Techniques to consider in the determination of BAT Chapter 4

4.23.5 Sulphur management system

Sulphur is an inherent component of crude oil. Part of this sulphur leaves the refinery in its
products, part of it is emitted to the atmosphere (already described in all the processes) and part
of it is recovered by some processes located in the refinery for this purpose (more information
about the sulphur split in a refinery in Section 1.4.1). Sulphur is an environmental issue that
cannot be addressed in an integrated manner if sulphur coming out with the products is not
considered. In other words, decreasing emissions from a refinery may result in the production of
fuels (products) that may later be burned in a way that is not environmentally efficient, thereby
jeopardising the environmental effort made in refineries.

Because it is such an integrated issue, proper sulphur management (See Annex VI) should also
consider other topics that are not within the objectives of this document. For example, a global
environmental impact assessment of sulphur dioxide emissions should contain:

1. Atmospheric emissions from processes generating SOx (furnaces, boilers, FCC, etc.). Those
issues are in fact included in this document in each of the process sections.

2. Atmospheric emissions from sulphur recovery units or of gases containing sulphur in an

H2S form before incineration. This category of sulphur is normally recovered, as shown in
Section 4.23.5.2.

3. Atmospheric emissions generated by sulphur contained in products for which more

stringent specifications already exist, such as gasolines, gasoils, etc. Those emissions cannot
be considered here because they do not fall within the scope of IPPC legislation, but they
should be considered as part of an integrated approach.

4. Atmospheric emissions generated by products with less stringent specifications (bunkers,

coke, heavy fuel oil). Typically, those products (heavy residues) contain high quantities of
sulphur. If they are not used in a proper way from the environmental point of view, the
emissions can jeopardise the integrated approach to reducing sulphur emissions from the
refinery sector. Another threat to this integrated approach is the exporting of those products
to countries with less environmental control.

5. Sulphur contained in non-fuel products such as bitumen or lubricants is typically not

identified as a problem.

In principle refiners have the following options and combinations thereof to reduce the SO2
emissions of the refinery:
increase the use of non sulphur containing gas (LPG, natural gas, etc.) discussed in
Section 4.10 Energy system
to lower the sulphur content of the fuels used (reduce the H2S content in the refinery fuel
gas with amine treating Section 4.23.5.1, gasification of heavy fuels Section 4.10,
hydrotreatment of fuels in Section 4.13.2 )
to use low sulphur crudes discussed in Sections 4.10 Energy system
increase the efficiency of the SRU discussed in Section 4.23.5.2 Sulphur recovery units
(SRU)
to apply end-of-pipe techniques to capture the SO2 from the fumes (namely flue gas
desulphurisation(FGD)) (those techniques are the ones discussed in Section 4.23.5.4and
have been considered in Sections 4.5 Catalytic cracking and 4.10 Energy system).
reduce SO2 emission from typically small contributors whey they become significant
part of the total emission. For example in the case of gas refineries, the overall picture of
the sulphur emissions change because small contributors in liquid-fired refineries
become significant.

In this section, only those processes dealing with the recovery of sulphur is going to be
considered. Between 17 to 53 % (average 36 %) of the sulphur is recovered in European

Mineral Oil and Gas Refineries 335

Chapter 4 Techniques to consider in the determination of BAT

refineries. H2S formed at various processes such as hydrotreating, cracking, and coking in a
refinery, finally ends up as contaminant in refinery fuel gas and treat gas streams. In addition to
H2S these gases also contain NH3 and to a lesser extent CO2 and traces of COS/CS2. H2S
removal from these gases is achieved by extraction with an amine solvent. After regeneration of
the solvent the H2S is released and sent to a Sulphur Recovery Unit (SRU).

4.23.5.1 Amine treating

Description
Before elemental sulphur can be recovered in the SRU, the fuel gases (primarily methane and
ethane) need to be separated from the hydrogen sulphide. This is typically accomplished by
dissolving the hydrogen sulphide in a chemical solvent (absorption). Solvents most commonly
used are amines. Dry adsorbents such as molecular sieves, activated carbon, iron sponge and
zinc oxide may also be used. In the amine solvent processes, amine solvent is pumped to an
absorption tower where the gases are contacted and hydrogen sulphide is dissolved in the
solution. The fuel gases are removed for use as fuel in process furnaces in other refinery
operations. The amine-hydrogen sulphide solution is then heated and steam stripped to remove
the hydrogen sulphide gas. In Figure 4.10 a simplified process flow diagram of an amine
treating unit is shown.

