3.2 - Ballaguet & Barrère-Tricca - Sulphur Cycle

3.
Sulphur cycle
3.2.1 Introduction no longer economically possible. This market is

now expected to exhibit a chronic oversupply. On
The removal of sulphur components from liquid a worldwide basis, approximately 60 million
and gas streams is required in many sectors of the metric tons of sulphur were produced in the year
hydrocarbon processing industry. With more 2000. It is generally assumed that the Claus
stringent fuel regulations and increasing process had produced 85% of this sulphur, 90% of
environmental concerns, together with the need to which being used for sulphuric acid (H2SO4)
process sourer crude oils and natural gases, production (60% of H2SO4 is used for fertilizer
sulphur recovery has become one of the leading production).
issues in emission reduction. The discussions below intend to give a general
The term sulphur cycle (Fig. 1) designates a idea of the capabilities of various sulphur
large number of processes widely used in the recovery processes, while taking into account the
refining industry, for purposes ranging from the nature of the stream. Compared to gas processing,
transformation and/or capture of sulphur petroleum refining is a source of gas with low
compounds contained in the petroleum fractions carbon dioxide (CO2) content; nevertheless, if
to their removal, generally as elemental sulphur. there is a catalytic cracking unit in the refinery
The general idea of the sulphur cycle is to scheme, the gas may contain some other
eliminate sulphur compounds from various contaminants such as carbonyl sulphide (COS),
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 refinery gas
and enrichment of H2S via solvent washing (e.g. sweet/
fuel gas
amines units); d) conversion of H2S into elemental
sulphur in the Sulphur Recovery Unit (SRU): Claus acid gas
SWS gas, NH3
and/or other processes (see Sections 3.2.3-3.2.4).
Elemental sulphur is the ultimate state of
incineration
recovery of the sulphur species. In the past, overall sulphur
recovered elemental sulphur had considerable recovery up to 99.9
value and was sold in the commercial
marketplace. However, as the hydrocarbon sulphur incineration
extraction industry continually recovers more
sulphur, the supply far exceeds demand and prices Fig. 1. Typical sulphur cycle
are driven down to levels where transportation is in the refining industry.
VOLUME II / REFINING AND PETROCHEMICALS 137

PROCESSES RELATED TO ENVIRONMENTAL ISSUES
organic sulphur, cyanides, ammonia and organic regenerator or stripper, together with a larger
acids. 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
3.2.2 H2S recovery processes a concentrated H2S feed stream, typically more
than 50%. On the other hand, as more CO2 is
Several factors must be considered when selecting rejected, more H2S can be converted to elemental
a gas treating process: processing temperature and sulphur in the Claus unit and, therefore, less
pressure, quality and quantity of sour gas to be sulphur dioxide (SO2) will be vented or removed
treated, product gas specifications and/or by a tail gas scrubber. Moreover, if there is a loop
subsequent processing requirements for the acid to recover H2S from TGT (Tail Gas Treating) and
gas as well as the produced gas. A few other it is sent to the Claus, then the minimum amount
factors, such as capital investment, operating of CO2 is essential to ensure amine and Claus
costs, climatic conditions and operability, bear an efficiencies. This loop generally utilizes a
impact on the final choice. Acid gas requirements reducing atmosphere to convert all of the
are linked to its final processing. A wide range of remaining sulphur species to H2S; the resulting
available processes dedicated to elemental sulphur acid gas is amine washed and the H2S stream is
recovery from H2S is described in Section 3.2.3. recycled to the Claus. These considerations
There are sweetening units in the refinery to demonstrate the interest in selective absorption or
recover H2S from acid gas streams. A typical Acid Gas Enrichment scheme (AGE), combining
refinery exhibits multiple absorbers and a two amine units (Fig. 2), one being H2S selective
common regenerator, as there are several units to provide highly H2S concentrated feed to the
where H2S is produced. Among the products to be Claus unit.
sweetened, one can find the following: fuel gas,
Liquefied Petroleum Gas (LPG), hydrotreater Amine process schemes
product and/or fuel gas and recycle gas, A very common amine design configuration
hydrocracker product and/or fuel gas and recycle includes one single absorber, one single
gas, cracker gases, and the remaining gases regenerator and all related equipment such as
generally combined. The solvent is then pumps, heat exchangers and filters. Fig. 3
regenerated in a single stripper and the acid gas, illustrates a typical gas treating plant using
produced at low pressure, is sent to the Claus unit, alkanolamine. After passing through an inlet
transforming H2S into sulphur, or to an equivalent separator and/or a liquid-gas separator to remove
unit. Chemical, physical or hybrid solvents are any entrained solids or liquids, the sour gas enters
those typically encountered in the industry. the bottom of the absorber. Generally, trays (or
Chemical sweetening technology has been used eventually packing) are used as internals for this
for over 70 years; alkanolamines are the most vessel, where the gas is contacted counter-currently
widely used of the many available solvents for with the solvent. The acid gas is absorbed
removal of H2S and CO2 from refinery and in the solvent and reacts with the amine.
natural gas streams. Depending on the application, the absorber may
The traditional way of operating sweetening have multiple amine feed entry points. Rich
units has been to remove CO2 along with H2S. amine solution leaving the absorber flows to the
Unfortunately, this CO2 removal causes several flash tank, where the solution pressure is reduced
problems. More energy is needed at the amine to flash the soluble hydrocarbons and to remove
Fig. 2. Acid gas sour gas sour gas

enrichment schemes.
H2S
sweet gas to Claus
TGT
H2S, CO2
CO2 H2S, CO2
vent / incineration
incineration
H2S to ClausTGT sweet gas
138 ENCYCLOPAEDIA OF HYDROCARBONS

SULPHUR CYCLE
Fig. 3. Amine unit, treated gas fuel gas acid gas

simplified
flow diagram.
absorber
stripper
raw
gas
lean
amine
the condensed hydrocarbons. From the flash tank, Many treating processes are available, though
the rich amine passes trough a lean/rich cross no single process is ideal for all applications. The
exchanger that ensures liquid preheating and initial selection must be based on required feed
flows to the top of the regenerator. The heat specifications together with feed parameters
provided by the reboiler is necessary to raise the including the composition, pressure, temperature,
rich amine to its boiling temperature, to break the and nature of the impurities. A more detailed
chemical bond between acid gas and amine, and approach follows, considering the percentage of
finally to produce enough steam, which reduces acid gas in the feed. CO2 concentration could
the partial pressure and allows the acid gas to be impose a selective removal of H2S to reduce the
stripped from the solvent. The stripped acid gas, regeneration duty of the amine unit. Finally, a
whose pressure depends on SRU requirements, given process is selected according to economics,
then typically flows to a Claus plant for sulphur reliability and versatility factors of the design,
recovery. The hot and lean amine is circulated while taking environmental constraints into
back from the reboiler to the absorber after account. As a result, gas processing in the
passing through the lean/rich exchanger, where it refinery is growing more complex. In fact, the
is used to preheat the rich amine, and lean solution challenge resides in choosing between various
cooler. Part of the solution is filtered to minimize solvents and process configurations. Hence, more
the quantity of potentially corrosive degradation upstream and downstream gas processing steps
products and the quantity of anti-foaming agents should be implemented, which results in a need
for better control of the absorber. for more equipment.
Other considerations may lead to more
complicated unit designs, including several flash Base for solvent selection
regeneration steps (especially for hybrid and Feed gas composition should be evaluated
physical solvents), several absorbers in series, prior to entering the absorber section of a solvent
several absorbers in parallel and split-flow unit. Contaminated gas damages the solvent and
configurations. An example of split-flow may cause corrosion, foaming, plugging, together
configuration is presented in Fig. 4, where a with products that do not meet specification
semi-lean amine stream realizes the bulk standards. The contaminants discussed include
sweetening, while a small stream of lean amine solids or dust, elemental sulphur, COS,
is used to reach the sweet gas specifications. mercaptans (RSH), carbon disulphide (CS2),

