascade
from the TGT unit to the other sweetening units.
New catalysts enable operation of the
hydrogenation step at lower temperatures (220°C
or below, depending on inlet gas composition),
greatly reducing energy consumption and
avoiding in line burners with their drawbacks
(soot deposit for some of them).
The total sulphur content of the emissions is
significantly lowered thanks to the following
factors.
• Absorption is improved by using a lower lean
solvent temperature, the solubility of H2S in
amine solvents decreasing with temperature.
• Stripping is improved utilizing a two-stage
regeneration, in which part of the amine
solvent flow is more deeply stripped. The
super-lean solvent is routed to the top tray of
the absorber, while the semi-lean solvent
comes in half way down the absorber.
• Inexpensive additive (i.e. strong acid) to the
amine solvent improves its regeneration,
156
to incinerator
quench final
amine
tower scrubber
reducing
gas
LP
amine
regeneration
waste water
to treatment
(SNS)
producing either a better solvent leanness,
thereby a lower off-gas H2S specification, or
the same solvent leanness with less steam.
Wet oxidation: redox processes
Redox processes allow direct oxidation of H2S
into elemental sulphur at ambient temperature,
with nearly 100% selectivity and conversion.
Redox processes are usually highly flexible and
are being used on a wide variety of H2S
containing gases, including gas from acid gas
enrichment units and from the Claus unit,
provided that the gas is mainly H2S (Nagl, 2001).
The main limitations of current redox processes
are their relatively high chemical costs, the
quality of the sulphur product, which is generally
not as pure as Claus sulphur and, for some
applications, the difficulty in directly treating
high pressure gases.
In redox processes, the H2S containing gas is
washed with a solution containing a redox
catalyst. In a first step, the aqueous solution
absorbs the H2S, which then reacts with the
oxidized form of the catalyst to yield elemental
sulphur as the catalyst is converted into its
reduced form. In a second step, the reduced form
of the catalyst is contacted with air and oxidized
prior to reuse. Redox catalysts are usually
ENCYCLOPAEDIA OF HYDROCARBONS

polyvalent metallic cations chelated with organic
ligands. The former vanadium salts used in the
Stretford process have now been replaced in all
major redox processes by iron complexes based
on Ethylene Diamine Tetra Acetic acid (EDTA),
Hydroxyethyl Ethylene Diamine Tri Acetic acid
(HEDTA) or Nitrilo Tri Acetic acid (NTA)
(McManus, 1998; Heguy and Nagl, 2003).
The main chemical reactions are:
[25] H2S2Fe3 S2Fe22H

