HYDRODESULFURIZATION OF PETROLEUM FRACTIONS AND

SUBSEQUENT RECOVERY OF SULFUR

INTRODUCITON:
Crude petroleum contains a variety of non-hydrocarbons, principally organic compounds
of sulfur, nitrogen and oxygen, but also organometallic compounds containing Ni and V
and occasionally Fe and As. Of these sulfur compounds are generally more prevalent and
of most concern in refining.
The sulfur content of crude oil generally range from virtually nil to 7or 8 wt% in extreme
cases, depending upon the source of the crude. In moderately high sulfur crude
containing sulfur 2 to 3 wt%.
Not only the sulfur contents of crude oils vary, but the relative amount of various classes
of sulfur compounds vary from crude to crude. Some generalizations, however, can be
made.
Both H2S and elemental sulfur are found dissolved in crude oils. These materials can be
responsible for corrosion problems in processing of the crude. Most of the H2S are
flashed off with the light hydrocarbon gases (methane, ethane) in gas separation units at
the oil field. Elemental sulfur, when present in crude oil as produced, is low in
concentration and because of its high boiling point remains in the heavy fractions upon
distillation.
In light straight run fractions, sulfur is typically present as aliphatic compounds. As the
boiling range increases, the sulfur compounds tend to be more cyclic, and in the heavier
fractions the sulfur is exclusively present in complex ring structure.
In gasoline the principle sulfur compounds include mercaptans, aliphatic sulfides,
aliphatic disulfides, and five- and six-membered ring cyclic sulfides. Thiophenes are
found in gasoline made by cracking heavier fractions, but are not usually present in
straight-run gasoline.
Few mercaptans occur above the gasoline boiling range. The predominant sulfur
structures in kerosene and gas oils are sulfides, cyclic sulfides, benzothiophenes, and
dibenzothiophenes.
In petroleum residues sulfur structures are similar to those in gas oils accounts for most
of the sulfur present. However, the most difficult sulfur in residues to remove by
Hydrodesulfurization is associated with asphaltenes.
Sulfur compounds are detrimental due to following reasons:
• Sulfur in fuels gets converted to SO2, which is corrosive to distillation equipment,
especially to condensers when water is present.
• Sulfur present in petroleum fractions can deposit on the catalyst surface as sulfide
during their treatment, causes catalyst to deactivate.
• SO2 has deep environmental impact, such as acid rain. It also has bad odour.
• Kerosene with high sulfur content burn in a lamp with a reddish fringe, smoke the
chimney and deposit on the chimney as a white film, which gradually darkens.
The overall process of sulfur removal by Hydrodesulfurization and subsequent recovery
of sulfur are related to one another. The hydrodesulfurization process involves catalytic
treatment with hydrogen to convert the various sulfur compounds present to hydrogen
sulfide. The hydrogen sulfide is then separated and converted to elemental sulfur by the

1
Claus process. From this point some of the hydrogen sulfide is oxidized to sulfur dioxide
by air and sulfur is formed by the overall reaction:

HYDRODESULFURIZATION OF PETROLEUM FRACTIONS

PURPOSES OF DESULFURIZATION:
In light petroleum products, such as LPG, naphtha, gasoline and even kerosene, sulfur
compounds are objectionable because sulfur compounds on burning produce SO2 that has
major environmental impact such as acid rain. Sulfur compounds are also responsible for
corrosion, the bad odor. The presence of sulfur compounds in gasoline tends to lower the
octane number. Furthermore sulfur poisons noble metal catalysts. Hence, desulfurization
is required with middle distillate fuels from high sulfur crude in order to meet product
specifications set for either environmental or competitive reasons.

SPECIFICATION OF SULFUR IN PETROLEUM FUELS:

Sulfur in petrol, ppm Sulfur in diesel, ppm

BS-II, 1993 500 500
BS-III, 2000 150 350
BS-IV, 2005 50 50

FEED STOCK OF HYDRODESULFURIZATION:

Feed streams to be treated in Hydrodesulfurization method are:
• Gasoline, kerosene, diesel streams from atmospheric distillation column.
• Atmospheric residue or vacuum residue before it’s fed to the catalytic cracker.
• Atmospheric or vacuum gas oils and deasphalted oil before they are fed to the
catalytic cracker.
• Cracked gasoline taken out from the thermal or catalytic cracker.
• Naphtha from atmospheric distillation column before it’s fed to the catalytic reformer.