Fig. 4. Amine unit, acid gas

split-flow
configuration.
treated gas
lean
amine
semi-lean fuel gas

absorber amine
stripper
raw
gas
Benzene-Toluene-Xylenes (BTX), heavy Solvents overview

hydrocarbons and mercury. Generic and speciality solvents are generally
The numerous possible processes available as divided into three categories: chemical solvents,
well as the amount of variables involved render physical solvents and hybrid (mixture of chemical
absolute determination impossible (Lallemand et and physical) solvents. The removal of acid gases
al., 2004). The feasibility and desirability of by the chemical solvent is brought about through
sulphur recovery leads to limitations on the a chemical reaction. Physical solvents remove
selection of sweetening processes. acid gases by absorption. Hybrid solvents utilize a
The quality of sulphur produced from a Claus combination of absorption and chemical reaction.
unit is quite sensitive to the presence of heavy
hydrocarbons in the acid gas. If the solvent absorbs Chemical solvents
large quantities of heavy hydrocarbons, an Amine processes utilize an aqueous solvent
additional process may be required on the acid gas containing a chemical reactant: an alkanolamine.
leaving the unit or a high efficiency burner must be On the one hand, hydrogen sulphide and carbon
installed in the Claus to destroy these components. dioxide are considered acid gases because they
Chemical and physical solvents are used over a dissociate to form weak acids in aqueous
wide variety of process conditions, ranging from solutions. On the other hand, alkanolamines are
medium pressure to atmospheric pressure for weak bases and react with the acid gases in the
refinery off-gas and Claus tail gas treating. Solvents absorber to form soluble acid-base salts. These
for H2S selectivity are employed for refinery soluble complexes are then reversed in the
applications with high CO2 slippage, tail gas regenerator at elevated temperature and low
treating and LPG streams. The absorption of H2S pressure. Reduced pressure in the regenerator
and the selectivity over CO2 could be controlled by allows acid gas release and regenerates the
kinetics and contact time, and are enhanced when solvent to be reused. Alkanolamines exhibit two
operating at low temperature. Consequently, it is important chemical properties. The amino group
desirable to lower the lean amine temperature and is responsible for weak reactivity of the base,
to run the absorber at a low temperature. allowing heat regeneration of the salt; moreover,

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

Table 2. Alkanolamines and their applications
Amine Solution Applications Comments

(% weight)
MEA 15-20 CO2 Low pressure
DEA 25-40 Refinery Commonly used
MDEA 25-50 Refinery and TGT Selective absorption
Formulated MDEA 40-50 H2S/CO2 Displacing other amine types, low aromatic absorption
DGA 50-60 Refinery Absorbs all sulphur compounds and aromatics
DIPA 25-55 Refinery Absorbs heavy HC and partially COS
may result from carbamate hydrolysis to application involves the removal of H2S, CO2 and
bicarbonate. Unlike common amines, hindered trace sulphur. The energy requirement and
amines are based on a steric hindrance provided circulation rate are relatively low (Lecomte et al.,
by a bulky hydrocarbon-hydroxyl chain adjacent 2003). In practice, process schemes combine flash
to the amino atom. Consequently, the reaction of and thermal regenerations.
CO2 with this amino group is no longer possible Another example of mixed solvents is
and the H2S selectivity is thus amplified. activated hot potassium carbonate (e.g. with
DEA). It is used for H2S and CO2 recovery. Since
Physical solvents the solvent is hot, which avoids any
Physical solvents are based on non-aqueous crystallization and lowers the viscosity,
solvent and physical absorption. They are regeneration does not require a great amount of
characterized by low volatility, low to moderate energy and is performed through low pressure
viscosity, high boiling point, and exhibit excellent flashing. Packing is preferred to trays for this
thermal and chemical stability. The solubility of technology, which allows process optimizations.
H2S, CO2, RSH, CS2 and SO2 is higher in physical The operating costs of this process are primarily
solvents than hydrogen, methane, oxygen and determined by the overall heat utilization in the
nitrogen. Nevertheless, heavy hydrocarbons are also refinery.
soluble in the physical solvents. Therefore, the flow
scheme takes this particularity into account with Main solvents and their applications
multi-step flashing to lower the pressure, followed An approach for initial solvent and process
by an inert stripping gas and/or a low energy selection should take into account several factors:
demand regeneration. This method is generally lean or rich gas, large or small flow, the amount
more complex than that of basic amine, though of sulphur, trace sulphur compounds,
attractive from an economic standpoint since the contaminants, pressure and site factors.
energy demand is low. The above is considered for
H2S selective recovery when the acid gas partial Amine solvents
pressure is greater than 4 bar and when the These include generic and hindered amines.
hydrocarbon content, particularly BTX, is low in All are used, but DEA and MDEA have probably
feed gas. been applied more in refinery and natural gas
sweetening industries in general. Up to now,
Hybrid solvents amine-based processes have dominated the gas
Hybrid solvents, or mixed solvents, are sweetening industry:
designed to merge the effects of chemical and • MEA is used for low-pressure applications and
physical solvents by mixing amine (40-60% by complete acid gas removal. It is a highly
weight), physical solvent (10-40% by weight) and reactive primary amine that exhibits low cost,
water (20-30% by weight). The process combines good thermal stability, partial removal of COS
the advantages of both solvents as it uses physical and CS2. However, MEA presents a low
solvent for acid gas bulk removal and chemical solvent vapour pressure, a highly corrosive
solvent to achieve gas specifications. Heavy nature, high-energy demand for regeneration,
hydrocarbon absorption remains one of the and the removal of acid gas is non-selective.
disadvantages of the hybrid process. Their • DEA is a secondary amine and one of the most

