Technical & Commercial Evaluation Of Processes

For Claus Tail Gas Treatment

Andr Le Gall, Dominique Gadelle

Process and Technology Division
Technip France
Paris La Dfense,
France

ABSTRACT
After its removal from crude oil, refinery sulphur is principally in the form of hydrogen sulphide (H2S). The
most common means of recovering the sulphur contained in H2S is the modified Claus process which
can recover from 90 to 97% of the sulphur contained in the acid gas feed. Recovery depends upon such
things as acid gas composition, age of the catalyst and number of reactor stages. The gas leaving a
modified Claus plant is referred to as tail gas that in the past was burned to convert the unreacted H2S to
less toxic but still undesireable SO2. The off-gas stream was then vented to the atmosphere.
Currently, all Western countries and many developing countries are tightening environmental regulations
to limit further the amount of sulphur that can be emitted to the atmosphere. There is therefore a need to
add Tail Gas Clean-Up Units in refineries.
TGCUs are quite expensive, often representing an investment of the same order of magnitude as the
original Claus plant. The proper selection of TGCU process is therefore of some importance to operators
whereas the choice is made complicated by the different performance levels and life cycle costs.
This paper compares a selection of the most popular Tail Gas Clean-Up (TGCU) processes based on
their sulphur recovery yield (%) and most importantly in terms of the recovery cost per tonne of SO2 ($/t).
Technical evaluations, capital and operating costs are compared. The paper is based on work performed
by TECHNIP FRANCE for the French energy conservation agency ADEME.

Presented at GPA Europe Technical Meeting

Paris
21st February, 2003

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Evaluation of TGCU Processes Page 1 of 22
1. INTRODUCTION
This paper describes a study conducted to compare the relative technical and economic merits of a wide
range of Tail Gas Clean-Up (TGCU) processes when compared to a conventional Claus unit. The study
covered the following areas: technical evaluations and capital and operating costs.
Selected processes were compared on the following basis: sulphur recovery (%) and estimated recovery
cost for SO2 ($/t).
The study was performed by TECHNIP FRANCE for the French energy conservation agency ADEME.

1.1 SULPHUR IN REFINERIES

The sulphur species after its removal from crude oil is generally in the form of Hydrogen Sulphide (H2S).
The most common means of recovering the sulphur contained in H2S is the modified Claus process. The
modified Claus plant can recover from 90 to 97% of the sulphur contained in its feed. The recovery
depends upon such things as feed composition, age of the catalyst and number of reactor stages. The
gas leaving a modified Claus plant is referred to as tail gas and, in the past was burned to convert the
unreacted H2S, which is lethal even at low levels (lethal concentration: 1 000 ppm after one min.), to SO2
which has a much higher toxic limit (lethal concentration: 2 500 ppm after one min.). The off-gas stream
was then vented to the atmosphere.
Currently, all Western countries and many developing countries limit the amount of sulphur that can be
emitted to the atmosphere. In Europe, the 1998 directive limits SO2 to a 1700 mg/Nm3 emission
"bubble" in which Claus effluent is a significant part. Allowable emission levels will be reduced during the
coming decade. New units must be equipped with TCCUs. There is also regulatory pressure to add a
TGCU to existing units. TGCUs are quite expensive, often costing an order of magnitude of Claus plant.

1.2 H2S IN REFINERIES

The feedstock to a refinery Claus unit is usually a combination of the following streams:
Regenerator overhead stream from a gas sweetening unit (off-gas coming from a FCC and a
gasoil HDS units),
Effluent stream from the Refinery Sour Water Stripping unit.

Typical feed conditions and properties for each stream are given in the following table.
Stream 1 Stream 2 Overall
Temperature (C) 40.0 90.0 42.0
Pressure (kpa) 170.0 170.0 170.0
Flowrate (kmole/h) 145.63 5.65 151.28
(kg/h) 4947.91 121.67 5069.58
Molecular Weight (kg/kmole) 33.98 21.53 33.51

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1.3 THE CLAUS PROCESS
The study considered the enhancement of sulphur recovery from an existing two reactor refinery Claus
unit as shown in the typical flowscheme below.
The tail gas unit receives the effluent from a Claus unit producing 100 t/d of liquid sulphur with sulphur
recovery of 96% weight.
This upstream Claus unit will include the following main equipment:
- One thermal stage,
- Two catalytic stages,
- One thermal incinerator,
- One daily sulphur storage pit.

Steam

#1 Reheater

Reaction Furnace #1 Reactor

and Waste Heat Boiler
Acid Gas &
SWS effluent
#1 Condenser

#2 Condenser
Steam
Air Blower Sulphur Sulphur

#2 Reheater
Tail Gas to
#2 Reactor Incinerator or
TGCU

#3 Condenser

Sulphur
Typical Two Stages Claus Unit

The above flowscheme is very typical. Various arrangement are available, depending on the relative ratio
of acid gas to sour water stripper gas, depending on the capacity, on the reheating arrangement (steam
heater, in-line burners, electric heaters, ), etc.
In refinery applications (relatively rich acid gas) sulphur recoveries range anywhere from 92 to 96% in a
two converter arrangement. A third converter will increase the recovery by 1 to 2 additional percent.
The recovery is based on the Claus reaction ; one third of the H2S in the feed gases is oxidized thermally
with air to form SO2. The latter then reacts with the remaining H2S to form elemental sulphur (Claus
reaction). Excess air is to be injected to ensure the destruction of hydrocarbons and/or ammonia present
in the feeds.
H2S + 3/2 O2 SO2 + 2 H2O (1)
2 H2S + SO2 3 S + 2 H2O (2)
In order to maximize sulphur recovery, precise air to acid gas ratio control is required in order to achieve
a 2 to 1 H2S to SO2 ratio.