CHEMISTRY OF HYDRODESULFURIZATION:
• REACTIONS INVOLVED:

The sulfur is present largely in the form of thiols, sulfides, and various thiophenes and
thiophene derivatives. Mercaptans and sulfides react to form hydrogen sulfide and
hydrocarbons.
RSSR’ + H2 RH + R’H + H2S

RSH + H2 RH + H2S

RSR’ + 2H2 RH + R’H + H2S

2
R and R’ are various hydrocarbon groups.
The reaction pathway for thiophene is

+2H2 H2S +C4H8 (mixed isomers)

S

Studies have indicated that the hydrodesulfurization and subsequent hydrogenation

reaction occur on separate sites. The thiophene ring is not hydrogenated before sulfur is
removed, although the first step may involve an essentially simultaneous removal of a
sulfur atom and donation of two hydrogen atoms to the structure.

For power-law expressions, the HDS reaction appears to be between ½ and first order
with respect to hydrogen at pressures above atmospheric. It is severely inhibited by basic
nitrogen compounds.

For benzothiophene, substituted or unsubstituted, the thoiphene ring is hydrogenated to

the thiophane derivative before the sulfur atom is removes, in contrast to the behavior of
thiophene. The following are the reaction pathways for benzothiophene and
dibenzothiophene are as follows:

CH2CH3
+H2 2H2 +H2S
S S

+H2 +H2S

These reaction equations illustrate that Hydrodesulfurization is accomplished by

cleavage of C-S bonds. C-H and S-H bonds replace these bonds.
In a similar manner, nitrogen and oxygen are removed catalytic hydrotreating by the
cleavage of C-N and C-O bonds. These basic reactions are:

Nitrogen-containing compounds + H2 nitrogen-free compounds + NH3

Oxygen –containing compounds + H2 oxygen-free compounds + H2O

3
These reactions occur in very small proportion at normal operating condition of
Hydrodesulfurization reaction.
In residue Hydrodesulfurization more severe conditions are required. Some amount of
hydrocracking reaction also occurs along with the above given side reactions.

PROCESS DESCRIPTION:
A typical flow diagram for distillate Hydrodesulfurization is shown in Fig-1. The oil feed
is mixed with fresh and recycled H2 and heated under pressure to the proper reactor
temperature. The oil-H2 mixture is charged to the reactor, passing down flow through the
catalyst. In the reactor, fresh feed is hydrogenated and a limited amount of
hydrogenation, isomerization and hydrocracking occurs to produce a small amount of C1
through C5 paraffins. In addition sulfur compounds are converted to H2S and nitrogen
compounds are converted to NH3. olefins are also saturated. These reactions are
exothermic and, in the case of vacuum gas oils and unsaturated feedstocks, reactor
temperature rise is regulated by cold recycle gas quench.
Reactor effluent is cooled and sent to a high-pressure separator where the oil is separated
from the H2S and H2-rich gas. H2S is scrubbed from the as and the H2 rich gas is recycled.
The liquid is passed through a low-pressure separator and stripper to remove the
remaining light ends and dissolved H2S. Fractionation of the liquid product is sometimes
employed, especially on heavier charge stocks.

PROCESS VARIABLES:
The major Hydrodesulfurization processing variables are discussed below: -

• Feed stock properties- as the concentration of sulfur, nitrogen, oxygen and/or olefins
increase, more severe hydrotreating conditions will be required to bring th
concentration down to any given level.
• Hydrogen partial pressure- generally increasing H2 partial pressure upto 4 Mpa, will
increase the rate of Hydrodesulfurization, if other conditions are held constant. It can
be shown that the H2 partial pressure can be altered by changing (1) total pressure (2)
gas circulation rate, or (3) the H2 purity of the circulating gas. At higher pressure the
degree of Hydrodesulfurization varies insignificantly (Fig-2)

90
%Conversion

80

70
1 2 3 4
Partial pressure of H2, Mpa Fig 2
In industrial Hydrodesulfurization plants total pressure is kept in the range of 3 to 7 MPa.
Fig-2
At higher pressure less coke precipitates on the catalyst.