SULPHUR CYCLE
widely employed for gas containing H2S, CO2, gas to absorb the acid gas constituents. Some
COS and CS2, due to an overall balance selectivity for H2S may be designed in the
between reactivity and corrosion. It is less absorber with a much lower energy cost than
reactive, has lower solvent vapour pressure amine processes, since regeneration is mainly
and lower corrosion potential than MEA, obtained through flashing and power recovery
coupled with a lower solvent cost. DEA is turbines. Hydrocarbon co-absorption,
non-selective and requires higher circulation especially for aromatics and olefins, is
rates in the sweetening unit. characteristic of physical solvents.
• DIPA is primarily used in European refineries • Methanol processes use a refrigerated (20°C
at 40-50% weight concentrations. Its steric or lower) mixture of methanol and water. A
hindrance provides a moderate selectivity for small amount of methanol is injected in the
H2S over CO2, which can be a disadvantage sour gas to prevent hydrate formation. Being
for Claus off-gas treatment applications. It that methanol has high solubility for
exhibits a partial removal of COS, though hydrocarbons, special attention is paid in the
hydrocarbon solubility takes place to some Ifpexol process to recover them in a three-
extent. Its cost is comparable to that of generic phase drum.
MDEA. • N-Methyl-2-Pyrrolidone (NMP) exhibits some
• DGA, like DGA agent, allows high solvent selectivity of H2S over CO2. The same can be
concentration. This highly reactive primary said of methanol, concerning hydrocarbon co-
amine removes COS, CS2 and (partially) absorption.
mercaptans. It shows excellent thermal • Morpholine process uses a mixture containing
stability and requires low circulation rates. n-formyl morpholine and n-acetyl morpholine.
However, DGA absorbs aromatics and is more This new process is of interest for bulk
expensive than both MEA and DEA, which removal or for sulphur trace removal.
must be considered for the sulphur recovery
design. Application of hybrid solvents
• MDEA is among the most recent amines and The solvent combination of both chemical and
is now displacing the other alkanolamines. In physical solvent results in a wide range of
highly concentrated solution, this tertiary applicability in terms of pressure and acid gas
amine is selective to H2S. It exhibits low content:
vapour pressure, high resistance to • Mixture of sulpholane (tetramethylene
degradation, low corrosiveness and low energy sulphone), DIPA and water and mixture of
demand for regeneration. However, its sulfolane, MDEA and water allow a high
reactivity is low and solvents price higher degree of removal, not only of H2S and CO2,
when compared to the above. In addition, the but also of trace sulphur compounds such as
removal of COS and CS2 is low. Formulated or RSH, COS, CS2. Disadvantages of this process
activated MDEA with primary or secondary include high hydrocarbon co-absorption and
amines allow CO2 absorption and are now sometimes a large solvent flow to obtain the
displacing primary and secondary amines in sweet gas specification.
refinery applications. Among the advantages, • Mixture of methanol, amine and water exhibits
MDEA absorbs the lowest amount of BTX, a high recovery for acid gas including trace
compared to DEA and MEA. sulphur compounds, such as mercaptans.
• Hindered amines are used as an attractive
approach for low-pressure acid gas Process design and simulation
enrichment. One disadvantage of this The solvent behaviour results from the
technology is the solvent cost of theses operating conditions and must be monitored.
proprietary amines, when compared to classic Process design is based on the equilibrium
acid gas enrichment based on selective between the dissolved gas and the solvent. The
MDEA. loading varies with the solvent concentration in
active species for a given H2S partial pressure. To
Application of physical solvents achieve a treated gas specification at the unit
Physical solvents are used with various outlet, it is necessary for the solvent entering the
process schemes. absorber to exhibit an H2S concentration lower
• DiMethyl ethers of PolyEthylene Glycol than that in the solvent in equilibrium with the
(DMPEG) are contacted with dehydrated sour exhaust gas leaving the absorber. Moreover, it is

known that H2S reacts with aqueous alkanolamine the reboiler. Steam or hot oil provides heat to the
at a faster rate than CO2, providing selectivity reboiler; a 3.5 bar saturated steam is
when used with special designs. The absorber recommended to avoid solvent degradation and
internal efficiency must be incorporated to take corrosion. The reflux ratio, ranging from 1 to 3, is
into account the selectivity in amine unit models. linked to the lean solvent specification.
This efficiency is then a function of the kinetic Filter. The solvent should be kept clean by
rate constants for the reactions between each acid using adequate mechanical filtration (5 or 10 mm)
gas and the amine, the physico-chemical and carbon filtration. The removal of FeS and
properties of the solvent, the pressure, the FeS-hydrocarbon materials from this equipment
temperature and the internal design variables. For avoids problems. A minimum 10-20% slipstream
trays, these variables include diameter, weir of the circulation unit should be submitted to
length, weir height and the number of trays. filtration. The filtration media is to be changed
Absorption and desorption of H2S (and CO2) when the solvent colour varies and heat stable
involve a heat effect in amine solutions as a salts should be prevented from building up.
chemical reaction takes place, and are a function Activated carbon filtration can reduce the need
of amine type, concentration and loading. This for antifoam.
leads to water evaporation and condensation in Amine solution control system. Solution
the absorber and in the regenerator; thus the water control leads to more reliable and trouble-free
content of the feed gas must be considered when operation. It is important to test the amine
predicting the temperature profile. behaviour with appropriate analytical techniques.
Commercial simulation software generally The operator should have the procedures, the
made use of thermodynamic models, such equipment as well as the expertise to perform the
as the one developed in 1976 by R.L. Kent and tests defined by the process or amine vendor.
B. Einsenberg, which are fitted using sets of Foaming, corrosion, solvent degradation and the
proprietary data. resulting unit loss in capacity may be the result of
inappropriate analytical tests or evaluation time-
Operating problems schedule. General analysis includes amine tests
The operating problems encountered in such (alkalinity titration, chromatographic spectrum),
units are usually linked to design; trouble free acid gas loading, water content, solids and ash
operation results from unit control and, in content, heat stable salt content and anion
particular, solution control. The parts of the unit analysis (ion chromatography). Moreover, a
that must be carefully checked will follow. specific test for foaming ability could be of great
Inlet scrubbing. The type and design of inlet interest to monitor the unit.
separation must be carefully considered, as they
are critical for trouble-free operation of the Process variables
solvent unit. They can vary from slug catchers, As the unit is properly designed, the main
removing condensed water and hydrocarbons, to variables in solvent processes include the
reverse flow filter or coalescers when sub-micron following.
range aerosols are expected. Quality of the feed. The unit is generally
Absorber. The diameter is determined by the designed for a specific feed or a range of H2S
feed gas flow rate and the solution circulation rate concentration. Since sweet gas quality depends on
by the type, concentration and equilibrium the feed characteristics, specifications could
loading of the amine. Trays are the most common eventually not be reached for some feed streams
internals, but random and structured packing can even using a higher flow rate or a more
be found. regenerated solvent.
Flash tank and lean/rich exchanger. Low Absorber and regenerator pressures. Absorber
pressure at the flash tank (3-6 bar) helps to pressure generally results from the pressure of gas
remove hydrocarbons, which reduces the amine at the exhaust of the previous refinery unit. A
foaming potential. Exchanger corrosion must be change in the regenerator pressure may be the
avoided in the rich amine line due to flashing acid result of a revamp of the SRU, when, for example,
gases at the outlet. Stainless steel metallurgy a higher sulphur recovery is required.
should be considered for low solvent Absorber temperature. Solvent temperature
concentration and high amine loading. must be higher than feed gas temperature,
Regenerator. The purpose is to strip the acid typically 5-8°C, to prevent condensation and
gas from the rich amine using steam generated by foaming.