1.4 CLAUS UNIT EFFLUENT STREAM

The Claus unit effluent stream (tail gas) properties are:
Temperature (C) 128
Pressure (kpa) 145
Flowrate (kmole/h) 434
(kg/h) 10657
Molecular Weight (kg/kmole) 24.6

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2. TAIL GAS CLEAN-UP PROCESS SCREENING
More than 20 processes for Tail Gas Clean Up have been developed over the years to meet the
environmental restrictions on sulphur emission from stationery sources.
TGCU processes can be broadly divided into four groups of processes, namely:
Dry bed processes,
Liquid Phase Sub-DewPoint Processes,
Liquid scrubbing processes,
Liquid Redox process.

The first and third categories can further be divided in sub-categories depending on the sulphur recovery
method used. It should be noted that some arrangements combine the capabilities of both Dry Bed and
Liquid Scrubbing processes.

2.1 DRY BED PROCESSES

The main process step is achieved on a solid catalyst.
Two paths have been followed:
Extend Claus reaction on a solid bed
Oxidise Sulphur compounds to SO2 prior to absorption, or reaction.

Extension of Claus Reaction on a Solid Bed

Several processes have been developed and have been widely used. Basically, they are variations of the
same process and differ mainly in the regeneration technique used:
Elf/Lurgi Sulfreen Process and derivatives (HydroSulfreen, DoxoSulfreen, ),
AMOCO Cold Bed Absorption (CBA),
MCRC Process

Direct Oxidation Processes

In order to overcome the limitation in conversion of the Claus catalysts, new catalysts have been
developed in order to promote either:
Direct oxidation of H2S to sulphur (such as Superclaus, MODOP, BSR Hi-Activity
technologies),
Claus reaction and direct oxidation of H2S to sulphur (such as Selectox
technology).

In a conventional Claus process unit, the conversion to sulphur is based on the oxidation (complete
oxidation) to SO2 and the subsequent production of elemental sulphur by the Claus reaction (reactions
(1) and (2).
Direct oxidation of H2S to sulphur can also be thermodynamically completed according to:
H2S + O 2 S +H2O (3)
In the absence of a catalyst, the rate of this reaction is very slow, and the reaction becomes noticeable
only above 300C. However, at these temperatures, the formation of SO2 is also accelerated and
proceeds according to the reaction (1) above, as well as from:
S + O2 SO2 (4)
3 S + 2 H2O 2 H2S + SO2 (2)
In order to limit SO2 formation and favour partial oxidation reaction (3) temperature should be limited well
below 300C, and a suitable catalyst developed. Several catalysts have been developed and form the first
family of processes listed above.

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In certain specific instances (lean gases with low H2S content where flame stability and impurities
destruction is of concern), catalysts able to promote both classical Claus reaction and direct oxidation
have been developed.

2.2 LIQUID PHASE SUB-DEWPOINT PROCESS

Clauspol family of processes
The Clauspol family of processes was developed by the French Institute of Petroleum (Institut Franais
du Ptrole IFP). The fundamentals of the process consist in extending the Claus reaction under sub-
dewpoint conditions in liquid phase.
The liquid phase consists in a non-volatile solvent containing dissolved catalyst (sodium salt of an
inorganic acid) which is a solvent for H2S and SO2, but not for liquid sulphur.
The Claus reaction: 2 H2S + SO2 3 S + 2 H2O can therefore proceed at low temperature (120C) and
is shifted further to the right as the produced sulphur is removed from the reaction medium, as it is not
soluble and separates.

2.3 LIQUID SCRUBBING PROCESSES

Broadly speaking, there are two main categories of Liquid Scrubbing processes, H2S scrubbing
processes and SO2 scrubbing processes. In the most commonly applied configurations, H2S or SO2 are
recycled to the upstream Claus Unit.
H2S Scrubbing Processes
This type of process is by far the most widely applied TGCU type of process. This type of process can
achieve overall sulphur recovery above 99.9%.
The concept underlying H2S scrubbing processes are:
Hydrogenation and hydrolysis of all sulphur compounds to H2S
Absorption of H2S by an Amine solution (generic amine or specialty amine)
Regeneration of the Amine solution and recycle of the H2S to the upfront Claus Reaction
Furnace.
SO2 Scrubbing Processes
This type of process is consists in converting, or recovering and recycling SO2. This part of the TGCU
unit is located downstream the thermal incinerator of the Claus Plant. This means that all sulphur
species (H2S, COS, CS 2, Sulphur) have been previously oxidized to SO2, therefore no
hydrolysis/hydrogenation step is required.
This family of processes offers therefore a potential for very high sulphur recoveries, provided SO2 can be
converted and/or recycled. Several processes are derived from flue gas desulphurization techniques, and
even if they have not been applied to Claus units tail gas, their main elements may have been referenced
for other applications.
Two types of solvents are used for SO2 absorption, either chemical absorption by an aqueous solution a
basis compound, or physical absorption. Roughly speaking physical absorption implies a higher
circulation flowrate of solvent, easier rich solvent regeneration, and potentially a reduced tendency to
enter into side-reactions leading to undesirable by-products. The advantages of chemical solvents are:
lower circulation rates and usually a better absorption capability.
The Wellman-Lord process has been the most widely used process of that kind since the early 60s. The
absorption media is a solution of Sodium Sulphite Na2SO3. Other processes have been developed more
recently, such as the Elsorb process which uses an aqueous solution of sodium phosphates, or the
Cansolv process which uses an amine based solvent. The ClausMaster process belongs to the same
family, using a phosphorus based solvent.