ACID GAS
FUEL GAS
TO SULPHUR
RECOVERY

WATER
MAKE-UP

ABSORBER REGENERATOR

FLASH GAS STEAM

SOUR GAS
TO FUEL GAS

LEAN
AMINE

FLASH DRUM

OPTIONAL

Figure 4.10: Simplified process flow diagram of an amine treating unit

The main solvents used are MEA (Mono ethanol amine), DEA (diethanol amine), DGA
(diglycol amine), DIPA (Di-isopropanol amine), MDEA (Methyl diethanol amine) and a
number of proprietary formulations comprising mixtures of amines with various additives. One
important issue concerning the selection of the type of amine is the selectivity concerning H2S
and CO2.

1. MEA has had a wide spread use, as it is inexpensive and highly reactive. However, it is
irreversibly degraded by impurities such as COS, CS2 and O2, and therefore is not
recommended to use when gases from cracking units are present.
2. DEA is more expensive than MEA but is resistant to degradation by COS and CS2 and
has obtained a wide spread use.
3. DGA is also resistant to degradation by COS and CS2 but is more expensive than DEA
and has the disadvantage to absorb also hydrocarbons.

336 Mineral Oil and Gas Refineries

Techniques to consider in the determination of BAT Chapter 4

4. DIPA, which is used in the ADIP process, licensed by Shell. It can be used for selective
H2S removal in the presence of CO2 and is also effective in removing COS and CS2.
5. MDEA is nowadays most widely used, MDEA has a similar characteristic as DIPA, i.e. it
has a high selectivity to H2S, but not to CO2. As MDEA is used as a 40 - 50 % solution
(activated MDEA) in water, this has also potential energy savings. Because of the low
selectivity for CO2 absorption DIPA and MDEA are very suitable for use in Claus Tailgas
amine absorbers, as these do not tend to recycle CO2 over the Claus unit. MDEA is
applied as a single solvent or as in proprietary formulation comprising mixtures.

Achieved environmental benefits

Sulphur is removed from a number of refinery process off-gas streams (sour gas or acid gas) in
order to meet the SOx emissions limits of the applicable regulation and to recover saleable
elemental sulphur. The amine treating unit produces two streams for further use/processing in
downstream units:
The treated gas stream usually can contain between 20 and 200 mg/Nm3 H2S (H2S content
depends on absorber operating pressure; at only 3.5 bar H2S level is 80 140. At higher
pressures as 20 bars the H2S level is around 20).
The concentrated H2S/acid gas stream is routed to the SRU for sulphur recovery (discussed
in next Section 4.23.5.2).

Cross-media effects

Source Flow Composition Comments

Effluent: Amine 10 - 50 t/yr Decomposed amine up In order not to disturb the
amine regenerator for a 5 Mt/yr to 50 % in water biotreater operation and to
blow down refinery meet effluent discharge
specifications on N-Kj an
storage tank or production
planning can be used to
control very small flow to the
WWTP
Waste 1: Amine filter plant FeS and salt deposits Removed by skid mounted
cleaning residue specific unit operated by a specialised
contractor (usually the filter
supplier)
Waste 2: Saturated plant Decomposition The saturated activated carbon
activated carbon specific products, heavy ends filling has to be replaced
from skid and amine emulsions occasionally for disposal or
mounted unit regeneration

Operational data
The use of selective amines should be considered, e.g. for a stream containing carbon dioxide.
Measures should be taken to minimise hydrocarbons entering the sulphur recovery system;
operation of regenerator feed drums should be controlled to prevent hydrocarbon accumulation
in, and sudden release from, the amine regenerator as this is likely to lead to an emergency shut-
down of the SRU.

