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Chapter 4

Techniques to consider in the determination of BAT

Corrosive salts, which concentrate during recycling, can be removed via ion exchange
techniques. Some proprietary solutions may be biodegradable under suitable conditions.
It is important also that the amine processes have sufficient capacity to allow maintenance
activities and upsets. This sufficient capacity can be achieved by having redundancy equipment,
apply load shedding, emergency amine scrubbers or multiple scrubber systems.
Applicability
Process off-gas streams from the coker, catalytic cracking unit, hydrotreating units and
hydroprocessing units can contain high concentrations of hydrogen sulphide mixed with light
refinery fuel gases. Emergency H2S scrubbers are also important.
Economics
The cost of upgrade the refinery amine treatment system (2 %) to meet 0.01 to 0.02 % v/v of
H2S in fuel gas is around 3.75 to 4.5 million EUR. This cost is battery limit costs based on 1998
prices and include such items as equipment, licence fees, foundations, erection, tie-ins to
existing plant and commissioning. They are an order of magnitude only. Site-specific factors
such as layout, available space and necessary modifications to existing plant could have a
significant impact. In some cases these factors might be expected to increase the costs by some
50 %.
Driving force for implementation
Reduce the sulphur content of flue gases.
Example plant(s)
Common technology used all over the world
Reference literature
[118, VROM, 1999], [211, Ecker, 1999], [19, Irish EPA, 1993], [268, TWG, 2001]
4.23.5.2 Sulphur recovery units (SRU)
H2S-rich gas streams from Amine Treating Units (see above section) and Sour Water Strippers
(see Section 4.24.2) are treated in a Sulphur Recovery Unit (SRU) normally a Claus process for
bulk sulphur removal and subsequently in a Tail Gas Clean-up Unit (TGCU, see later in this
section) for trace H2S removal. Other components entering the SRU include NH3, CO2 and to a
minor extent various hydrocarbons.
4.23.5.2.1 Claus Process

Description
The Claus process consists of partial combustion of the hydrogen sulphide-rich gas stream (with
one-third the stoichiometric quantity of air) and then reacting the resulting sulphur dioxide and
unburned hydrogen sulphide in the presence of a activated alumina catalyst to produce
elemental sulphur.
OFF-GAS
TO STACK

STEAM

ACID GAS

LINE BURNER
REACTORS

MAIN BURNER

LINE BURNERS

AIR

230-300C
0.3 barg

STEAM

BFW
BFW

INCINERATOR
REACTOR

200-220C
0.2 barg

TAIL GAS
TO TGT
STEAM

SULPHUR PIT

SULPHUR

Figure 4.11: Simplified process flow diagram of a sulphur recovery unit (CLAUS) unit
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The capacity of the Claus plants can be increased with the use of oxygen instead of air
(OxyClaus process) however this has not any beneficial effect in the efficiency of the Claus
plant. Use of this process increase capacity up to 200 % in existing Claus sulphur recovery
units, or for a more economical design of Claus sulphur units.
Achieved environmental benefits
Number of Claus reactors
1
2
3

Efficiency (%H2S converted)


90
94 - 96
97 - 98

Table 4.36: Efficiencies of the Claus process

Cross-media effects
Emissions based on 20000 t/yr SRU

Source

Flow

Emissions:
CO2, SO2,
NOx

Incinerator
off-gas

0.2 % of total
H2S-load to
the SRU

Effluent:

Knock-out drum for


water in SWS offgas
Spent SRU catalyst

0.02 m3/h

Waste

plant specific

Composition
min/max
SO2 1500
mg/Nm3 Through
presence of NH3
non-catalytic
deNOxing takes
place
H2S: 50 mg/l;
Phenol: 100 mg/l;
NH3: 2000 mg/l
Mainly Al2O3

Comments
Amount of SO2 released depends
on total sulphur production and
overall sulphur recovery