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2.4 LIQUID REDOX PROCESSES
Since the beginning of this century, various Redox (or Liquid Phase Oxidation) processes have been
developed to absorb both H2S and NH3 from mainly town gas or coal gas by the formation of Ammonium
Sulphate and of elemental sulphur. The initial objective was to overcome the limitations of the existing
Iron Sponge processes and to develop a regenerable, reusable oxidation medium. Among the processes
developed, those still in commercial application are:
The Stretford Process, which has been widely used since the 50s and uses ADA
(anthraquinone disulphuric acid) as an oxygen carrier in an aqueous solution containing
carbonate and vanadate.
The Sulferox process and the LO-CAT process which both use Iron Complex solutions as
oxygen carriers.

2.5 OTHER PROCESSES

A significant number of other TGCU processes have been developed over the years, some of which have
now been abandoned, or have not yet reached a commercial status, others are similar in essence to
processes described above.

3. SELECTION OF REPRESENTATIVE PROCESSES

TGCU processes, as outlined above, were grouped in families of processes which share several
common features. Therefore, in the framework of the evaluation study, it was considered (at least for cost
estimate purposes) acceptable to restrict the evaluation to one, or possibly two, significant
representatives of each family.
The licensed processes selected for study were as follows:
Dry Bed Sub-DewPoint processes:
Sulfreen with alternatives (HydroSulfreen and DoxoSulfreen)
Cold Bed Adsorption

Liquid Phase Sub-DewPoint processes:

Clauspol II

Catalytic Oxidation:
Superclaus 99

H2S Scrubbing :
Technip KTI-RAR

Liquid Redox :
US Filters LO-CAT (now owned by Merichem)

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3.1 SULFREEN PROCESS
The Sulfreen Process is a dry-bed, sub-dewpoint absorption process based on the extension of the
Claus reaction. The reactor operates below the dew point of sulphur (125-150C) to form elemental
sulphur. The reaction is extended, and the recovery enhanced, first because the equilibrium is
thermodynamically favoured at low temperature, and second, because the Sulphur is absorbed on the
catalyst, therefore shifting further the reaction to the right:
2 H2S + SO2 3 S + 2 H2O
The Sulfreen process basically consists in two (occasionally three for large capacities) Sulfreen reactors
in series with the Claus reactors. Activated Alumina is used as a catalyst.
As the sulphur accumulates on the catalyst, the activity decreases and the beds have to be regenerated
thermally. During the regeneration step, sulphur is desorbed and the catalyst activity is restored to full
activity by part of the TGCU tail gas which has been preheated in a dedicated heater. Once the
regeneration is achieved, the catalyst bed is cooled to the operating temperature.
Sulphur from the hot regeneration stream is condensed in a dedicated condenser.
Typical overall Sulphur recoveries are in the order of 98.5 to 99.5% depending on the Claus Unit
arrangement. COS and CS 2 are not converted, nor recovered.
To date, there have been more than 40 Sulfreen units licensed, with capacities ranging from 5 to 2200
MTPD (expressed as Claus Unit feed sulphur).
The following figure is a simplified process diagram of a two-reactor system (one in absorption, one in
regeneration).
To Incinerator

Sulfreen Sulfreen
Reactor #A Reactor #B

Claus Unit
Tail Gas

Circulation
Blower Sulphur
Closed

Adsorption
SULFREEN Process Opened
Regeneration
Reactor A in adsorption

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3.2 HYDROSULFREEN PROCESS
COS and CS 2 in the effluent from a Sulfreen Unit can represent about 50% of the residual Sulphur. To
overcome this limitation, a conversion step is added upstream of the first Sulfreen reactor.
This conversion step performs the hydrolysis of COS and CS 2 to H2S and is performed on an activated
Titanium oxide Claus catalyst such as Procatalyse CRS31. This reactor operates at about 300C. The
Claus reaction takes place in the HydroSulfreen reactor and produced sulphur is condensed in a
dedicated condenser. The preheat of the Claus unit tail gas to the HydroSulfreen reactor is performed by
a separate coil in the Sulfreen regeneration heater.
After sulphur condensation, the effluent from the hydrolysis reactor is routed to the Sulfreen section,
similar to the one described above.
Typical overall Sulphur recoveries are in the range of 99.5 to 99.7%.
To date, there have been 4 HydroSulfreen units licensed, with capacities up to 400 MTPD (expressed as
Claus Unit feed sulphur).
The schematic process diagram is given below:

To Incinerator

Regeneration
Air Heater

Hydrolysis
Reactor

Sulfreen Sulfreen
Reactor #A Reactor #B

Sulphur

Circulation
Claus Unit Blower Sulphur
Closed
Tail Gas
Adsorption
Opened
Regeneration
HYDROSULFREEN Process