Utility consumption per tonne of H2S removed in an amine treating unit is approximately:

Electricity (kWh/t) Steam consumed (kg/t) Cooling water (m3/t, T =10C)

70 80 1500 - 3000 25 - 35

Usually a fresh solvent make up rate of 10 - 50 t/yr is required to maintain solvent strength for a
5 Mt/yr refinery.

Amine solutions should be re-used wherever possible and where necessary, suitably treated
before disposal which should not be to land. Recycling of monoethanoleamine-solutions:

Mineral Oil and Gas Refineries 337

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
STEAM TO STACK
ACID GAS LINE BURNER
REACTORS INCINERATOR
REACTOR
MAIN BURNER
LINE BURNERS
230-300C 200-220C
AIR STEAM 0.2 barg TAIL GAS
0.3 barg
TO TGT
BFW
BFW STEAM

SULPHUR PIT SULPHUR

Figure 4.11: Simplified process flow diagram of a sulphur recovery unit (CLAUS) unit

338 Mineral Oil and Gas Refineries

Techniques to consider in the determination of BAT Chapter 4

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 Efficiency (%H2S converted)

1 90
2 94 - 96
3 97 - 98

Table 4.36: Efficiencies of the Claus process

Cross-media effects

Emissions based on 20000 t/yr SRU

Source Flow Composition Comments
min/max
Emissions: Incinerator 0.2 % of total SO2 1500 Amount of SO2 released depends
CO2, SO2, off-gas H2S-load to mg/Nm3 Through on total sulphur production and
NOx the SRU presence of NH3 overall sulphur recovery
non-catalytic
deNOxing takes
place
Effluent: Knock-out drum for 0.02 m3/h H2S: 50 mg/l; To be treated in the SWS
water in SWS off- Phenol: 100 mg/l;
gas NH3: 2000 mg/l
Waste Spent SRU catalyst plant specific Mainly Al2O3

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

Mineral Oil and Gas Refineries 339

Chapter 4 Techniques to consider in the determination of BAT

Fuel (MJ/t) Electricity Steam produced Cooling water

(kWh/t) (kg/t) (m3/t, T=10 C)
1000 1600 60 - 75 1500 - 2000 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 Approximate Approximate
range capital cost operating cost per
(EUR million year (EUR million)
installed)
Upgrade SRU with O2 enrichment to 100 t/d 2.1 - 5.3 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.

340 Mineral Oil and Gas Refineries

Techniques to consider in the determination of BAT Chapter 4

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 cobalt-
molybdenum 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.

OFF-GAS
TO INCINERATOR
TAIL GAS
FROM SRU RETURN ACID
SCOT BURNER GAS TO SRU
NATURAL GAS QUENCH
WATER COOLER
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.

Mineral Oil and Gas Refineries 341

Chapter 4 Techniques to consider in the determination of BAT

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 hydro-
quinone. 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 by-
product 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

342 Mineral Oil and Gas Refineries

Techniques to consider in the determination of BAT 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 Expected additional Expected SO2 emissions

recovery yield sulphur recovered (Dry Basis)
Process (%) t/d mg / Nm3
Claus 96.01 - 13652
Superclaus 98.66 2.77 4631
Sulfreen 99.42 3.56 2010
Beavon 99-99.9 - -
CBA 99 - 99.50 3.65 1726
Clauspol 99.5 99.9
Clauspol II 99.60 3.75 1382
SO2 abatement 99.9
HydroSulfreen (1) 99.67 3.82 1066
DoxoSulfreen (2) 99.88 4.04 414
RAR 99.94 4.10 242
LO-CAT II (3) 99.99 4.16 18
SCOT 99.5-99.99
(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 Flow Composition Comments
min/max
Effluents Sour water from 1m3 / tonne S H2S: 50 mg/l; To be treated in the SWS
quench column for produced Phenol: 100 mg/l;
SRU off-gas (2 m3/h) NH3: 2000 mg/l
Waste: Spent TGCU Regeneration 2 - 8 % Ni/Mo on Spent Claus catalyst is pyrophoric
SCOT catalyst and disposal Al2O3, and needs purging with N2
20 - 100 t/yr S: 5 - 15 %;
Coke: 10 - 30 %

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

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Chapter 4 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