To be treated in the SWS

The reduction of SO2 leads to an increase of the CO2 emission. For example for a 100 t/d
sulphur claus plant, the application of three reactors would lead to an emission of 4.8 tonnes of
sulphur per day at a cost of 8.5 tonnes of CO2 per day.
Operational data
Feed/air ratio control, temperature control of the furnace, reactors and condensers and good
demisting of liquid sulphur, especially from the final condenser exit gas stream are
important parameters in obtaining maximum sulphur recovery. Good control and
availability is crucial as a technique, to deliver any design targets. In this line, the use of
state-of-the-art control and monitoring systems can be seen as an important technique. Use
of a tail gas analyser linked to the process control system (feedback control) will aid
optimum conversion during all plant operating conditions, including changes to sulphur
throughput
To have a SRU configuration with sufficient capacity for the H2S feed to the unit including
the sourest crude oil to be used is important. The duplication of the SRU capacity is
important to consider to obtain low sulphur emissions. This enough capacity also should
consider to allow the scheduled maintenance activity to proceed every two years, without a
significant increase of sulphur emissions.
To have utilisation factors close to 100% increase how efficient the units are used. Those
capacity factors should plan also major turnaround maintenance.
use a good furnace burning-zone design and effective furnace temperature and oxygen
control systems where sour water stripper off-gases are a feed stream, because the process
must also be designed and operated to complete the destruction of ammonia. Ammonia
breakthrough may lead to deposition and blockages of catalyst beds by ammonium salts (eg
carbonate/sulphate) and these SRUs need to be monitored for evidence of this.
The utilities necessary in the SRU are summarised in next table
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Techniques to consider in the determination of BAT

Fuel (MJ/t)

Electricity
(kWh/t)
60 - 75

1000 1600

Steam produced
(kg/t)
1500 - 2000

Cooling water
(m3/t, T=10 C)
0 - 20

In some cases, the SRU need a pilot flame when the H2S concentration is so low that a stable
flame cannot be achieved.
Applicability
Fully applicable
Economics
Abatement

Plant size
range

Approximate
capital cost
(EUR million
installed)
2.1 - 5.3

Approximate
operating cost per
year (EUR million)

Upgrade SRU with O2 enrichment to


100 t/d
1.6 (costs are for
increase throughput from100 t/d to 170 t/d.
oxygen)
They are battery limit costs based on 1998 prices and include such items as equipment, licence fees,
foundations, erection, tie-ins to existing plant and commissioning. They are an order of magnitude only.
Site-specific factors such as layout, available space and necessary modifications to existing plant could
have a significant impact. In some cases these factors might be expected to increase the costs by some
50 %.

Another example of the upgrade of SRU with oxygen enrichment (Oxyclaus)


Economics: For a reference 200 tpd sulphur recovery unit (Claus and tail gas unit) requiring
99.9 % overall sulphur recovery, capital cost savings of $2 - 3 million are achievable with
oxygen enrichment as compared to an air only design. Based on typical pipeline oxygen costs of
$35 per tonne, even if oxygen enrichment were used 100 % of the time, it would take over
8 years for oxygen costs to equal the increamental capital saving.
Example of the economics of the installation of a third Claus reactor.
Capacity of process: 30000 t/yr sulphur production (sulphur recovery efficiency 94 - 96 % for a
two stage unit); Volume of gas: 60 million m3/yr; Pollutant initial concentration: 34000 mg
SO2/m3 (1.2 % molar or 2.3 % weight, rest considered as air) The investment cost to build a new
third reactors is between EUR 2 and 3 millions and the operating cost around EUR 0.1 million
per year.
Driving force for implementation
Reduction of sulphur emissions
Example plants
In the market, it exists more than 5 licensors of this process. The Claus process is public domain
and virtually applied at any refinery. Two stages Claus process is the most common in Europe.
More than 30 Oxyclaus systems are in operation in the world.
Reference literature
[250, Winter, 2000], [258, Manduzio, 2000], [115, CONCAWE, 1999], [45, Sema and Sofres,
1991], [181, HP, 1998], [114, Ademe, 1999]
4.23.5.2.2 Tail Gas Treatment Unit (TGTU)

Description
Current methods for removing sulphur from the hydrogen sulphide gas streams are typically a
combination of two processes: the Claus process (See section above) followed by a tail gas
clean-up or treatment unit. Since the Claus process by itself removes about 96 % (2 stages) of
the hydrogen sulphide in the gas stream, the TGTU processes are often used to further recover
sulphur.
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More than 20 processes for TGTU have been developed in order to enhance the recovery of
Sulphur compounds from natural gas and/or refinery sources. TGTU processes can be broadly
divided according to the principles applied:
-

Dry bed processes, where the main process step is achieved on a solid catalyst. Two paths
have been followed within this group: a) Extend Claus reaction on a solid bed, b)Oxidise
sulphur compounds to SO2 prior to absorption, or reaction.

Liquid Phase Sub-DewPoint processes, consisting of extending the Claus reaction under
sub-dewpoint conditions in liquid phase.

Liquid scrubbing processes. There are two main categories, H2S scrubbing processes and
SO2 scrubbing processes. In the most commonly applied configurations, H2S or SO2 are
recycled to the upstream Claus Unit.