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3.3 DOXOSULFREEN PROCESS
This process is based on a direct oxydation of H2S into sulphur, with oxygen.
At the outlet of a conventional Sulfreen, or HydroSulfreen process, the sulfur conversion cannot proceed
further due to the reduced H2S and SO2 concentration, and due to the water partial pressure which tends
to shift the conversion to the left. The DoxoSulfreen concept is based on two ideas:
the upstream units are operated to get a slight excess of H2S, compared to the quantity
necessary to maintain the Claus ratio, therefore a nearly total SO2 conversion takes place on
the conventional Sulfreen catalyst:
10 H2S + SO2 3 S + 2 H2O + 8 H2S
the remaining H2S is oxidised to elemental Sulphur according to
2 H2S + O2 2 S + 2 H2O
A simplified process flow diagram is given below:

Closed To Incinerator
Adsorption
Opened
Regeneration

DoxoSulfreen
Sulfreen
Reactors
Reactors
A&B
A&B

Claus Unit
Tail Gas Circulation
Blower

Regeneration
Heater

Sulphur
DOXOSULFREEN Process

The gas from the Sulfreen reactors is further cooled to 100-130C, and fed to a second catalytic stage
together with a stream of air so that the direct oxydation of the residual H2S can take place.
Both SULFREEN and oxydation beds are regenerated through a common regeneration loop.
Activated Carbon was initially used as a catalyst in the oxidation step (thus the initial name of
CarboSulfreen), this catalyst being currently replaced by a new oxidation catalyst developed by
Procatalyse.
The DoxoSulfreen Process has demonstrated its ability to recover Sulfur up to the 99.8% level. This
process can be used in combination with an Hydrolysis step (HydroSulfreen) in front of the Sulfreen
reactors.
The CarboSulfreen version is currently in operation in two German refineries.

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3.4 CBA PROCESS
The Cold Bed Adsorption Process is based on the same fundamentals than the Sulfreen Unit, e.g.
performing additional Claus Reaction at low temperature, with subsequent adsorption on the catalyst and
a required thermal regeneration step.
The difference with the Sulfreen process lies in the fact that the hot gas source for regeneration is taken
from the outlet of a Claus reactor. Several configurations are available depending on the number of Claus
converters. The temperature of the regeneration gas is around 335 to 350C. Typically, the feed to the
CBA reactor in adsorption is at a temperature of 225C.
Several variations the Process flowscheme are available, depending on the number of Claus and CBA
reactors. These arrangement range from 1 Claus + 2 CBA reactors to up to 5 CBA reactors. The most
popular arrangements are 1 Claus + 2 CBA reactors and 2 Claus + 2 CBA reactors.
A schematic flow diagram of an arrangement with 2 Claus Reactors and 2 CBA reactors is enclosed
below.

Acid Gas &

SWS effluent Reaction Furnace
and Waste Heat Boiler

Steam R3 R4
Air from
CBA #1 CBA #2
Blower

Sulphur
Condenser #1

R1 R2 Condenser #3
Claus #1 Claus #2

Closed

Sulphur
Opened Condenser #4
Sulphur
Condenser #2 To Incinerator
CBA Process, R3 in regeneration Sulphur

Sulphur Recoveries of 99.3% and 99.4% are expected respectively with a 1+2 and 2+2 arrangements.
About 30 CBA Units are in operation or at design stage with capacities ranging from 2 to 2000 MTPD
(expressed as Claus Unit feed sulphur).
The CBA technology cannot be considered as a true add-on TGCU technique. Generally speaking, CBA
should be considered at the early stages of the Claus + TGCU design when sulphur recoveries at or
above 99% are contemplated. Adding CBA reactors downstream of an existing Claus Unit, although
feasible, is rather delicate as it implies a significant amount of piping work.

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3.5 SUPERCLAUS PROCESS
Two main principles are applied in the SuperClaus process:
- Operating the Claus plant with excess H2S to minimize the SO2 content in the Claus tail gas. This
feature simplifies and makes more flexible the air ratio control.
- Selective oxidation of the remaining H2S in the Claus tail gas by means of specific catalyst which
efficiently convert the remaining H2S in the presence of water vapour and excess oxygen to
elemental sulphur only.
H2S + O2 S + H2O
This reaction takes place in a specific converter (oxidation reactor), downstream of a two or three
reactors traditional Claus unit.
COS and CS 2 produced in the Claus section are not converted. Recoveries up to 99% (typically 98.5 to
98.7%) are achievable downstream a two reactors Claus Unit. Getting over 99% would require a third
Claus reactor and/or and hydrogenation/hydrolysis step. For instance the so-called SuperClaus 99.5
process includes such and hydrogenation/hydrolysis step. Jacobs Comprimo has announced recently
the development of a new catalyst to be used upfront of the SuperClaus reactor. This new arrangement
has been named EuroClaus.
An overall flowscheme of a SuperClaus arrangement is given by the following diagram:

Steam

#1 Reheater
Reaction Furnace
#1 Reactor
Acid Gas & and Waste Heat Boiler
SWS effluent