4
• Temperature – higher temperature will increase the rate of Hydrodesulfurization
and the other desired reactions to remove contaminants. In Hydrodesulfurization of
petroleum fractions temperature is maintained at a level not above 390 oC in order to
suppress the reactions of hydrocracking In the temperature range of 400-450 oC,
hydrocracking reactions become predominant, the yield of desired product
diminishes, and H2 consumption increases.
• Space velocity (LHSV)- when holding all other conditions constant, increasing space
velocity will cause product H2S to increase. Increasing either the rector temperature
and/or H2 partial pressure can in some cases offset this effect. In mild operations,
space velocities range from 7 to 10 or even as high as 15. In more severe operations,
space velocities are usually between about 3 and 6,and in the most severe conditions
space velocities typically vary between 0.8 and 2.
• Catalyst aging and gas recycle rate- if the feedstock contain high amount of unstable
olefins, other heavy contaminants which can deposit on the catalyst, then catalyst
aging can be relatively fast and pressure drop problems could lead to early shut down
of the unit. As recycle rate, is governed by economic considerations although it has
marked effect on the carbon lay down on the catalyst. A high recycle rate keeps the
catalyst cleaner and prolongs active life of catalyst
• Ranges of conditions used for various types of Light oil Hydrodesulfurization:

General feed stock type Virgin Cracked blends of virgin

and cracked
Severity Mild Intermediate
Feedstock sulfur, ppm 100-700 100-3000
Feedstock nitrogen, ppm <2 2-30
Feedstock oxygen, ppm <10 10-100
Feedstock olefins, vol% <1.0 5-40
Operating conditions:
LHSV 7-15 3-6
Total pressure, psig 200-400 400-700
H2 partial pressure, psig 60-150 150-400
Gas rate, SCF/bbl 200-400 400-1000
Average temperature, oC 230-315 280-360

ADVANTAGES OF HYDRODESULFURIZATION:
• Desulfurized gas oils from the high sulfur crude can be fed to the catalytic cracker, as
Hydrodesulfurization of feed stock allows it to be cracked without excessive SO2
emissions in the regenerator flue gas.
• Hydrodesulfurization of naphtha is widely applied for preparing charge for catalytic
reforming. The main purpose is to remove sulfur but denitrogenation, deoxygention,
and olefin saturation reactions occur simultaneously with Hydrodesulfurization.
These reactions are beneficial since the noble metal catalysts used in reforming can
be poisoned by olefins, oxygen and nitrogen as well as sulfur in the feedstocks.
• Hydrodesulfurization process uses cheap H2 for desulfurization, provided by catalytic
reforming.
• The extent of sulfur removal is good, above 90% desulfurization being readily
obtained.

5
• Sulfur is removed in the form of H2S is another advantage of the process, as H2S
being gaseous, may readily be completely separated from the purified liquid
hydrocarbon and then be fed to sulfur recovery unit for subsequent recovery of sulfur.
• Hydrotreating of Lube Oil Base Stocks reduces sulfur content and also increases its’
viscosity index, stability, improves colour.

DISADVANTAGES OF HYDRODESULFURIZATION:
• After Hydrodesulfurization of gasoline obtained by cracking, their octane no
diminishes considerably (by 5-10 numbers). Gasoline of these kinds should be
subjected to Hydrodesulfurization not separately, but in a mixture with straight run
gasoline.
• In case of residue Hydrodesulfurization, more severe conditions are required. Under
these severe condition some amount of hydrocracking reactions may take place along
with Hydrodesulfurization giving rise to undesired products.
• High boiling fractions (e.g. thiophene) being lethargic towards H2 render
Hydrodesulfurization more difficult.

CATALYSTS:
The most commonly used Hydrodesulfurization catalyst consist of cobalt oxide and
molybdenum oxide (CoMo), or nickel oxide and molybdenum oxide (NiMo), dispersed
on high surface area alumina supports. Mo is generally regarded as the active
desulfurization component, with Co or Ni acting as promoter which increases catalyst
activity.
The catalysts are made with metals in their oxide state. In the active state they are in the
sulfide state, which is obtained by sulfiding the catalyst either prior to use or with the
feed during actual use.
CoMo catalysts are by far the most popular choice for Hydrodesulfurization, particularly
for straight-run petroleum fractions. NiMo is often used instead of CoMo where higher
activity for polyaromatics saturation pr nitrogen removal is required, or more refractory
sulfur compounds such as those in cracked stocks must be desulfurized.