SULPHUR CYCLE
Space velocity. Absorption is affected by 3.2.3 The Claus process

hydrodynamics. It is especially important to
control space velocity when slow kinetic for CO2 The objective of the Claus process is to recover
is opposed to equilibrium absorption of H2S in a elemental sulphur (Sx, with x between 2-8
selective removal. depending on the temperature) from gas streams
When all of these items are well established, containing hydrogen sulphide (H2S) stripped from
changes in operating conditions may lead to the gas sweetening solvents (see Section 3.2.2). The
following problems: Claus process produces elemental sulphur by the
Amines losses. They could be either partial oxidation of H2S:
physical-mechanical or chemical based. Excessive
[9] H2S1/2 O2 1/8 S8H2Oheat (209 kJ)

solution losses are generally linked to solution

foaming. The Claus plant effluent gases are either sent to
Foaming. Foaming will not occur if no an incinerator or to a TGT unit (see Section
extra-unit contaminant is present in the streams. 3.2.4), depending on the local air pollution
Classical contaminants include corrosion control regulations. The final effluent gas, which
inhibitors, additives, liquids or solids entering the cannot be valorized, is incinerated to convert all
unit and dissolved degradation products (FeS). of the sulphur compounds to sulphur dioxide
The above leads to decreased efficiency, (SO2) in a thermal or catalytic incinerator. Being
unattainable specification and solvent losses. of very good quality, the elemental sulphur
Some additives (silicon-based) are used to lower produced in the SRU, Claus or Claus plus TGT, is
the surface tension of liquids, and thus reduce used as a basic chemical in the industry. The
foaming. Use of an antifoam agent should be properties of elemental sulphur are well described
considered a short-term measure. in various literature (Meyer, 1976; Shuai and
Corrosion. Corrosion in amine units requires Meisen, 1995).
very special attention. Amine and degradation In the original Claus process, reaction [9] was
products may cause severe corrosion to the carried out in a single step over a catalyst. Since
equipment. Industry experience has pointed out the heat of the reaction was dissipated only by
three key corrosion issues: exceedingly high flow radiation, high sulphur recovery was very difficult
velocities, air entries leading to corrosive to obtain. A very important modification to the
degradation products and excessive reboiler Claus process was made in 1940, which allowed
temperatures. These issues are resolved through energy recovery, increased process capacity and
proper design and operating practices (Bonis et eliminated the issue of maintaining, in the
al., 2004) for units working with high amine catalytic reactor, the low temperature favouring
concentrations (up to 40% weight for DEA). As high sulphur recoveries. In this modified-Claus
long as amine degradation products are identified process (Fig. 6), reaction [9] is carried out in two
as key factors, MDEA is expected to be stages.
significantly less corrosive than DEA, due to a In the first stage, the thermal section, one-
higher stability coupled with a lower degradation third of the H2S is oxidized to SO2 with air or
product concentration. oxygen enriched air at high temperature
Impact of feed gas composition on sulphur (generally 925-1,200°C):
removal unit efficiency. The composition of the
[10] H2S3/2O2 SO2H2Oheat (518 kJ)

acid gas leaving the acid gas removal unit has an

impact on sulphur recovery efficiency. This reaction is highly exothermic and is not
If the H2S content is low, acid gas enrichment limited by equilibrium. The unburned H2S in the
is recommended. Basically, H2S, hydrocarbons and acid gas reacts with the SO2 (obtained through
ammonia contents would establish the criteria for reaction [10], to yield the stoichiometric H2S/SO2
sulphur recovery efficiency and designs. The ratio of 2:1) to form elemental sulphur vapour:
conventional sulphur plant could then be converted
[11] 2H2SSO2
3/2S22H2O

to oxygen enrichment so as to process more sour

gas and destroy the remaining impurities. This reaction is endothermic and is limited by
Nevertheless, if the solvent has been changed equilibrium. About 60-70% of the conversion of
either to process more acid gas or for economic H2S to elemental sulphur occurs in the thermal
reasons, the downstream sulphur recovery units stage. An important function of the thermal
generally need some equipment modifications for section is also to destroy the impurities that may
capacity expansion. be present in the feed acid gas stream, such as

thermal stage catalytic stage
HP or MP
air steam optional 3rdd catalytic stage
H2S catalytic catalytic

reactor reactor
or direct
burner erator
muffle furnace
re-heater
re-heater
re-heater
0-150°C
waste heat boiler LP LP LP
steam steam steam
S S S
Fig. 6. Typical Claus process scheme (straight-through design).
ammonia (NH3), hydrocarbons, etc. During the original Claus process is still implemented to treat
thermal stage, side reactions also occur in the very low H2S concentrations gases, though in this
presence of CO2 or hydrocarbons, which produce case, it is referred to as direct oxidation process.
COS and CS2. There are a number of different process
In the second stage (i.e. catalytic section), the configurations for the modified-Claus process,
overall conversion of H2S to elemental sulphur is depending mainly on the H2S concentration in the
increased in a series of catalytic reactors (1 to 3) Claus feed gas.
by reaction of the generated SO2 and the
unreacted H2S over fixed beds of Claus catalysts Chemistry and thermodynamics of the Claus
at much lower temperatures (190-360°C): process
In principle, ideal performance is achieved
[12] 2H2SSO2
3/8 S82H2Oheat (108 kJ)

when all stoichiometric requirements for the basic

Reaction [12] is called the Claus reaction. The process reactions are satisfied under the most
use of appropriate catalysts at selected favourable thermodynamic conditions, and
temperatures optimizes the Claus reaction yield equilibrium is reached at all points in the process.
and also allows COS and CS2 produced in the While thermodynamic favourability determines
thermal stage to be eliminated. High-Pressure ideal performance, the practicable capability is
(HP) steam is generated in the Waste Heat Boiler dictated by the kinetic limitations imposed by the
(WHB), in which the gases are cooled from the operating conditions and plant equipment.
high flame temperature to the lower catalytic
reactor (converter) temperature (see again Fig. 6). Thermodynamics
Sulphur condensers are provided to condense and The basic design of a typical modified-Claus
separate the elemental sulphur formed after the plant can be best understood by looking at the
thermal stage and after each catalytic reactor. The thermodynamic equilibrium curves calculated for
heat released by the Claus reaction is recovered as the reaction of pure hydrogen sulphide (H2S) with
Low-Pressure (LP) steam in each sulphur air (Fig. 7):
condenser. Product removal, lower catalytic
[13] H2S1/2 O2
1/xSxH2O

converter temperatures and an increased number

of catalytic converters enhance sulphur recovery. Calculations are based on the principle of
Table 3 presents the typical, total sulphur recovery minimization of the Gibbs free energy. All three
of the modified-Claus process depending on the curves were calculated without sulphur removal
number of catalytic reactors used. from the system. The difference between the
Nowadays, sulphur recovery plants are based upper and lower curves (see again Fig. 7) results
on the modified-Claus process, although the from the sulphur vapour species under

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.