#1 Condenser

FRC
#2 Condenser
Trim Air Steam
Control Sulphur Sulphur

Air Blower
#2 Reheater Steam

#2 Reactor to Trim Air #3 Reheater

AIC
Control Air
H2S : 0.8 to
1.5 % vol. O2 : 0.5 to
2% vol.
AIC

#3 Condenser SuperClaus
Tail Gas to
Reactor Incinerator
Sulphur #4 Condenser
Sulphur

SuperClaus 99 Process

SUPERCLAUS technology was initially developed by Stork Engineers & Contractors B.V. (now part of
the Jacobs group), and introduced to the industry in 1988. Revamping of an existing Claus Plant to a
SuperClaus configuration is relatively straight-forward. A three stage Claus Unit can easily be revamped
simply by changing the 3rd stage catalyst (plus some piping and minor equipment modifications).
The catalyst used is an Alumina based catalyst coated with iron oxide and chromium oxide layers. It
ensures 80 to 90% H2S to be oxidized to sulphur. Other sulphur species (COS, CS 2, SO2) will pass
through the catalyst as lost recovery, hence the need to operate the upfront Claus Unit with a high H2S to
SO2 ratio at the outlet of the second Claus converter. The catalyst is not sensitive to water.
More than 80 plants have been licensed worldwide, with capacities ranging from 7 to 700 MTPD
(expressed as Claus Unit feed sulphur).

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3.6 CLAUSPOL PROCESS
The Clauspol process consists mainly in an absorber/reactor fitted with several layers of packing. The
Claus Unit Tail Gas from the last condenser is fed to the bottom part of the Clauspol reactor where it is
counter-currently washed with the solvent. The Tail Gas from the reactor is then sent to the downstream
incinerator. The reactor operates at about 120C. This temperature, together with a relatively long
residence time, permits a certain degree of COS and CS 2 hydrolysis.

Tail Gas
to Incinerator

Clauspol
Reactor

HW

Claus Tail Gas

Sulphur
Drum
Catalyst Make-Up

Solvent to Recovery
Liquid Sulphur
CLAUSPOL II Process

The sulphur produced, being only slightly miscible with the solvent, is collected at the bottom of the
absorber/reactor as a separate liquid phase, given its higher density.
As the reaction is exothermic, the heat of reaction is dissipated by the solvent recirculation loop which is
continuously circulated and cooled by a water cooler.
Several versions of the Clauspol process have been developed since its initial introduction over 25 years
ago.
The initial version was named Clauspol 1500. Its Sulphur recoveries were in the range of 98.5% to 99.3%.
More than 30 Units with capacities up to 600 MTPD (expressed as feed to the upfront Claus Unit) have
been implemented. The Clauspol II version was commercially introduced in 1993 and differs in the
method used for solvent temperature control. The initial Clauspol 1500 temperature control was
performed by water injection, whereas in the Clauspol II an indirect cooling through a heat exchanger is
used.
It allows a recovery of about 99.6% of sulphur. 4 Units have been licensed with global capacities ranging
from 25 to 350 MTPD and recoveries from 99 to 99.8% sulphur.

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3.6.1 Clauspol 99.9+
A more recent development of the Clauspol technology is the Clauspol 99.9+. The enhancement of this
version lies in a desaturation loop. Under normal operating conditions, the elemental sulphur in solution
(e.g. dissolved) in the solvent is about 2% wt. The amount of sulphur vapour left in the tail gas to the
incinerator is therefore in equilibrium with this amount of dissolved sulphur. This represents
approximately 300 ppmv sulphur equivalent in the tail gas. In order to further reduce this amount the
overhead tail gas has to be contacted with a stream with less dissolved sulphur. Hence the idea of a
desaturation loop as depicted on the following flowscheme. This o l op can be added to an existing
Clauspol II Unit.

Tail Gas
to Incinerator

Steam
Clauspol
Reactor

HW

Claus Tail Gas CW

Steam

Sulphur
Drum
Catalyst Make-Up

Solvent to Recovery
Liquid Sulphur
CLAUSPOL 99.9+ Process

An overall recovery of 99.9% is claimed, provided that the hydrolysis of COS and CS 2 have reached a
significant level in the upfront Claus Unit.

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3.7 RAR PROCESS
This type of process is by far the most widely applied TGCU type of process which can achieve overall
Sulphur recovery above 99.9%.
The concept underlying H2S scrubbing processes are:
Hydrogenation and hydrolysis of all sulphur compounds to H2S
Absorption of H2S by an Amine solution (generic amine or specialty amine)
Regeneration of the Amine solution and recycle of the H2S to the upfront Claus Reaction
Furnace.

A general process arrangement is given by the following scheme:

H2S recycle
to Claus Unit
Tail Gas
to Incinerator CW

Electric
Heater (1) Absorber
Regenerator
Hydrogen
Make-Up (1) Quench
Tower

Hydrogenation
Reactor CW

CW Steam

Claus Tail Gas

Sour
Water

(1) Other arrangement possible (e.g. RGG)

Typical H2S Scrubbing Process

Hydrogenation reactions are as follows:

SO2 + 3 H2 2 H2O + H2S
Sn + n H2 n H2S

Hydrolysis reactions are as follows:

COS + H2O CO2 + H2S
CS 2 + 2 H2O CO2 + 2 H2S
CO + H2O CO2 + H2

Before the tail gas from the Claus section can be hydrogenated/hydrolyzed, it has to be preheated to
above 280C, in order to activate the hydrolysis/hydrogenation (usually a CoMo type catalyst).
Preheating can be performed in different ways, either by direct combustion or by indirect heating by
means of high pressure steam or hot oil. Typically, all the CS 2 and about 90% of the COS are converted.
Direct combustion is required when no external reducing gas source (Hydrogen and/or CO) is available to
complement the hydrogen and CO present in the Claus tail gas.
Before the reduced gas enters the downstream Amine Unit, it has to be cooled down to the maximum
extent to enhance the absorption by the solvent. This is typically performs in two steps. First the gas is
cooled in a Waste Heat Boiler, generating steam at low pressure, and then it is contacted with cold
water in a quench tower. A gas/gas exchanger may also be used.