Utilities Utilities Catalyst Chemical Operation Recovered
TOTAL
Consumption Production Consumption Consumption Cost Sulphur
Process k$ / y k$ / y k$ / y k$ / y k$ / y k$ / y k$ / y
Sulfreen 52 -6 37 n/a 20 -24 79
HydroSulfreen 82 -22 74 n/a 20 -26 128
DoxoSulfreen 125 -29 264 n/a 30 -27 363
CBA 36 n/a 13 n/a 10 -25 34
Superclaus 106 -32 44 n/a 10 -19 109
Clauspol II 52 n/a 26 26 20 -25 99
RAR 133 n/a 16 10 30 -28 161
LO-CAT II 138 n/a 15 148 30 -28 303

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 Approximate Approximate operating

range 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
Tailgas treatment unit to improve SRU 50 t/d 3.5 Operating cost relatively
recovery to 99.8 % 100 t/d 4.4 low
250 t/d 6.3
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.

344 Mineral Oil and Gas Refineries

Techniques to consider in the determination of BAT Chapter 4

Without Licence, Catalysts Licence, Catalyst and

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 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

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 k EUR %
INDIRECT COSTS
Detailed Engineering 8.0 27
Field Supervision 1.6 5
Owner 2.4 8
Subtotal 12.0 40
DIRECT COSTS EQUIPMENT
Materials 7.3 25
Catalysts and Chemicals 0.6 2
Subtotal 7.9 27
DIRECT COSTS - NON EQUIPMENT
Subcontracts 8.6 29
Temporary Construction & Consumables 0.4 1
Subtotal 9.0 30
Total Capital 28.9 97

EXPENSE
Licensing Fee 0.5 2
Subtotal 0.5 2
Final Total 29.4 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.

Mineral Oil and Gas Refineries 345

Chapter 4 Techniques to consider in the determination of BAT

Name of the technique EUR/tonne SO2 EUR/tonne SO2

abated (1) abated (2)
3rd reactor 32
Stand Alone Scot 321-538 32
Cascade Scot Common 32
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 Number of installations all over the world

Beavon More than 150 installations
Clauspol More than 50 units
Sulfreen/Hydrosulfreen More than 150 units in operation
Superclaus 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.

346 Mineral Oil and Gas Refineries

Techniques to consider in the determination of BAT Chapter 4

Driving force for implementation

Processes for odour and emission control features.

Example plants
More than 1000 applications worldwide.

Reference literature
[181, HP, 1998]

4.23.5.4 Sulphur dioxide abatement techniques

Flue gas desulphurisation is a technique by which SO2 is removed from flue gases or other
waste gases. The process often involves an alkaline sorbent which captures SO2 and transforms
it to a solid product. SO2 in refinery waste gases may have unabated concentration levels of
1500 - 7500 mg/m3. Various FGD methods exist with varying SO2 removal efficiencies. The
FGD market is dominated by the so-called wet lime/limestone process followed by spray dry
scrubbers, and the application of sorbent injection and regenerable processes. More information
can be found in the Waste gas waste water BREF [312, EIPPCB, 2001].

Systems either of the regenerable or the non-regenerable type, do exist for SOx removal only,
but also for simultaneous removal of dust and NOx. Most of these combined processes are still
in the development phase, but some are commercially available already. They are or may
become competitive with systems consisting of separate units for SO2 elimination (i.e. wet
scrubbers) and NOx removal (i.e. SCR).

Description
Additive injection (AI) and Spray Dry Absorber (SD) are scrubbing processes that remove SO2
according to the same principle as WS (reacting with a Ca-based sorbent) however, without the
complicating requirements for producing a high-grade gypsum by-product (i.e. prescrubbing
and oxidising). The by-product is a mixture of sulphites, sulphates and fly-ash for which there
are few or no useful applications.

The AI-process provides moderate SO2 removal at relative low sulphur loads. A dry sorbent is
injected in the furnace. The sorbent used is limestone or hydrated lime (for small boilers, more
active sodium bicarbonate (NaHCO3) is injected in the flue gas duct).