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 COS and CS2 lower the Claus sulphur
provides a simplistic overview of Claus furnace recovery, unless their conversion to H2S is
chemistry showing what are considered the more achieved by hydrolysis at the relatively high
important reactions that occur in the furnace in temperatures found in the first catalytic converter.
the absence of hydrocarbon contaminants, but in It has been well established that the design and
the presence of CO2. Chemistry occurring in the mode of operation of the furnace can significantly
Claus reaction furnace may be split into two influence the degree to which hydrocarbons are
types: combustion reactions occurring in the converted to COS and CS2.
oxygen-rich region; reactions proceeding in the Ammonia (NH3) destruction is also a problem
oxygen-free (anoxic) region driven when treating refinery Sour Water Stripper (SWS)
by the high temperature resulting from off-gas.
combustion reactions.
The carryover of hydrocarbons with the acid Chemistry in catalytic stages
gas into the Claus reaction furnace further Sulphur recovery in catalytic stages is
complicates the reactions. The hydrocarbon governed by two main catalytic reactions: the
impurities may range from complex alkanes to Claus reaction [12] and the hydrolysis of COS
BTX. Although thermodynamic considerations and CS2 (according to reactions [19] and [20],
suggest that these hydrocarbons should fully respectively).
combust to CO2 and H2O, the rate at which they
[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 In terms of contribution to sulphur recovery,
will be in competition with H2S for a restricted the Claus reaction is by far the most important.
oxygen supply. In the event that hydrocarbons are However, the efficiency of the COS and CS2
not fully combusted, it is expected that they will hydrolysis becomes increasingly important and
produce CO, C, COS and CS2 through reactions 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).

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

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 furnace. According to the Claus reaction, the air needed
The Claus is the technology of choice for for combustion is one-third of that required for the
gases containing high concentrations of H2S complete combustion of H2S. Consequently, the Claus
and/or large quantities of sulphur. Nevertheless, furnace operates far away from complete combustion in
when H2S content is lower than 30% and/or the the straight-through design. A minimum temperature of
amount of sulphur is less than 10-20 tons of 925°C is generally considered to sustain a stable flame.
sulphur per day (t S/d), some other processes are A higher flame temperature is often required to destroy
often more economical. contaminants when present.
Rich acid gases (H2 S50%) Medium acid gases (10%H2 S50%)
The H2S content of the Claus acid gas feed When H2S concentration is low, the stability of
encountered in most refineries is around 80%. It is the flame cannot be reached and the straight-
treated in the simplest, straight-through Claus process through design is no longer a good choice. The
where all of the acid gas is processed in the reaction following possibilities must therefore be chosen.

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

temperature (Bohme and Sames, 1999). For hydrocarbons produce complex carbonaceous
example, the condensation of elemental sulphur materials that are carried into the catalytic
on the catalytic converters can be avoided by reactors, gradually deteriorating catalyst
maintaining their temperature above the sulphur performance. In addition, hydrocarbons can be
dewpoint of the gas mixture. fed directly to the first catalytic converter without
When the feed gas contains contaminants, a being burned when a split-flow design is utilized.
higher flame temperature is often required to These hydrocarbons can also cause catalyst
destroy them. Ammonia, heavy hydrocarbons, deterioration.
BTX, mercaptans and cyanides are among the Regarding mercaptans and cyanides, the same
contaminants most often encountered. general considerations must be applied for the
As regards ammonia, it is typically provided Claus unit. For other processes, such as redox or
by the off-gas of the SWS of the refinery. The scavenger processes, problems connected to
Claus unit is considered the best place to destroy chemical odours and disposal must be carefully
this off-gas, which also contains H2S, thanks to considered.
its high furnace temperature. NH3 must be
destroyed in the reaction furnace, otherwise
sulphur trioxide (SO3) can form due to the 3.2.4 Tail gas treatment
following reactions:
The modified-Claus process has continually
[21] 2NH35/2O2 2NO3H2O

improved since 1940. However, this process can
[22] 2NOO2 2NO2 generally achieve only up to 98% sulphur
[NO2] recovery for a three-stage configuration. With
[23] SO2
SO3
new environmental requirements, sulphur
recovery efficiencies of 98.5-99.95% are now
SO3 causes severe downstream problems like required. Regulations differ from country to
corrosion, catalyst deactivation and salt formation. country and may even vary between different
Two methods are available to successfully destroy regions within the same country:
NH3 using the following reaction: • In Canada, plants with a capacity of 50 t S/d
should achieve a total sulphur recovery of
[24] 2NH33/2O2 N23H2O

98.5%, increasing to 99% for plants with a

The first method involves a split-flow reaction capacity of 2,000 t S/d.
furnace design; the second requires a high- • In Europe, the 1998 ‘bubble concept’ for SO2
intensity reaction furnace burner. It is essential emissions is often applied, whereby all SO2
for NH3 to be almost completely destroyed, being emission sources in one refinery can be
that ammonia concentrations even as low as pooled and the total SO2 emission limit of
500-1,000 ppm by volume (ppmv) can cause 1,700 mg/Nm3 should be met in the flue gas.
problems. This emission limit will be reduced in the
As for BTX and heavy hydrocarbons, acid gas coming decades. In Germany, strict
may contain these compounds since solvent units regulations (TA-Luft) are in place and require
are able to co-absorb them together with H2S. sulphur recoveries of 99.8% for plants with a
Feed stream must be analysed and the necessary capacity of 20-50 t S/d and 99.5% for plants
measures must be taken to keep them from with capacities over 50 t S/d.
entering the Claus catalytic section, as they may • Japan requires recoveries over 99.8% and
cause catalyst deactivation, plugging and off- Taiwan demands levels as high as 99.95%.
specification sulphur for market purposes (e.g. • In the United States, it depends on the
green sulphur compared to bright yellow sulphur). individual state. For example, in Texas
When acid gases of high H2S content are refineries, for new facilities, the recovery must
processed, the temperature in the reaction furnace be between 96 and 99.8%, depending on the
is usually high enough to result in the complete sulphur production capacity. However, it
combustion of all hydrocarbons to CO2 and water, seems that 99.9% recovery efficiency is
and no carbonaceous material deposition is becoming a regulatory standard for sulphur
experienced. However, at the low combustion recovery plants with a capacity of 20 t S/d or
temperature occurring in straight-through plants, greater.
processing gases with less than approximately Thus, the modified-Claus process has to be
40-50% H2S, cracking and partial combustion of supplemented with another process designed to