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Besides reducing the gas temperature, the purpose of the quench tower is to provide a buffer protection
of the downstream Amine unit in case of upsets of the Claus section. Amine solvents are very sensitive
to SO2 which produces Heat Stable Salts in the Amine Solution, and therefore a good control of the pH of
the circulating water will give an indication of SO2 breakthrough before it reaches the Amine absorber.
H2S is absorbed by a countercurrent flow of lean amine as the tail gas flows up in the low pressure
absorber. The overhead stream containing typically 10 to 250 ppmv H2S, depending on the solvent used,
is sent to the thermal incinerator before being discharged to atmosphere. The rich amine from the bottom
of the absorber is pumped to the regenerator where H2S is stripped by means of steam reboilers. The
overhead stream is recycled back to the reaction furnace of the Claus section. The operating pressure of
the regenerator is set so as to allow a direct recycle.
In certain instances where the operating pressure at the outlet of the Claus section is not sufficient to
feed the scrubbing section, a dedicated blower has to be installed. It is usually located downstream of
the quench tower.
There have been numerous variations of this type of process, initially developed by Shell (SCOT process)
using various types of Amines and of process configurations in order to:
Maximize the H2S absorption,
Minimize the CO2 coabsorption,
Reduce capital cost,
Reduce operating costs.

Several Licensor currently propose variations on the H2S scrubbing process, using solvents available on
the market place, or in some instances proprietary solvents. Overall sulphur recovery ranges from 99.9 to
99.99% depending mainly on solvent selection.
The following development will list the technologies available, and outline potential specific arrangements.
It is restricted mainly to Refinery applications.
RAR is a generic name for various developments in Tail Gas Clean Up and Acid Gas Enrichment from
Technip KTI Spa. For instance, the Multipurpose RAR combines, for lean gases (e.g. with low H2S
content) the Acid Gas Enrichment and the Tail Gas H2S scrubbing in the same absorber. This
arrangement achieves a dramatic capital cost reduction compared to two separate Acid Gas Enrichment
and Tail Gas Clean Up units.

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Evaluation of TGCU Processes Page 15 of 22
3.8 LO-CAT PROCESS
The LO-CAT Process is currently offered for license by US-Filter, a subsidiary of Vivendi. The process
was initially developed at the beginning of the seventies by ARI Technologies, which investigate a range
of chelating agent which would insure iron solubility under a wide range of pH.
The ARI LO-CAT process has been licensed more than 120 times, mainly for small capacities and for
applications such as Sour Natural Gas treatment (small fields), bio-gas applications, amine treaters acid
gas treatment, A few references only exists for TGCU, although the process is fully applicable.
Several arrangements of the LO-CAT II process have been developed depending on the nature of the gas
to be treated.
For gases such as natural gas, or CO2 gas containing H2S (for beverage purpose), a scheme with a
separated absorber is usually applied. The absorber is a column fitted with specific internals, and a
separate oxidizer is provided. This arrangement prevents the treated gas to be contaminated with air.
For gases for which air ingress/contamination is not of concern, the so-called Autocirculation
arrangement is used. This arrangement would be the preferred one for a TGCU Unit.

Vent

Claus Tail Gas

Autocirculation
Vessel Air Intake
Filter

Air Blower
Wash Water
MELTER System

Vent
Belt Filter Sulphur Cake Wash Water

Steam

Slurry
Filtrate Return Pump Sulphur
Tank
Separator

Sulphur Slurry Pump

US-Filter LO-CAT II Process Liquid Sulphur

Absorption and regeneration are performed in a single vessel divided in two sections: the Centerwell and
the outer space where aeration with air is performed. The purpose of the Centerwell is to separate the
sulphite ions from air in order to minimize by-product formation (e.g. thiosulfate). The difference in
aeration (and therefore of density) between the Centerwell and the outer space give sufficient driving force
for solution circulation between the absorption and the regeneration zones without the need of a specific
pump.
The last type of processing scheme is called the aerobic unit and is used to treat air contaminated with
H2S. All reactions take place in the same vessel, at the expense of increased by-product formation, but
with the advantage of a reduced capital cost.
As for all the CIP processes, the sulfur produced is under the form of a sulfur cake, which after washing
in a belt filter (other types of filters may be used, depending of factors such as unit capacity) contains
more than 35% wt of water and a few percent of solution. Should higher sulphur purity be required, then a
sulphur melter section is to be installed.
LO-CAT process can produce a Tail Gas with as low as 10 ppmv H2S. COS, CS 2 and SO2 being
practically inert for the solution, the overall recovery downstream of a Claus Unit is limited to about 98.5
to 99%. Should a higher recovery be required, then an hydrogenation/hydrolysis step is required
upstream of the LO-CAT section.