[26] 2Fe22H1/2O2 2Fe3H2O

[27] global reaction: H2S1/2O2 SH2O

Usually the two distinct steps of the process,
which are H2S oxidation [25] and Fe2 oxidation
[26], are performed in separate vessels; the redox
solution is circulated between the two. Absorption
is performed at the pressure of the gas to be treated
and regeneration or oxidation of the solution is
conducted at atmospheric pressure. The elemental
sulphur forms nearly instantaneously in the
absorber vessel when the sour gas comes in contact
with the oxidized solution. Solid sulphur is then
separated from the solution (flotation, filtration,
centrifugation, etc.), generally under atmospheric
pressure. The recovered sulphur is contaminated
with the iron catalyst and degradation products
composed of organic and inorganic salts. In order to
produce Claus quality sulphur, this sulphur needs to
be treated by water washing and/or smelting. The
organic ligands used in the catalytic solution are
slowly oxidized during process operation. A
continuous catalyst make-up prevents an efficiency
decrease due to degradation and catalyst losses in
the sulphur product. Chemical cost is usually in the
range of several hundreds of US dollars per ton of
sulphur produced and is the most important factor
in the overall treatment cost. Since iron based
catalyst and its degradation products are non-toxic
and/or easily biodegradable, the ‘redox’ sulphur
will generally be easily disposed in landfills, or sold
for agricultural use as fertilizer.
As previously shown, the most common method
for high pressure gas desulphurization remains H2S
extraction with an amine unit, followed by a Claus
unit or a low pressure redox unit; the
depressurization of this mixture, prior to the
atmospheric air oxidation step in the redox process,
can lead to severe foaming and plugging problems.
Despite these difficulties, the direct treatment of
high pressure gases with redox processes remains
attractive as up to 50% investment savings could be
gained, as compared to conventional methods (Le
Strat et al., 2001). In the Sulfint HP process, sulphur
VOLUME II / REFINING AND PETROCHEMICALS
SULPHUR CYCLE
particles are then removed from the solution before
its depressurization, thanks to a continuous high-
pressure filtration. Dissolved gas, which is low for
aqueous solution compared to organic solvents,
easily separates in a flash drum; moreover, foaming
tendency is tremendously reduced, as no sulphur
particles are found down the filter.
Other processes, such as Crystasulf, are based
on organic solvent that facilitates larger sulphur
crystals at the price of solvent coabsorption.
Dry oxidation: Superclaus
The Superclaus process (Lagas et al., 1989) was
introduced to the industry in 1988 as a new
development of the Claus process. More than 70 units
have been licensed worldwide, ranging from
3-1,000 t S/d. The Superclaus unit consists of a thermal
stage, followed by three catalytic stages with sulphur
removal by condensation between each stage. Two
reactors are filled with standard Claus catalysts, while
the third reactor is filled with a proprietary selective
oxidation catalyst known as Superclaus catalyst
(Fe2O3 on silica support for the last generation). The
thermal stage is operated under oxygen-deficient
conditions, in so that the H2S/SO2 ratio in the furnace
is much higher than the conventional 2:1. As a result,
the second catalytic reactor outlet gas contains a large
excess of H2S over SO2. In the last catalytic reactor
(i.e. the Superclaus reactor), the catalyst oxidizes the
H2S to elemental sulphur (reaction [13]) with an
efficiency of over 85%. The Superclaus reactor
temperature must be between 200 and 300°C in order
to avoid sulphur vapour condensation and oxidation of
the gas phase. No reverse Claus reaction between
sulphur and water to form H2S and SO2 may occur. In
addition, COS and CS2 are not hydrolysed. A total
sulphur recovery efficiency of up to 99% can be
obtained with the Superclaus-99.
Attaining over 99% requires a third Claus reactor
and/or a hydrogenation/hydrolysis step, prior to the
selective oxidation step. For instance, the
Superclaus-99.5 process includes such a
hydrogenation/hydrolysis step. Since the selective
oxidation catalyst is not sensitive to water, there is no
need to condense water downstream of the
hydrogenation reactor. In such a case, sulphur
recoveries range from 99-99.5% (for rich H2S feeds).
Oxidation to SO2 plus SO2 scrubbing
The basic principle behind these processes lies
in the incineration or catalytic oxidation of Claus
tail gas streams to convert all sulphur species to
SO2, followed by SO2 scrubbing and recycle of
the SO2 stream to the Claus unit. The total
capacity of the Claus process is thus increased.
157
PROCESSES RELATED TO ENVIRONMENTAL ISSUES

Table 6. SO2 scrubbing processes

Process name Scrubbing medium Licensor

Wellmann Lord Sodium sulphite solution Kvaerner Process Technology
Clintox Physical absorbant (glycol ether based) Linde
Inorganic aqueous solution made
Labsorb/Elsorb from caustic and phosphoric acid Belco Technologies
(sodium phosphate buffer)
Cansolv Proprietary aqueous diamine solvent Cansolv Technologies
ClausMaster Dibutyl butyl phosphonate Monsanto Enviro-Chem Systems
Dow Chemical’s proprietary Turbosox
Turbotak Turbosonic Technologies
amine-based sorbent
Centaur activated carbon, a proprietary catalyst
Clausorb Parsons Energy & Chemicals Group
developed by Calgon Carbon

These processes can achieve an extremely high
sulphur recovery of over 99.9%. The main
difference between the processes resides in the
different scrubbing mediums employed to remove
SO2 (Table 6). Established SO2 recovery systems
for Claus incinerator tail gas include the Wellman
Lord process (Keeping […] 1994) and the Clintox
process. In recent years, there has been strong
interest to develop new processes of this type
(Connock 1999a; SO2 removal […] 2004):
Cansolv, ClausMaster, Labsorb (based on the
Elsorb), Clausorb, and Turbotak.
3.2.5 Safety and environmental
issues
Liquid sulphur produced in the modified-Claus
process contains 150-400 ppm wt of residual
hydrogen sulphide in the form of both dissolved
hydrogen sulphide (H2S) and hydrogen
polysulphides (H2Sx) in equilibrium with sulphur.
H2S/H2Sx equilibrium is temperature
dependent: at 130°C, H2S/H2Sx10, and at
150°C, H2S/H2Sx1.
The decomposition of H2Sx to elemental
sulphur is a very slow reaction:
[28] H2Sx (liquid) 