Some typical metal compositions for commercially available catalysts are given below:

Metal , wt% CoMo NiMo

Cobalt 2.5
Nickel 2.5
Molybdenum 10.0 10.0
Hydrodesulfurization catalysts are generally either in the form of spheres or cylindrical
extrudates, though currently some catalyst manufacturers are reporting advantages of
shaped extrudates. Some typical ranges of catalyst properties are listed below: -

Nominal catalyst diameter, in 1/8 to 1/20

6
 Average range for extrudates, in ~¼
3
Packed catalyst density, lb/ ft 30 –50
Surface area, m2/g 200-300

Over the past few years, novel processing techniques for metal oxide materials have been
developed at National University of Singapore(NUS), which include HDS related
catalysts. In particular, CoO, Co3O4, CoAl2O4, Ru/Al2O3, MgAl/Al2O3, CoAl/Al2O3
Co/ZrO2, Ni/ZrO2, Co/Ni/ZrO2, MoO2, MoO3, and PbMoO4 have been synthesized. In
addition to these active catalysts, new generation-catalyst carriers of ZrO2, Al2O3, SiO2-
ZrO2 with a large surface area and controlled porosity have been prepared. As this class
of catalytic materials is closely related to the commercial catalysts (e.g., Co/Mo/Al2O3
and Ni/Mo/Al2O3) for hydrodesulfurization, the existing work at NUS can be easily
extended to the development of new generation hydrodesulfurization catalysts for super-
clean petroleum production

DEACTIVATION OF CATALYSTS:
CoMo and NiMo catalysts on alumina carrier serve for 2-3 years. The effective life of
catalysts depends on pore structure and total pore volume. It’s also dependent upon the
particular feedstock being processed and the operating conditions employed.
Hydrodesulfurization catalysts get deactivated due to two following reasons: -

• Coke deposition-during Hydrodesulfurization operation carbon gets deposited on the

catalyst pores, thus plug the catalyst pores, causing deactivation of catalysts. During
normal service life of catalysts 15% or more coke precipitate on the catalyst.
• Metal deposition- metals such as Ni, V may be present in small amount within the
feedstock of Hydrodesulfurization. These metals also can get precipitate on small
pores of catalysts. During 2-3 years of normal service life of catalysts 12-25% of
metal can deposit on the catalysts.
Due to deactivation of catalysts, operating temperature of Hydrodesulfurization increases,
to get a desired level of conversion. After temperature reaches an allowable maximum,
the catalyst has to be regenerated.

REGENERATION OF CATALYSTS:
Since catalyst activity is mainly lost due to coke deposition in pores, burning off coke
carries out regeneration. It’s done as follows: -
The system is first blown with circulation gas and then filled with an inert gas.
Regeneration is then carried out in a gas-air or steam-air atmosphere at a pressure of 0.3-
0.4 MPa and a temperature not above 550 oC in the zone of a catalyst. The circulation of
gas (steam) per m3 of catalyst is 400-500 m3/h. the content of O2 in the inert gas (steam)
at the reactor inlet is maintained at the following levels (%vol): 0.5 at the beginning of
the of regeneration, upto 2 at the end of regeneration, and 2-2.8 during burning-through
of the catalyst. The end of the coke burning is determined by temperature drop in the
reactor. When the O2 concentration at the inlet and outlet becomes constant, the pressure
is reduced to 2 MPa and temperature is raised up to 550 oC to burn though the catalyst for

7
4 hours. At the end of regeneration, the system is blown with an inert gas and the reactor
can be put back into operation.

RECOVERY OF SULFUR BY CLAUS PROCESS

PLACEMENT OF CLAUS PLANT :

Claus process is widely used in refineries, natural gas and coking plant.
Feed streams are to b treated from:
• Hydrodesulfurisation unit.
• Fluid Catalytic Cracking unit.
• Sour water Stripper unit.

FEED STOCK:
Feed sulfur content depends solely on source, which is a key design and operating
parameter. Different processes are applied depending on the different types of crude
being processed.

1. Rich feed – The general process description applies to a process receiving an

acid gas feed stock containing 50% or more H2S. This is commonly referred to
as “Rich feed” or “straight through” process.
2. Lean feed-
• The H2S percentage can be handled at 25-30% by addition of pure O2 to the
reactor air. Acid gas bypass and inline burners can also be used to do the job
when H2S concentration is low.
• A lean acid gas; 10 to30% H2S requires bypassing part (upto 2/3) of the acid gas
around the main combustion chamber with preheating the acid gas and air.
Replacing some or all of the combustion air, with pure O2 is another way to treat
lean gas.
• A very lean acid gas; less than 10% H2S, requires that pure sulfur be burnt to
SO2 and then combined with the H2S I the first catalytic bed.
Feed gases may contain carbon sulfur compounds, primarily COS and CS2; these are
usually formed by side reactions in the high temperature burner.