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Evaluation of TGCU Processes Page 16 of 22
4. COMPARISON METHODOLOGY
4.1 TECHNICAL COMPARISON
In order to present a comparison as accurate as possible of existing Tail Gas Clean-Up technologies, the
different processes were compared on the same basis: this implied a common definition for the inlet
Claus Tail Gas, climatic conditions, available utilities.
A common basis of design was issued to each licensor of the selected processes and a evaluation
package obtained.
Subsequently, the performance of each process (percentage of sulphur removal, utility consumption)
was analysed and the different technologies compared.

4.2 CAPITAL COSTS

Each licensor was requested to provide its own estimate of capital cost. To ensure the consistency of
the costs prepared by licensors, Technip carried out an independent estimate of the capital cost for each
process based on its normal estimating procedure using project data for similar units.
The estimate is given with an accuracy of + 30%, but more importantly, the methodology used to develop
the estimate of each TGCU process and the parent Claus Unit is the same in all cases which ensures
internal consistency.
The capital cost is the total installed cost including engineering, procurement and construction in France.
Are excluded from the above estimate the impact on the refinery environment and existing installations,
such as the impact on any existing Sour Water Stripper, steam systems, firewater and buildings, control
room and other site facilities.

4.3 OPERATING COSTS

The costs related to operator supervision, utility consumption and production and the revenue from sale
of the additional sulphur produced were based on European averages.
Catalyst, solvent and chemical costs used for the economic evaluations were provided by the process
licensors.
The climatic conditions are those of Western Europe.

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Evaluation of TGCU Processes Page 17 of 22
5. RESULTS
5.1 PROCESS PERFORMANCE

5.1.1 Expected Overall Sulphur Recovery and Additional Recovered Sulphur

The following table indicates the expected overall sulphur recovery yield, the resulting additional
recovered sulphur and the dry basis sulphur emission (in the form of SO2) after incineration.
Expected Sulphur Expected Additional Expected Sulphur
Recovery Yield Sulphur Recovered Emission (Dry Basis)
Process Licensor (%) t/d mg / Nm 3
Claus - 96.01 - 13652
Sulfreen Lurgi 99.42 3.56 2010
HydroSulfreen (1) Lurgi 99.67 3.82 1066
DoxoSulfreen (2) Lurgi 99.88 4.04 414
CBA BPVI 99.50 3.65 1726
Superclaus (3) Jacobs 98.66 2.77 4631
Clauspol II IFP 99.60 3.75 1382
RAR KTI 99.94 4.10 242
LO-CAT II (4) US Filter 99.99 4.16 18

(1) Sulfreen reactors and hydrolysis section

(2) Sulfreen reactors, hydrolysis section and DoxoSulfreen reactors
(3) Technip estimate
(4) As LO-CAT II tail gas cannot be incinerated, sulphur is in the form of H2S.

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Evaluation of TGCU Processes Page 18 of 22
 5.1.2 Expected Streams Flows and Compositions
The tables below give the expected TGCU exhaust compositions for sulphur compounds as well as
compositions of the streams emitted to atmosphere after being incinerated at 800C with an O2 excess
of 3% vol. (on a wet basis).
The two first columns deal with the reference Claus unit alone, depicting respectively the tail gas at the
outlet of the third condenser and the stream from stack to atmosphere after being incinerated at 800C
with an O2 excess of 3% vol. on a wet basis.

Claus Sulfreen HydroSulfreen DoxoSulfreen

Tail Gas Vent Tail Gas Vent Tail Gas Vent Tail Gas Vent

Pressure (bar g) 0.45 0.00 0.05 0.00 0.05 0.00 0.05 0.00
Temperature (C) 128.2 800.0 140.1 800.0 140.1 800.0 125 800.0
Flowrate (kmole/h) 434.037 759.701 432.415 752.434 429.950 747.966 429.052 750.759

H2S (kmole/h) 3.261 0.000 0.265 0.000 0.250 0.000 0.071 0.000
CS2 (kmole/h) 0.051 0.000 0.050 0.000 0.005 0.000 0.005 0.000
COS (kmole/h) 0.239 0.000 0.240 0.000 0.024 0.000 0.024 0.000
SO2 (kmole/h) 1.630 5.400 0.133 0.781 0.125 0.452 0.013 0.161
S1 eq. (kmole/h) 0.162 0.000 0.043 0.000 0.043 0.000 0.043 0.000

CBA SuperClaus Clauspol RAR LO-CAT

Tail Gas Vent Tail Gas Vent Tail Gas Vent Tail Gas Vent Vent

Pressure (bar g) 0.03 0.00 0.05 0.00 0.05 0.00 0.05 0.00 0.05
Temperature (C) 126 800.0 132.0 800.0 120.0 800.0 41.0 800.0 52.1
Flowrate (kmole/h) 438.090 764.918 457.704 756.371 432.395 758.930 310.039 555.311 449.785

H2S (kmole/h) 0.370 0.000 0.143 0.000 0.121 0.000 0.084 0.000 0.005
CS2 (kmole/h) 0.020 0.000 0.051 0.000 0.043 0.000 0.000 0.000 0.000
COS (kmole/h) 0.000 0.000 0.239 0.000 0.144 0.000 0.000 0.000 0.000
SO2 (kmole/h) 0.190 0.680 1.304 1.812 0.061 0.542 0.000 0.084 0.000
S1 eq. (kmole/h) 0.080 0.000 0.024 0.000 0.130 0.000 0.000 0.000 0.000