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

gas in the Clauspol unit (e.g. entrained liquid gas to incinerator

sulphur, sulphur vapour, COS and CS2,
which are partially hydrolysed). The basic 120-130°C
Clauspol II process allows sulphur recoveries up
to 99.8%, provided that COS and CS2
have been hydrolysed down to 300 ppmv of gas/liquid
sulphur or less in the catalytic stages of the contactor
Claus plant, by using a TiO2-based catalyst. The solvent
Clauspol process is a very simple and temperature
continuous process. It requires neither hydrogen control
nor blower and there is no recycling of H2S back
to the Claus unit. Investment and operating costs Claus
are low, making the Clauspol II process the tail gas
cheapest TGT technology available on the catalyst
market from 99.4-99.8% sulphur recoveries. make-up
Under normal conditions, the carbon steel
corrosion rate in Clauspol units is avoided by liquid sulphur
applying simple rules regarding the design,
construction and operation of the unit (Barrère-
Tricca et al., 2000). Fig. 10. Clauspol II process scheme.
The latest main developments of the Clauspol
process are described below.
• The Clauspol II process circulates a sulphur- the equilibrium is thermodynamically favoured at
saturated solvent that contains small amounts low temperature and, secondly, since the sulphur
of liquid sulphur. The liquid sulphur vapour is adsorbed on the catalyst. The Sulfreen process
pressure, though low, contributes to sulphur basically consists of two (occasionally three for
losses in the effluent from 350 ppmv With its large capacities) Sulfreen reactors in series with
desaturation loop, the Clauspol Booster 99.9 the Claus reactors. As the sulphur accumulates on
process eliminates the liquid sulphur phase in the catalyst, its activity decreases and the catalyst
the solvent and circulates an unsaturated beds have to be regenerated thermally at
solvent. This allows sulphur recoveries of over 250-300°C. During the regeneration step, sulphur
99.9%. is desorbed and the catalyst is restored to full
• The desalter has been recently developed to activity by part of the preheated TGT gas. Once
prevent the accumulation of solid salts on the regeneration is achieved, the catalyst bed is
reactor packing. cooled to the operating temperature. Sulphur from
The desaturation loop and the desalter treat the hot regeneration stream is then condensed.
only a fraction of the solvent from the Typical overall sulphur recoveries are in the
recirculation loop. They are small, simple, easy to 98.5-99.5% range, depending on the Claus unit
install on existing units and easy to operate. They arrangement. COS and CS2 are not hydrolysed.
can be shut down without shutting down the basic Two enhanced versions of the Sulfreen process
Clauspol II section. are also available and enable higher sulphur
recoveries to be reached.
Dry subdewpoint processes: Sulfreen processes The Hydrosulfreen process is based on the
The Sulfreen process (Willing and Linder, pre-treatment of the Claus tail gas by hydrolysis
1994) was developed in the early 1970s. There are of COS and CS2 to H2S and direct oxidation of
more than 50 references worldwide ranging from H2S into elemental sulphur.
10-2,200 t S/d (single train). The Sulfreen process These reactions are performed by contacting the
(Fig. 11) is based on the continuation of the Claus Claus tail gas with a TiO2-based catalyst at about
reaction [12], between the residual H2S and SO2 300°C. This pre-treatment is followed by a basic
present in Claus tail gas, on a dry catalytic bed at Sulfreen reactor. A Claus plant with two catalytic
low temperature (120-150°C). Activated alumina stages and a Hydrosulfreen unit can achieve an
is used as the catalyst. The Sulfreen process overall sulphur recovery efficiency
produces 99.9% pure bright yellow sulphur. The of over 99.5%.
Claus reaction is extended and the sulphur The Doxosulfreen process is based on a
recovery enhanced. This occurs, firstly, because post-treatment after a Sulfreen unit or an

SULPHUR CYCLE
Fig. 11. Sulfreen Sulfreen reactors

process scheme. heater
Regeneration step:
S is removed
by vaporization to incinerator
in hot tail gas.
Reaction step:
H2S and SO2 react on the - 0°C
250-300 °C 120-1
- 50°
0 C
Sulfreen alumina catalyst,
produced S is adsorbed. fuel air
gas
Claus tail
gas
condenser
blower sulphur
Hydrosulfreen unit. The upstream units are hydrogenation reactor at a temperature of

operated to get a slight excess of H2S in order to approximately 320-340°C and is cooled in two
reach a nearly total SO2 conversion on the stages. The hot gases are cooled to about
Sulfreen reactor. Therefore, the remaining H2S at 160-200°C by passing through the tube-side of a
the outlet of the Sulfreen reactor is oxidized with shell-and-tube heat exchanger or waste heat
air to elemental sulphur at a low temperature boiler. The gas is then further cooled to 40°C by
(100-130°C). Both Sulfreen and oxidation direct contact with circulating water in a quench
reactors are regenerated through a common tower. During gas cooling, most of the water
regeneration loop. The oxidation catalyst is based vapour contained in gas is condensed and mixed
on copper and optimized special alumina. with the circulating water. Since the circulating
The Doxosulfreen process is capable water is in a closed loop system, the condensed
of reaching an overall sulphur recovery water must be removed from the system to
of up to 99.9%. maintain a constant water level in the tower. The
water leaving the system contains a few ppm of
Reduction to H2S plus H2S scrubbing H2S and is typically recycled to the SWS unit for
An entire family of TGT processes exists H2S recovery. The cooled gas leaves the top of the
based on the reduction of sulphur compounds to quench tower and is sent to the absorber, where it
H2S, followed by H2S scrubbing, and recycling of is washed counter-currently with a lean H2S
the H2S stream to the Claus unit. The SCOT solvent. Various types of solvent can be employed,
process was the first to be developed and is the but a selective amine is normally used (e.g.
most widespread, with more than 200 units MDEA). The choice of the solvent depends on the
constructed all over the world since 1973, and tail gas composition (see Section 3.2.2). The
with single train capacities of up to 2,500 t S/d. downward flowing solvent contacts the upward
The other TGT processes of this family flowing gas and absorbs nearly all of the H2S and
(Sultimate, BSR/Amine, Resulf, RAR, ARCO, some CO2 when present. The absorber off-gas
HCR, etc.) are more or less designed and operated typically contains 150 ppmv of H2S or less and is
in accordance with the SCOT concept (van den sent to the Claus incinerator. The rich solvent
Brand and Roos, 2002). The Claus tail gas is leaving the absorber bottom is pumped through a
heated to about 300°C using a heat exchanger or lean/rich solvent regenerator, where the H2S (and
in-line burner (Fig. 12). The heated gas is mixed eventually CO2) are removed by steam stripping.
with a reducing gas containing hydrogen and Acid gas from the regenerator is recycled to the
passes through a fixed bed of CoMo/alumina Claus thermal stage. Lean solvent from the
catalyst or NiMo/alumina catalyst, where all regenerator is returned to the absorber.
sulphur components are converted into H2S. Two The aims of developments in recent years were
types of reactions occur: hydrolysis and to lower the total sulphur content of the emissions
hydrogenation. The tail gas leaves the to less than 50 ppmv (comparable to 99.95% total