CH4 + SO2 COS + H2O + H2

CO + S COS

8
CO2 + H2S COS + H2S
CH4 + 2S2 CS2 + 2H2S
2CO + S2 CO2 + CS2

The higher the hydrocarbon content of a Claus gas stream, the more COS/CS2 is
likely to be formed.

DESCRIPTION OF CLAUS PROCESS:

Removal of sulfur from acid gases by Claus process was started 100 years ago. First
the H2S gas is separated from the host gas stream using amine extraction method.
This process separates H2S by absorbing it in amine solution and then evaporating
the H2S off. This then becomes the feedstock of Sulfur Recovery process. This
separated H2S is fed to the Claus unit, where it’s converted in two steps:

THERMAL STEP:
One third of the H2S fed is partially oxidized with controlled amount of air. This is
doe in a reaction furnace at high temperature (1000-1400 oC). The pressure of the
stream is in the 3-8 psig range and retention time in the reaction furnace is 0.5 – 1.25
sec. The reaction gases will contain a mixture of H2S, SO2, and sulfur. In this step
more than 70% H2S get converted into sulfur. The compounds NH3, mercaptans and
cyanides if present in the feed, should have to be destroyed by combustion,
otherwise this compounds will react with H2S to produce compounds that plug
catalytic reactor.
The reaction corresponding to Thermal Step is as follows:
2H2S + 2O2 SO2 + S + 2H2O

CATALYTIC STEP:
To convert more H2S to sulfur, thermodynamics suggest lower temperature in the
catalytic region. Before entering catalytic converters sulfur must be condensed from
the gas steam to prevent condensation of sulfur on the catalyst surface and to
improve thermodynamic equilibrium yield. The temperature of the reactor should be
as low as possible but should be kept above sulfur dew point, provided the rate of
reaction is first enough. Dew point is generally the limiting factor, since good
catalysts are available to achieve fast reaction. The temperature maintained in this
step is 200 - 300oC; lower limit is the dew point of sulfur (120oC). To maximize the
conversion of H2S to sulfur, generally three catalytic stages are used. The retention
time in the catalytic reactor is 1.0-2.0 sec. Sulfur removal by condensation, gas
reheat between each stage, and lower temperature in successive converters also
helps to maximize removal of sulfur. The reaction corresponding to the catalytic
step is as follows:

9
2H2S + SO2 3S + 2H2O
In a three step process first reactor inlet at 230-250 oC and third reactor inlet at 150-
190 oC. This allows for maximum reaction of COS and CS2 in the first reactor and
maximum H2S-SO2 reaction in the 2nd and 3rd reactor beds. The sulfur recovery in
this step can be as high as 98%.

INCINERATION STEP-
If H2S in the tail gas coming out of the 3 rd catalytic reactor is below the limit set by
the local regulatory authority, then the remaining H2S is burnt to SO2 and released in
the atmosphere.
This is done by raising tail gas temperature to 530 oC in an incinerator fired by fuel
gas. An access of O2 is required in the incinerator chamber to burn the tail gas.

TAIL GAS TREATING UNIT-

If H2S in the tail gas coming out of the 3rd catalytic reactor is above the limit set by
the local regulatory authority, then the tail gas stream is further treated for more
recovery of sulfur.
The process involves reducing the sulfur to H2S and then absorbing or reacting H2S
in downstream processing units, for example in SCOT unit, an inline burner is
utilized followed by indirect re-heater with supplemental H2S addition to form
reducing gases which enters the reactor containing cobalt- molybdenum catalyst bed
allowing both the hydrolysis hydrogenation reactions to convert all sulfur to H2S.
After passing through a quench tower the stream enters amine absorber where H2S is
selectively absorbed. The off gas passes to incinerator. The rich mine is regenerated
and H2S recovered is fed back to the Claus unit for further recovery of sulfur.

DETAILED PROCESS DESCRIPTION OF CLAUS PROCESS:

The Sulfur Recovery Unit consists of the following sections:
• A knock out drum for the feed gas stream and fuel gas stream
• A Claus section, consisting of a thermal stage and three reactor stages
• A SUPER CLAUS stage
• A thermal incinerator, burning the tail gas and vent gas of the sulfur
Degassing system
• Sulfur pit with degasifying facilities and sulphur yards.