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Evaluation of TGCU Processes Page 19 of 22
5.2 CAPITAL AND OPERATING COST ESTIMATES

5.2.1 Capital Costs Estimates

Usual practice is to relate the capital cost of the TGCU to the one of the upfront Claus unit. The following
table gives estimates of such a ratio, for a 100 MTPD Claus unit (including catalyst) in a Refinery
environment.
Without Licence, Licence, Catalyst and
Catalysts and Chemicals Chemicals included
Process (%) (%)
Sulfreen 29.2 30.9
HydroSulfreen (1) 44.7 47.6
DoxoSulfreen (2) 67.0 76.0
CBA 35.4 36.1
Superclaus (3) 12.3 15.3
Clauspol II 33.7 37.3
RAR 67.2 67.5
LO-CAT II 46.8 49.0
(1) Sulfreen reactors and hydrolysis section
(2) Sulfreen reactors, hydrolysis section and DoxoSulfreen reactors
(3) Technip estimate
The reference to the upstream sulphur unit is indicative and corresponds to the way this kind of
comparison is usually presented in the literature. This comparison should be taken with care when
comparing with other studies, as the capital cost of a sulphur unit may vary for a number of reasons
which are developed below:
Capacity and degree of modularization
Small size plants (capacities below approximately 60 to 80 MTPD on rich gas) could be
preassembled in one of several modules, therefore reducing the erection cost which otherwise can
represent between 30 and 40% of the total erected cost of the unit. In addition, for capacities up to
200 MTPD, several pieces of equipment in the sulphur recovery unit could be grouped in the same
vessel or shell (Claus reactors #1 and #2, Claus condensers #2 and #3), therefore minimizing the
equipment cost.
Sulphur recovery unit capital cost estimate is based on separate equipment with no modularization.
This estimate was performed in a manner consistent with the downstream TGCU Units. This estimate
is probably on the high side of capital cost, therefore reducing the ratio TGCU / SRU.
Acid Gas quality
Depending on the acid gas H2S content, the impact on the sulphur recovery unit and the TGCU
configuration can be different.
The following points shall also be highlighted:
The same methodology was followed for each unit, which provides internal consistency.
The estimated accuracy for capital cost estimate is + 30%.
CBA capital cost is the most difficult cost to estimate, as, depending of the actual configuration of
the Claus unit, the extent of piping works modification may vary from Plant to Plant. The current
capital cost assumes that modifications to piping and equipment are minor.

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Evaluation of TGCU Processes Page 20 of 22
5.2.2 Operating Cost Estimates
The estimate of operating costs, including sulphur produced, utilities and chemicals as well as additional
manpower expense are given below.
OPERATING COST
Operation Recovered TOTAL
Cost Sulphur
Process k$ / y k$ / y k$ / y
Sulfreen 103 -24 79
HydroSulfreen 154 -26 128
DoxoSulfreen 390 -27 363
CBA 59 -25 34
Superclaus 128 -19 109
Clauspol II 124 -25 99
RAR 189 -28 161
LO-CAT II 331 -28 303

5.3 ESTIMATED RECOVERY COST OF SO2

The estimated ranges for recovery cost of SO2 for each process are given in the following table.
Expected Sulphur Expected Additional Recovery Cost
Recovery Yield Sulphur Recovered Ranges of SO2
Process (%) (t / d) ($ / t)
SuperClaus 98.66 2.77 137 / 202
Sulfreen 99.42 3.56 154 / 256
CBA 99.50 3.65 150 / 266
Clauspol II 99.60 3.75 176 / 292
HydroSulfreen 99.67 3.82 224 / 370
DoxoSulfreen 99.88 4.04 404 / 624
RAR 99.94 4.10 284 / 477
LO-CAT II 99.99 4.16 271 / 409

Calculations have been performed based on the following hypothesis:

- The TGCU cost includes license fee, catalyst and first fill of chemicals. These investments are
financed by a fully reimbursable 10-year loan with a 6% interest rate.
- The catalyst lifetime is 3 years (part of the operating costs). The related investment every 3 years is
financed by a fully reimbursable 3-year loan with a 6% interest rate.
- The solvent and chemical make-up (part of the operating costs) were calculated on a yearly basis as
a cash expense.
- The consumption and production of utilities as well as the manpower costs were considered
constant over time.
- The price of sulphur was also considered constant over time.

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Evaluation of TGCU Processes Page 21 of 22
 6. CONCLUSIONS
The conclusion is in the form of a graphical comparison showing for each TGCU studied
q Overall sulphur recovery for the Claus plant plus TGCU (%)
q The range of costs for recovery of non-rejected SO2 for each TGCU studied reflecting the +/-30%
accuracy of the capital cost estimate.

Recovery Cost of TAIL GAS CLEAN-UP Yield (%)

SO2 ($ / t)
700 100.00

600

500 99.50

400

300 99.00

200

100 98.50

Estimated Recovery Cost of SO2 Sulphur Recovery Yield

GPA Europe Technical Meeting, Paris, 21st February, 2003

Evaluation of TGCU Processes Page 22 of 22