Liquid Redox process. Liquid phase oxidation processes to absorb H2S.

The first and third categories can further be divided in sub-categories depending on the sulphur
recovery method used. It should be noted that a strict distinction between dry beds and liquid
scrubbing processes may become uneasy as some arrangement combine the capabilities of both
types of processes. Some processes belonging to the four groups above-mentioned are further
explained below; this list is not intended to be exhaustive:
The H2S Scrubbing process is by far the most widely applied. The concept underlying H2S
scrubbing processes are:
- Hydrogenation and hydrolysis of all sulphur compounds to H2S passing it through a cobaltmolybdenum catalyst with the addition of a reducing gas
- 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.
Several Licensor currently propose variations on the H2S scrubbing process, using solvents
available on the market place, or in some instances proprietary solvents.
TAIL GAS
FROM SRU

OFF-GAS
TO INCINERATOR
RETURN ACID
GAS TO SRU

SCOT BURNER
QUENCH
WATER COOLER

NATURAL GAS
AIR

WATER
MAKE-UP
ABSORBER

REGENERATOR

REDUCTION
REACTOR
STEAM

STEAM

BFW

SOUR WATER
TO SWS

Figure 4.12: Simplified process flow diagram of a tail gas Claus unit (SCOT) unit

The Sulfreen process is a dry-bed, sub-dew point absorption process based on the extension of
the Claus reaction, i.e. catalytic oxidation of H2S to S. Basically consists of two (occasionally
three for large capacities) Sulfreen reactors in series with the Claus reactors. Activated Alumina
is used as a catalyst. Regeneration is needed since the sulphur accumulates on the catalyst
decreasing its activity. Sulphur from the hot regeneration stream is condensed in a dedicated
condenser. Two variations are used: Hydrosulfreen and DoxoSulfreen.
The HydroSulfreen adds a conversion step upstream of the first Sulfreen reactor, to perform the
hydrolysis of COS and CS2 to H2S with the help of a activated Titanium oxide Claus catalyst.
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The Claus reaction takes place in the HydroSulfreen reactor and produced sulphur is condensed
in a dedicated condenser
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; then the remaining H2S
is directly oxidised to elemental Sulphur
In the Beaven process, the hydrogen sulphide in the relatively low concentration gas stream
from the Claus process can be almost completely removed by absorption in a quinone solution.
The dissolved hydrogen sulphide is oxidized to form a mixture of elemental sulphur and hydroquinone. The solution is injected with air or oxygen to oxidize the hydro-quinone back to
quinone. The solution is then filtered or centrifuged to remove the sulphur and the quinone is
then re-used. The Beaven process is also effective in removing small amounts of sulphur
dioxide, carbonyl sulphide, and carbon disulphide that are not affected by the Claus process.
These compounds are first converted to hydrogen sulphide at elevated temperatures in a cobalt
molybdate catalyst prior to being fed to the Beaven unit.
The CBA (cold bed absorption), process is very similar to the Sulfreen process except in the
fact that the CBA process uses a hot process stream indigenous to the Claus process to
accomplish regeneration of the sulphur loaded catalyst bed. The hot process stream is part of the
effluent of the first Claus reactor. Several configurations are available depending on the number
of Claus converters.
The Clauspol is a process where the tail gas is put in contact with a solvent (polyethylene
glycol) and the reaction of H2S and SO2 is catalysed by a dissolved catalysts. (sodium salt of an
inorganic acid) which is a solvent for H2S and SO2, but not for liquid sulphur.The Claus reaction
can therefore proceed at low temperature (120 C) and is shifted further to the right as the
produced sulphur is removed from the reaction medium, as it is not soluble and separates.
The Superclaus process is based on two principles:
- Operating the Claus plant with excess H2S to minimise 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.
This reaction takes place in a specific converter (oxidation reactor), downstream of a two or
three reactors traditional Claus unit. The catalyst used is an alumina based catalyst coated with
iron oxide and chromium oxide layers.
The LO-CAT process. 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 byproduct formation (e.g. thiosulphate). 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.
The SO2 abatement from the Claus plant is a process that uses a physical scrubbing mechanism
to remove SO2 from the incinerated tail gas of a Claus plant. The recovered SO2 is recycled to
the inlet of the Claus plant unit.
Achieved environmental benefits
Tail gas treatment units increase the overall recovery of H2S decreasing the sulphur emissions
from the refinery. For example, if a refinery has a 100 t/d SRU, with a two stage Claus reactor
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Chapter 4

emits around 5 t/d of sulphur. If a tail gas clean-up process is included in such a refinery the
emissions of sulphur may be reduced to 0.5 t/d, representing that a reduction of 90 % of the
sulphur emissions from the sulphur recovery units. Next table shows the expected overall
sulphur recovery yield, the resulting additional recovered sulphur and the dry basis sulphur
emission (in the form of SO2 specie) after incineration, of the tail gas treatments considered in
this Section.