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CATALYST AND CHEMICALS
1. CLAUS CATALYST : These catalysts are installed in the Claus reactor
• 1st & 2nd reactor : CRS-31 , 85 wt % titanium oxide
• 2nd & 3rd reactor : CR-3S , 98 wt % alumina with 2400 wt PPM Na2O

2. SUPERCLAUS CATALYST : It is a catalyst for selective oxidation and

consists of
• Aluminium oxide 50% volume
• SiO2 with iron (III) oxide / phosphate 50% volume
The catalyst is premixed by 50% / 50% volume basis by manufacturers.

3. CERAMIC BALLS : A layer of ceramic balls is installed in the reactor as

support bed. Type of ceramic ball is Denstone 57.

• CLAUS SECTION : By the reactions described before , sulfur is formed in

vapour phase in the main burner and combustion chamber.
The primary function of waste heat boiler is to remove the heat generated in main burner.
The secondary function of waste heat boiler is to utilize removed heat to
produce MHP stream.
The process gas from the waste heat boiler is passed into the 1st sulphur condenser,
where the formed sulphur is removed from the gas.
The process gas leaving the sulphur condenser still contains a considerable concentration
of H2S and SO2. Therefore, the essential function of the following equipments is to
convert these components to sulphur.
In the 1st, 2nd and 3rd reactor stages, the H2S and SO2 again react to form sulphur but
this time at lower temperatures.
In the SUPERCLAUS stage, the remaining H2S is selectively oxidized to sulphur. For
this reason it is essential that the combustion in the main burner is such that in the
downstream of the 3rd reactor stage, the amount of H2S in the range of 0.5 – 0.7 volume
% and the SO2 concentration is as low as possible.
Before entering the 1st reactor, the process gas flow is heated by indirect steam to obtain
the optimum temperature for a high conversion of H2S and SO2 to elemental sulfur and
simultaneously a high conversion of COS and CS2 to H2S and SO2.
The effluent gas from the 1st reactor is routed to 2nd sulphur condenser.
The process gas flow is next routed to 2nd steam reheater and then to 2nd reactor where
equilibrium is established. The sulphur is condensed in the 3rd sulphur condenser.

11
From the 3rd sulphur condenser, the process gas is routed to 3rd steam reheater , then
passed to the 3rd reactor where equilibrium is established . The sulphur is condensed in
the 4th sulphur condenser.

• SUPERCLAUS SECTION : The process gas from the 4th sulfur condenser is
routed to the fourth steam re-heater then passed to the reactor. Before it enters the
reactor, a controlled amount of air is added. Proper mixing is obtained in a static
mixer. The formed sulphur is condensed in the 5th sulphur condenser. ASulphur
coalescer is installed downstream of the last sulphur condenser to separate
entrained sulphur mist.
The sulphur condensed and separated in the condensers and coalescer is drained via the
sulphur locks and the sulphur cooler into the sulphur pits.
The tail gas leaving the coalescer still contains an amount of H2S which is dangerous if
released directly to atmosphere. Therefore, the gas is thermally incinerated, converting
residual H2S and sulphur vapor to SO2 in presence of oxygen. After the gas is cooled in
incinerator ,waste-heat boiler and superheater it is routed to the stack . In the incinerator
and waste-heat boiler, MHP steam is produced and in the superheater MHP steam from
the unit is superheated before evaporation.

• SULPHUR STRIPPING PROCESS : The process sulphur contains H2S

partially dissolved and partially present in the form of polysulphides ( H 2SX ).
Without treatment of the sulphur, the H2S should be slowly released during
storage and transport. An explosive mixture may be created due to exceeding the
lower explosive limit of H2S in air, which may vary from 3.7 volume % H2S at
130OC to 4.4 volume % H2S at ambient condition. The shell sulphur degassing
process has been developed to degasify liquid sulphur to 10-ppm wt H2S/H2SX
which is the safe level to avoid exceeding the lower explosive limit.

The function of this process is to enhance the decomposition of polysulfide

and to strip the H2S from the sulphur. Simultaneously, the greater part is oxidised to
sulphur. The air decreases the partial pressure of H2S and causes agitation and circulation
of the sulphur.

In this way, the H 2S content is reduced from approximately from 350 to less
than 10 ppm wt. The reduced H2S together with the air is routed to the thermal
incinerator, in which it is oxidised to SO2 . The degassed sulphur is pumped on level
control to sulphur yard.