 H2S (dissolved)

approximately 3.5% by volume at 150°C in air.
During handling, storage and transportation,
when sulphur is agitated and cooled, H2S is
released from the sulphur. The H2S concentration
in the surrounding atmosphere can reach toxic
level, fire and explosion limits. Therefore, the
industry must produce liquid or solid elemental
sulphur with a maximum value of 10 ppm wt of
hydrogen sulphide (H2S  H2Sx). Liquid sulphur
should be degassed for the following main
reasons: a) safe storage and transportation of
liquid sulphur; b) safer working conditions for
personnel handling liquid sulphur; c) less
corrosion in sulphur storage tanks, transport
piping and road tankers/ships; d) lower hydrogen
sulphide emissions into the atmosphere; e) higher
sulphur strength thanks to the formation of
polymeric form of sulphur Sx; the solid sulphur
produced from undegassed liquid sulphur is more
friable.
The principle of the degasification processes
of liquid sulphur is to release the dissolved H2S
gas and to accelerate the decomposition of the
H2Sx to H2S. The release of the dissolved H2S is
obtained by agitation of the liquid sulphur. The
decomposition of the H2Sx to H2S can be
accelerated by means of a catalyst, reducing the
energy consumption and the equipment size. The

released H2S gas must be removed from the gas

(x1)S (liquid)
space above the sulphur by flushing with a sweep
H2S dissolved in the liquid phase passes into gas (air, Claus tail gas or inert gas). Air seems to
the gaseous phase by physical desorption: be the best sweep gas. Indeed, tail gas still
contains residual H2S, therefore the degassing
[29] H2S (dissolved) 
 H2S (gas)



rate is reduced because the H2S available in the

The H2S content in the atmosphere becomes liquid sulphur tends to be in equilibrium with
progressively more dangerous above 50 ppmv H2S in the gaseous phase. Air contributes to
and is even lethal at 600 ppmv. The lower degassing by promoting the direct oxidation of
explosion and flammability limit of H2S is H2S to elemental sulphur through oxygen. Using

158 ENCYCLOPAEDIA OF HYDROCARBONS


Fig. 13. Continuous
Aquisulf scheme. LP steam
sulphur from
Claus plant
TGT unit
1st compartment
air as sweep gas prevents accumulation of
pyrophoric iron sulphide (FeS) formed on carbon
steel surface by reaction with H2S. This
accumulation generally occurs when using inert
gas sweeping. The physical desorption of
dissolved H2S shifts to the right the equilibrium
of reactions [28] and [29]. Sweep gas quantity
should be designed in such a way that the H2S
concentration is 1.5% by volume, maximum.
Several sulphur-degassing processes have been
developed. The first widely implemented is the
Aquisulf process (Nougayrede and Voirin, 1989),
with more than 45 references from 15-1,200 t S/d
(single train). This process is based on the
following two principles: mechanical degassing
by agitation and pulverization to favour gas-liquid
contact; chemical degassing by catalyst injection
to speed up the decomposition of H2Sx.
The Aquisulf process is available in batch and
continuous versions. In the continuous version
(Fig. 13), the liquid sulphur pit consists of two or
more compartments. The sulphur in the first
compartment is pumped and mixed with the
catalyst and sprayed back into the compartment.
The liquid sulphur overflows from a weir to the
second compartment. The liquid sulphur is again
pumped and sprayed in this tank to provide more
agitation. The original catalyst was
NH3. However, problems associated with
ammonium salts have resulted in the
development of a proprietary Aquisulf liquid
catalyst, which does a better job than NH3 of
decomposing the H2Sx and does not result in
solid salt formation. Other degassing processes
are available, such as D’CAASS (Fenderson and
Allison, 2000), HySpec and MAG.
VOLUME II / REFINING AND PETROCHEMICALS
SULPHUR CYCLE
ejector
to incinerator
catalyst injection
level degassed sulphur
control to storage
sweep gas
(inert/tail gas)
2nd compartment
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experience with the Clauspol process, in: Sulphur 2000.
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Bohme G., Sames A. (1999) The seven deadly sins of sulphur
recovery, in: Sulphur 99. Proceedings of the international
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Bonis M. et al. (2004) A critical look at amines. A practical
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Brand K. van den, Roos I. (2002) Shell’s new low-cost
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Clark P.D. et al. (2002) How do Claus catalysts really work?,
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Jean-Pierre Ballaguet
Cécile Barrère-Tricca
Institut Français du Pétrole
Vernaison, France
ENCYCLOPAEDIA OF HYDROCARBONS