Expected sulphur
recovery yield

Expected additional
sulphur recovered

Expected SO2 emissions


(Dry Basis)

(%)
96.01

t/d

mg / Nm3
13652

Process
Claus

2.77
98.66
4631
Superclaus
3.56
99.42
2010
Sulfreen
99-99.9
Beavon
3.65
99 - 99.50
1726
CBA
99.5 99.9
Clauspol
3.75
99.60
1382
Clauspol II
99.9
SO2 abatement
3.82
99.67
1066
HydroSulfreen (1)
4.04
99.88
414
DoxoSulfreen (2)
4.10
99.94
242
RAR
4.16
99.99
18
LO-CAT II (3)
99.5-99.99
SCOT
(1) Sulfreen reactors and hydrolysis section
(2) Sulfreen reactors, hydrolysis section and DoxoSulfreen reactors
(3) As LO-CAT II tail gas cannot be incinerated, sulphur is in the form of H2S specie.

Table 4.37: Expected overall sulphur recovery yield, the resulting additional recovered sulphur
and the SO2 emissions (dry basis) after incineration

Cross-media effects
The reduction of SO2 leads to an increase of the CO2 emission. For instance the application of a
tailing gas treatment would lead to a SO2 reduction of 96 % (if compared with the three reactor
option), however at an increase for CO2 of 110 %. For example for a 100 t/d sulphur claus plant
with three reactors, the application of a TGTU would reduce the emissions of SO2 to 0.1 t/d but
at a price of increasing the CO2 emissions to 18 t/d.
Emissions based on 20000 t/yr SRU/TGCU.

Source
Effluents

Waste:
SCOT

Sour water from


quench column for
SRU off-gas
Spent TGCU
catalyst

Flow
1m3 / tonne S
produced
(2 m3/h)
Regeneration
and disposal
20 - 100 t/yr

Composition
min/max
H2S: 50 mg/l;
Phenol: 100 mg/l;
NH3: 2000 mg/l
2 - 8 % Ni/Mo on
Al2O3,
S: 5 - 15 %;
Coke: 10 - 30 %

Comments
To be treated in the SWS
Spent Claus catalyst is pyrophoric
and needs purging with N2

Table 4.38: Cross-media effects associated to some of the TGTU

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Techniques to consider in the determination of BAT

Operational data
Good control and availability is crucial as a technique, to deliver any design targets. The
estimate of operating costs, including sulphur produced, utilities and chemicals as well as
additional manpower expense are given in the following table:
OPERATING COST ESTIMATE

Process
Sulfreen
HydroSulfreen
DoxoSulfreen
CBA
Superclaus
Clauspol II
RAR
LO-CAT II

Utilities
Consumption

Utilities
Production

k$ / y
52
82
125
36
106
52
133
138

k$ / y
-6
-22
-29
n/a
-32
n/a
n/a
n/a

Catalyst
Chemical
Operation
Consumption Consumption
Cost
k$ / y
37
74
264
13
44
26
16
15

k$ / y
n/a
n/a
n/a
n/a
n/a
26
10
148

k$ / y
20
20
30
10
10
20
30
30

Recovered
Sulphur

TOTAL

k$ / y
-24
-26
-27
-25
-19
-25
-28
-28

k$ / y
79
128
363
34
109
99
161
303

Table 4.39: Operating costs of some TGTU units

Applicability
Applicable to both new and existing plants. Capacities range from 2 to more than 2000 tonnes
of sulphur per day from the combined Claus/tail gas treatment units.
Economics
The cost of the SRU depends strongly on the type of tail gas treatment. Following several tables
show some examples of economics of the TGTUs.
Abatement

Plant size
range

Approximate
Approximate operating
capital cost
cost per year
(EUR million
installed)
SRU including Tailgas treatment unit
50 t/d
12
New SRU operating cost
(TGTU) to give>99 % S recovery
100 t/d
19
approximately equal to
250 t/d
35
existing costs.
Tailgas treatment unit to improve SRU
50 t/d
1.6
Operating cost relatively
recovery to 99 %
100 t/d
2.1
low
250 t/d
2.9
Operating cost relatively
3.5
Tailgas treatment unit to improve SRU
50 t/d
low
4.4
recovery to 99.8 %
100 t/d
6.3
250 t/d
They are battery limit costs based on 1998 prices and include such items as equipment, licence fees,
foundations, erection, tie-ins to existing plant and commissioning. They are an order of magnitude only.
Site-specific factors such as layout, available space and necessary modifications to existing plant could have
a significant impact. In some cases these factors might be expected to increase the costs by some 50 %.