12
 CLAUS PROCESS VARIABLES:

• H2S/SO2 RATIO-
The stoichiometry in the equation shows that at 2:1 ratio for H2S: SO2 Claus
plant efficiency will be highest. Such ratio control requires reliable analysis of
H2S: SO2 ratio and a control system to adjust air flow into the unit to maintain
the H2S/SO2 ratio at 2:1.
• TEMPERATURE-
According to thermodynamic equilibrium curve, conversion in the catalytic
converters will be high at low temperature, but it should be above the dew point
of sulfur (120oC).
An interesting aspect of Claus process is strange behavior of molten sulfur. The
temperature of the molten sulfur should be controlled carefully. If the sulfur is
allowed to cool too much it can begin to polymerize. Below is the characteristic
viscosity curve associated with molten sulfur.

35 x 104

Viscosity (cP)

0 200 300 600 900

Temperature (oC)

• COS AND CS2 CONVERSION-

Presence of COS and CS2 is undesirable from the standpoint of carrying to
completion of Claus reaction. Significant reaction of COS and CS2 is possible by
operating 1st converter with an outlet temperature around 315oC.

COS +H2O H2S + CO2

13
 CS2 + 2H2O 2H2S + CO2

CS2 has 2 moles of sulfur for every 1mole of CS2, which magnifies its
contribution to sulfur emission. To get maximum conversion of COS and
CS2 in the first converter, it’s operated at temperature higher than optimum.
It’s more tough to get COS and CS2 converted than H2S/SO2 conversion.
• Retention time of reacting gases at elevated temperature.
• Space velocity (GHSV) of feed gas in the catalytic converter.
• Selection of optimum sulfur condensation and feed gas reheat scheme.
• Catalytic converters should operate above sulfur dew point.

ADVANTAGES OF CLAUS PROCESS:

• Well-proven technology.
• Can produce bright sulfur upto 99% purity.
• Can be designed to convert COS, CS2 and destroy NH3.
• Relatively lower cost due to net steam production. The net steam
production is 2.6 t steam / t sulfur yield.

DISADVANTAGES OF CLAUS PROCESS:

• Requires an acid gas feed stream relatively rich in H2S (usually more than
15-20%).
• Maximum sulfur recovery is about 98-99% for Claus process, which

often requires subsequent Tail gas treating unit or SUPERCLAUS step
to follow Claus process for more than 99% sulfur recovery.

DEEVLOPMENT IN SULFUR RECOVERY PROCESS TECHNOLOGIES:

Different process technologies are available other than Claus process for sulfur recovery
are described below. These processes differ in percentage of sulfur recovery.

SUPERCLAUS:

SUPERCLAUS is a selective oxidation method for sulfur recovery from acid
gases, with the objective to get reaction yield more than 99% without any further tail

gas clean up. The tail gas stream is fed to a reactor filled with SUPERCLAUS

14
 catalyst (direct oxidation). The catalyst oxidizes H2S to sulfur in presence of O2 at
efficiency more than 85%. The reaction corresponding to this step is as follows:

H2S + ½ O2 S+ H2O

OXYCLAUS PROCESS:
The modified Claus reaction is carried out with direct oxidation combustion by using
proprietary thermal reactor. Considerable cracking of H2S to H2 and sulfur occurs in the
hot flame core as the thermodynamic equilibrium is approached.
CLINSULF:
It’s catalytic direct oxidation method in gas phase. The catalytic reaction between H2S
and O2 is performed in an internally cooled reactor. Clinsulf unit recovers sulfur 92-96%
relative to the input.
COPE:
The sulfur producing capacity of typical Claus process can be increased through partial to
complete replacement of combustion air with pure O2. sulfur recovery will be 95-98%.
SELECTOX-
Recover sulfur from low H2S concentration acid gas streams (< 30-vol% H2S), selectox
and recycle selectox units resemble Claus units, except the burner and reaction furnace
are replaced by a fixed bed of Selectox catalyst. Sulfur recovery is about 90-98%.
SULFREEN-
This process is based on well- known Claus reaction in which H 2S and SO2 in a tail gas
can be catalytically converted to elemental sulfur. Sulfur recovery ranges from 99-99.9%.

CATALYSTS:
Nowadays the catalysts mostly used in Claus process are active alumina catalysts. Apart
from that titania is also in use. Claus unit conversion is significantly improved using
catalysts that resist deactivation due to poisoning. A set of new generation catalysts are
given below,

Superclaus catalyst: the catalyst consists of 50% / 50% vol. mixture of Al2O3 and silica
carrier materials. The active component is Fe2(SO4)3.
AA-100: activated alumina catalyst. It ensures maximum catalytic activity and excellent
conversion.
S-100: most robust alumina catalyst in the world. Especially useful in plants where
severe operating conditions require an exceptionally strong product.