Fig. 12. Sultimate to incinerator

process scheme. to Claus thermal stage
quench final
and cooling amine
tower scrubber
air reducing
heater gas
natural
gas
Claus
tail gas
reduction
reactor LP
steam
cooler amine
regeneration
waste water
to treatment
(SNS)
sulphur recovery) and to significantly reduce producing either a better solvent leanness,
investment and operating costs. thereby a lower off-gas H2S specification, or
In order to reduce capital costs, it is possible the same solvent leanness with less steam.
to use a common amine regeneration section for
the TGT unit as well as for the existing amine Wet oxidation: redox processes
desulphurization unit. To reduce operating costs, Redox processes allow direct oxidation of H2S
it is also possible to use the solvent in cascade into elemental sulphur at ambient temperature,
from the TGT unit to the other sweetening units. with nearly 100% selectivity and conversion.
New catalysts enable operation of the Redox processes are usually highly flexible and
hydrogenation step at lower temperatures (220°C are being used on a wide variety of H2S
or below, depending on inlet gas composition), containing gases, including gas from acid gas
greatly reducing energy consumption and enrichment units and from the Claus unit,
avoiding in line burners with their drawbacks provided that the gas is mainly H2S (Nagl, 2001).
(soot deposit for some of them). The main limitations of current redox processes
The total sulphur content of the emissions is are their relatively high chemical costs, the
significantly lowered thanks to the following quality of the sulphur product, which is generally
factors. not as pure as Claus sulphur and, for some
• Absorption is improved by using a lower lean applications, the difficulty in directly treating
solvent temperature, the solubility of H2S in high pressure gases.
amine solvents decreasing with temperature. In redox processes, the H2S containing gas is
• Stripping is improved utilizing a two-stage washed with a solution containing a redox
regeneration, in which part of the amine catalyst. In a first step, the aqueous solution
solvent flow is more deeply stripped. The absorbs the H2S, which then reacts with the
super-lean solvent is routed to the top tray of oxidized form of the catalyst to yield elemental
the absorber, while the semi-lean solvent sulphur as the catalyst is converted into its
comes in half way down the absorber. reduced form. In a second step, the reduced form
• Inexpensive additive (i.e. strong acid) to the of the catalyst is contacted with air and oxidized
amine solvent improves its regeneration, prior to reuse. Redox catalysts are usually

SULPHUR CYCLE
polyvalent metallic cations chelated with organic particles are then removed from the solution before
ligands. The former vanadium salts used in the its depressurization, thanks to a continuous high-
Stretford process have now been replaced in all pressure filtration. Dissolved gas, which is low for
major redox processes by iron complexes based aqueous solution compared to organic solvents,
on Ethylene Diamine Tetra Acetic acid (EDTA), easily separates in a flash drum; moreover, foaming
Hydroxyethyl Ethylene Diamine Tri Acetic acid tendency is tremendously reduced, as no sulphur
(HEDTA) or Nitrilo Tri Acetic acid (NTA) particles are found down the filter.
(McManus, 1998; Heguy and Nagl, 2003). Other processes, such as Crystasulf, are based
The main chemical reactions are: on organic solvent that facilitates larger sulphur
crystals at the price of solvent coabsorption.
[25] H2S2Fe3 S2Fe22H

[26] 2Fe22H1/2O2 2Fe3H2O

Dry oxidation: Superclaus
The Superclaus process (Lagas et al., 1989) was
[27] global reaction: H2S1/2O2 SH2O

introduced to the industry in 1988 as a new

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

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 approximately 3.5% by volume at 150°C in air.
sulphur recovery of over 99.9%. The main During handling, storage and transportation,
difference between the processes resides in the when sulphur is agitated and cooled, H2S is
different scrubbing mediums employed to remove released from the sulphur. The H2S concentration
SO2 (Table 6). Established SO2 recovery systems in the surrounding atmosphere can reach toxic
for Claus incinerator tail gas include the Wellman level, fire and explosion limits. Therefore, the
Lord process (Keeping […] 1994) and the Clintox industry must produce liquid or solid elemental
process. In recent years, there has been strong sulphur with a maximum value of 10 ppm wt of
interest to develop new processes of this type hydrogen sulphide (H2S H2Sx). Liquid sulphur
(Connock 1999a; SO2 removal […] 2004): should be degassed for the following main
Cansolv, ClausMaster, Labsorb (based on the reasons: a) safe storage and transportation of
Elsorb), Clausorb, and Turbotak. liquid sulphur; b) safer working conditions for
personnel handling liquid sulphur; c) less
corrosion in sulphur storage tanks, transport
3.2.5 Safety and environmental piping and road tankers/ships; d) lower hydrogen
issues sulphide emissions into the atmosphere; e) higher
sulphur strength thanks to the formation of
Liquid sulphur produced in the modified-Claus polymeric form of sulphur Sx; the solid sulphur
process contains 150-400 ppm wt of residual produced from undegassed liquid sulphur is more
hydrogen sulphide in the form of both dissolved friable.
hydrogen sulphide (H2S) and hydrogen The principle of the degasification processes
polysulphides (H2Sx) in equilibrium with sulphur. of liquid sulphur is to release the dissolved H2S
H2S/H2Sx equilibrium is temperature gas and to accelerate the decomposition of the
dependent: at 130°C, H2S/H2Sx10, and at H2Sx to H2S. The release of the dissolved H2S is
150°C, H2S/H2Sx1. obtained by agitation of the liquid sulphur. The
The decomposition of H2Sx to elemental decomposition of the H2Sx to H2S can be
sulphur is a very slow reaction: accelerated by means of a catalyst, reducing the
energy consumption and the equipment size. The
[28] H2Sx (liquid)

H2S (dissolved)

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

SULPHUR CYCLE
Fig. 13. Continuous ejector

Aquisulf scheme. LP steam to incinerator
catalyst injection
sulphur from level degassed sulphur

control to storage
Claus plant
TGT unit
sweep gas
(inert/tail gas)
1st compartment 2nd compartment
air as sweep gas prevents accumulation of References