Usual practice is to relate the capital cost of the TGCU to the one of the up front Claus unit. The
following table gives estimate of such ratio, for a 100 t/d Claus unit (including catalyst) in a
refinery environment.

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Without Licence, Catalysts


and Chemicals

Licence, Catalyst and


Chemicals included
(%)
30.9
47.6
76.0
36.1
15.3
37.3
67.5
49.0

(%)
Process
29.2
Sulfreen
44.7
HydroSulfreen (1)
67.0
DoxoSulfreen (2)
35.4
CBA
12.3
Superclaus
33.7
Clauspol II
67.2
RAR
46.8
LO-CAT II
(1) Sulfreen reactors and hydrolysis section
(2) Sulfreen reactors, hydrolysis section and DoxoSulfreen reactors

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 greatly.
A particular example of the cost of a three stages Claus plant plus TGTU superclaus process is
shown in the following table:
3rd Stage Claus plus super-Claus (1997)
DESCRIPTION
INDIRECT COSTS
Detailed Engineering
Field Supervision
Owner
Subtotal
DIRECT COSTS EQUIPMENT
Materials
Catalysts and Chemicals
Subtotal
DIRECT COSTS - NON EQUIPMENT
Subcontracts
Temporary Construction & Consumables
Subtotal
Total Capital
EXPENSE
Licensing Fee
Subtotal
Final Total

k EUR

8.0
1.6
2.4
12.0

27
8
40

7.3
0.6
7.9

25
2
27

8.6
0.4
9.0
28.9

29
1
30
97

0.5
0.5
29.4

2
2
99

Table 4.40: Economics of tail gas treatment units of the sulphur recovery units

Another example of the cost of a TGTU unit reports that for a Clauspol unit treating a typical
Claus unit tail gas, combined production of 100 tonnes of sulphur per day (ISBL 1998 Gulf
Coast location), the investment (excluding engineering and license fees) came up to 3 million
US$.
The following table shows specific costs data for SO2 abatement under the assumptions outlined
in Annex IV.

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Name of the technique

EUR/tonne SO2
abated (1)

EUR/tonne SO2
abated (2)
32
32
32

3rd reactor
Stand Alone Scot
321-538
Cascade Scot Common
regenerator
Super Claus
155-228
32-161
Super Claus + Claus Stage
32-160
Clauspol
198-330
32
Sulfreen
174-288
32-160
Hydro-sulfreen
253-417
32-160
CBA/AMOCO cold real
169-300
absorption
(1) [346, France, 2001]. Bases for calculation in Annex IV
(2) [115, CONCAWE, 1999] Bases for calculation in Annex IV
Driving force for implementation
Reduction of sulphur emissions and recovery of sulphur.
Example plants
Technique
Beavon
Clauspol
Sulfreen/Hydrosulfreen
Superclaus

Number of installations all over the world


More than 150 installations
More than 50 units
More than 150 units in operation
More than 70 commercial plants

Table 4.41: Approximate number of commercial installations in the world

Reference literature
[195, The world refining association, 1999], [112, Foster Wheeler Energy, 1999], [309,
Kerkhof, 2000], [257, Gilbert, 2000], [115, CONCAWE, 1999], [107, Janson, 1999], [181, HP,
1998], [114, Ademe, 1999], [45, Sema and Sofres, 1991], [346, France, 2001]
4.23.5.2.3 Sulphur storage

Description
In order to reduce the emissions of H2S from the storage and transport of liquid sulphur, the
amount of H2S and polysulphides in the sulphur can be reduced to <10 ppm by oxidation or
treatment with a suitable additive.
Reference literature
[268, TWG, 2001]
4.23.5.3 Hydrogen sulphide and light mercaptan removal
Description
The system works with a fixed-bed or batch-type granular reactant.
Achieved environmental benefits
Processes for odour and low emission control features.
Applicability
Applications to waste water sytems, land oil tanker vent, oil storage and transportation, and
bitumen plants.
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Mineral Oil and Gas Refineries

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