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SRC-99ti: this is high performance titania catalyst, optimized for very high COS and CS2
conversion. This product also provides excellent resistance o sulfation in downstream
converters.
CRS-31: it’s a new generation very high performance Claus catalyst based on promoted
TiO2. It’s suitable for all converters; recommended for all H2S concentrations as well as
for direct oxidation, lean gas treatment TGT process.
CR-3S: it’s an alumina catalyst with optimized Na2O content. It also shows excellent
performance in sub dew point TGT units.
KTK-3: it’s a titania based catalyst, particularly useful in first reactor in the presence of
oxygen. It can be used as sulfation resistant and for weak acid gas treatment.

PROPERTIES OF CTALYSTS:
The Claus catalysts should have the following properties:
o Macroporocity- catalysts should be macro porous to enhance bulk molecular
diffusion of Claus reaction product elemental sulfur, which is a mcromolecule
(S6,S8 etc.). The recommended range of macroporocity is 0.15-0.18 cc/g.
Macroporocity higher than optimum is detrimental because it creates void space,
which limits surface area per given reactor volume.
o Surface area- surface area of fresh catalysts should be as high as 300-400 m2/g.
Catalyst surface area decreases with size due to various reasons.
o COS / CS2 conversion – high rate of conversion of COS and CS2 is appreciated at
the catalyst bed of first reactor.
o H2S / SO2 conversion – Using suitable Claus catalysts H2S conversion can be
possible as high as 99%.
o Physical properties – the catalyst must posses sufficient crush strength
(min∼ 30lbs.) to withstand several years of continuous operation. In addition low
attrition and abrasion values are required to prevent dusting during loading.

DEACTIVATION OF CLAUS CATALYST ACTION:

o Coating by sulfur - caused by too low an entering temperature, less than sulfur
dew point, which allows condensation of sulfur on the catalyst surface.
o Glossy carbon or tar coatings- all hydrocarbons are not combined with O2 in the
reaction furnace and waste heat boiler and deposit here.
o Sulfation- SO2 will react directly with catalysts, O2 can be present in actual Claus
process streams and be the main cause of catalyst sulfation, i.e, in situ oxidation
of chemisorbed SO2. The proposed chemical reaction for sulfation on the alumina
catalysts surface is given by

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 Al2O3 + 3SO2 + 3/2 O2 Al2(SO4)3

o Thermal aging – it’s a time temperature effect. Poorly controlled regeneration

causes rapid aging, otherwise it’s a slow process at normal operating temperature.
Due to this surface area of catalysts decrease gradually.
o Hydrothermal aging- it accelerates deactivation of alumina based catalysts by
surface hydration effects.

REGENERATION OF CLAUS CATALYSTS:

Claus catalysts aren’t generally regenerated in commercial SRU. Catalyst life is 3-4
years. They are rejected after constant use till their activity goes below certain limit. If
catalysts get deactivated within short period of operation, then only they are regenerated.
Catalyst activity can be regenerated by different methodologies according to the cause of
deactivation. The different methods are listed below,
• The interaction between SO2, O2 and alumina is greater at higher
temperature and partial pressure of O2. Reversly, a reduction by H2S or by
mixture of H2S and SO2 starts at 280-300 oC. The velocity of this reaction is
very high in the range of 250-340oC compared to velocity of sulfation
reaction. When contacted to H2S the chemisorbed SO2 or superficial sulfate
reacts to sulfur and water. The reaction is given by,

Al2(SO4)3 + H2S Al2O3 + 4SO2 + H2Os

As long as the surface area of the catalyst is above 150cm2/gm and if the activity
decreases due to accidental sulfation, an improvement can be expected by operation of
the 2nd reactor at the following conditions
I. Increase the H2S content of the reactor to 2-3 volumes.
II. Catalyst temperature should be increased to 300-400oC.
III. Maintain these conditions for 24 hours.
IV. The H2S /SO2 ratio should be around 4:1 (i.e., H2S rich).
• Heat soak - here catalyst bed temperature is hotter than usual, i.e.,
increased by 28-42oC. This heat soak drives sulfur out from catalyst. H2S /
SO2 ratio is 2:1 normally.

• If carbon or sulfur burn offs are attempted then,

I. Controlled burn off to remove deposited carbon.
II. Controlled burn off to remove deposited sulfur.

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