pyrophoric iron sulphide (FeS) formed on carbon
Barrère-Tricca C. et al. (2000) Thirty years of operating
steel surface by reaction with H2S. This experience with the Clauspol process, in: Sulphur 2000.
accumulation generally occurs when using inert Proceedings of the international conference, San Francisco
gas sweeping. The physical desorption of (CA), 29 October-1 November.
dissolved H2S shifts to the right the equilibrium Bohme G., Sames A. (1999) The seven deadly sins of sulphur
of reactions [28] and [29]. Sweep gas quantity recovery, in: Sulphur 99. Proceedings of the international
should be designed in such a way that the H2S conference, Calgary (Alberta), 17-20 October.
concentration is 1.5% by volume, maximum. Bonis M. et al. (2004) A critical look at amines. A practical
Several sulphur-degassing processes have been review of corrosion experience over four decades, in:
developed. The first widely implemented is the Proceedings of the Gas processors association annual
Aquisulf process (Nougayrede and Voirin, 1989), convention, New Orleans (LA), 14-17 March.
with more than 45 references from 15-1,200 t S/d Brand K. van den, Roos I. (2002) Shell’s new low-cost
SCOT process, in: Sulphur 2002. Proceedings of the
(single train). This process is based on the international conference, Wien, 27-30 October.
following two principles: mechanical degassing Chasing the elusive last 1 or 2 %. (Claus sulphur recovery
by agitation and pulverization to favour gas-liquid process used in petroleum refineries) (Special reports:
contact; chemical degassing by catalyst injection sulphur recovery in refineries) (1997), «Sulphur»,
to speed up the decomposition of H2Sx. September-October, 41-47.
The Aquisulf process is available in batch and Clark P.D. et al. (2002) How do Claus catalysts really work?,
continuous versions. In the continuous version in: Proceedings of the 52nd Laurance Reid Gas conditioning
conference, Norman (OK), 24-27 February, 153-176.
(Fig. 13), the liquid sulphur pit consists of two or
Connock L. (1998) Approaching the limit: 99.9+ % sulphur
more compartments. The sulphur in the first recovery, «Sulphur», July-August 34-55.
compartment is pumped and mixed with the Connock L. (1999a) New SO2 scrubbing technologies abound.
catalyst and sprayed back into the compartment. (Special reports: refinery sulphur), «Sulphur», July-August,
The liquid sulphur overflows from a weir to the 53-56.
second compartment. The liquid sulphur is again Connock L. (1999b) Understanding your Claus reaction
pumped and sprayed in this tank to provide more furnace, «Sulphur», January-February, 34-42.
agitation. The original catalyst was Connock L. (2003) Enhanced sulphur recovery, «Sulphur»,
NH3. However, problems associated with May-June, 29-39.
ammonium salts have resulted in the Fenderson S., Allison T. (2000) Sulphur degassing retrofit
made easy with the D´GAASS process, in: Sulphur 2000.
development of a proprietary Aquisulf liquid
Proceedings of the international conference, San Francisco
catalyst, which does a better job than NH3 of (CA), 29 October-1 November, 247-261.
decomposing the H2Sx and does not result in Heguy D.L., Nagl G.J. (2003) Consider optimized iron-redox
solid salt formation. Other degassing processes processes to remove sulphur, «Hydrocarbon Processing»,
are available, such as D’CAASS (Fenderson and 82, 53-57.
Allison, 2000), HySpec and MAG. Heinrich G., Kasztelan S. (2001) Hydrotreating, in:

Leprince P. (edited by) Conversion processes, Paris, Technip, Meyer B. (1976) Elemental sulfur, «Chemical Reviews», 76,
533-573. 367-388.
Keeping abreast of the regulations. (Sulphur emissions Nagl G. (2001) Liquid redox enhances Claus process,
restrictions) (Improved claus sulphur recovery) (1994), «Sulphur», May-June, 1-6.
«Sulphur», March-April, 35-59.
Nougayrede J., Voirin R. (1989) Liquid catalyst efficiently
Kent R.L., Einsenberg B. (1976) Better data for amine removes H2S from liquid sulfur, «Oil & Gas Journal», July,
treating, «Hydrocarbon Processing», 55, 87-90. 65-69.
Lagas J.A. et al. (1989) Claus process gets extra boost, Paskall H.G. (1979) Capability of the modified-Claus process,
«Hydrocarbon Processing», April, 40-42.
Calgary (Alberta), Western Research & Development, 19-45.
Lallemand F. et al. (2004) A new look at amines. Extending Shuai X., Meisen A. (1995) New correlations predict
the gas industry ‘workhorse’to new limits, in: Proceedings
of the Gas processors association annual convention, New physical properties of elemental sulfur, «Oil & Gas Journal»,
Orleans (LA), 14-17 March. 93, 50-55.
Lecomte F. et al. (2003) Hybrisol, a new gas treatment process SO2 removal. Regenerable SO2 capture makes headway (2004)
for sour natural gases, in: Proceedings of the Laurance «Sulphur», July-August, 37-44.
Reid Gas conditioning conference, Norman (OK), 25-27 Sulphur recovery catalysts. A broad selection (1995), «Sulphur»,
February, 281-310. January-February, 40-50.
Lee C.H., Moore A. (1997) Oxygen enhanced Claus Willing W., Linder T. (1994) Lurgi’s TGT processes and
operation. A case study, «Petroleum Technology Quarterly», new operational results from sulfreen plants, in: Sulphur
July, 73-75. 1994. Proceedings of the international conference, Tampa
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McManus D. (1998) Hydrogen sulphide removal from gas Cécile Barrère-Tricca
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European chapter meeting, London, 18 February. Vernaison, France

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3.

3.2.1 Introduction no longer economically possible. This market is

VOLUME II / REFINING AND PETROCHEMICALS 137

Fig. 2. Acid gas sour gas sour gas

H2S to ClausTGT sweet gas

138 ENCYCLOPAEDIA OF HYDROCARBONS

Fig. 3. Amine unit, treated gas fuel gas acid gas

VOLUME II / REFINING AND PETROCHEMICALS 139

Fig. 4. Amine unit, acid gas

semi-lean fuel gas

Benzene-Toluene-Xylenes (BTX), heavy Solvents overview

140 ENCYCLOPAEDIA OF HYDROCARBONS

absorption and then require a substantial amount [3] H2CO3

of heat for regeneration.

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

substituted on the nitrogen atom, while primary and

The reaction between acid gases and

substantial amount of heat. Reaction type differs for R1R2NH2

the molecule, H2S reacts instantaneously with

slower than H2S absorption. This reaction requires

VOLUME II / REFINING AND PETROCHEMICALS 141

Table 2. Alkanolamines and their applications

Amine Solution Applications Comments

142 ENCYCLOPAEDIA OF HYDROCARBONS

VOLUME II / REFINING AND PETROCHEMICALS 143

144 ENCYCLOPAEDIA OF HYDROCARBONS

Space velocity. Absorption is affected by 3.2.3 The Claus process

solution losses are generally linked to solution

acid gas leaving the acid gas removal unit has an

to oxygen enrichment so as to process more sour

VOLUME II / REFINING AND PETROCHEMICALS 145

thermal stage catalytic stage

H2S catalytic catalytic

Fig. 6. Typical Claus process scheme (straight-through design).

when all stoichiometric requirements for the basic

converter temperatures and an increased number

146 ENCYCLOPAEDIA OF HYDROCARBONS

Table 3. Total sulphur recovery 100

VOLUME II / REFINING AND PETROCHEMICALS 147

Chemistry in the thermal stage with the sulphur rich environment:

hydrocarbons in the feed acid gas must be taken

particularly important as it becomes involved in a

as well as affecting the amount of hydrogen

do so is questionable since the CH bond is

kinetic factors will affect the fate of the

1,200°C 1,000°C 600°C

waste heat boiler

burner reaction furnace

148 ENCYCLOPAEDIA OF HYDROCARBONS

VOLUME II / REFINING AND PETROCHEMICALS 149

Name Company Type Activity

DR Axens Activated alumina Active bed support and Claus reaction

AM Axens Promoted activated alumina Oxygen scavenger and Claus reactions

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

* also for IGCC cogeneration plants

150 ENCYCLOPAEDIA OF HYDROCARBONS

VOLUME II / REFINING AND PETROCHEMICALS 151