The SNOX process combines high removal of SO2, NOx and particulates. More information see
Section 4.23.8

The seawater scrubbing process uses the natural alkaline - bicarbonates - of seawater to remove
SO2. This implies a potential for high removal efficiencies. The discharge will contain sulphate
and chlorine ions - which are a natural constituent of seawater.

In the Walther (WA)-process, SO2 is absorbed by spray injection of aqueous ammonia, yielding
ammonium sulphite. The sulphite is subsequently oxidised to sulphate. The ammonium salt
solution from the scrubbing section is concentrated in an evaporation unit and granulated. The
end-product is a marketable fertiliser.

The Wellman Lord (WL)-process is the most widely used regenerable process. The process is
based on sodium sulphite/bisulphite equilibrium.

Present-day Wet Limestone Scrubber (WS)-systems are very much improved and less complex
than the earlier systems. Generally a limestone/water slurry is used as the sorbent. Gypsum is
produced by oxidation (aeration) in the sump of the absorber.

Mineral Oil and Gas Refineries 347

Chapter 4 Techniques to consider in the determination of BAT

Achieved environmental benefits

Desulphurisation SO2 reduction (%) Other benefits

technique
Additive injection (AI) and > 92 Like with WS the SD-system combines good
Spray Dry Absorber (SD) removal of SO2, SO3, chlorine and fluorine (> 90 %
on sulphur compounds, 70 - 90 % on the halides).
AI-process 50 - 70
Seawater scrubbing 99 The acidic effluent from the absorber flows by
gravity to a water treatment plant. Here, air is
blown into the water to convert the absorbed SO2
into dissolved sulphate and to saturate the seawater
with oxygen (COD treating). The pH is adjusted
back to neutral partly by added seawater and partly
by aeration. The effluent from the treatment plant
is discharged directly back to the sea.
SNOX 99.9 Up to 95 % for nitrogen oxides. Particulates are
essentially completely removed.
Walther > 88 Product that can be sell as fertiliser. This product
has to meet certain criterias (especially heavy metal
content)
Wellman Lord 98 Sulfur is recovered as a product. For the removal of
(100 mg/Nm3). SO3, ammonia is injected, which leads to the
formation of ammoniumsulphate. Ammonium
sulphate may be used as a fertiliser under certain
circumstances (especially heavy metal content).
Wet Limestone Scrubber 90 - 98 If the chlorine content is low, this system produces
no waste water.

Table 4.42: Achieved environmental benefits of the desulphurisation processes

Cross-media effects

Desulphurisation technique Cross-media effects

Additive injection (AI) and Spray As the by-product generated by these techniques contains unreacted lime, it
Dry Absorber (SD) requires conditioning before disposal.
AI-process The disposal of the by-product requires similar care as for SD.
Seawater scrubbing Some fly ash with associated heavy metals and organic substances is
transferred to the seawater.
SNOX
Walther The process does not generate solid by-products or liquid waste. If
particulates with possible content of metals are present in the flue gas they
appear together with the product.
Wellman Lord Dust: NH3 is injected to prevent the formation of SO3. Therefore up to 80 %
of the ash consists of (NH4)2SO4, which can be used as a fertiliser or as a
basic material for NH3 production.
Waste water from the pre-scrubber has a sour water quality with a pH of
around 2 and must be neutralised and stripped. The purified water may still
contain up to 100 mg/l ammonia, but most often, values are in the range of 10
to 50 mg/l.
Wet Limestone Scrubber Waste water generated by the gypsum dewatering process contains suspended
solids and trace elements (metals, chlorides) and is to be treated by
sedimentation, flocculation and filter pressing. The filter cake is disposed of
by landfill and the purified water is drained to sewer.
Iron chelating, solvent extraction, Those techniques generally produce a lot of waste.
NaOH adsorption or molecular
adsorption

Table 4.43: Cross-media effects of the desulphurisation processes

348 Mineral Oil and Gas Refineries

Techniques to consider in the determination of BAT
Operational data
Desulphurisation technique
Additive injection (AI) and
Spray Dry Absorber (SD)
AI-process
Seawater scrubbing
Walther
Wellman Lord
Wet Limestone Scrubber
Table 4.44: Operational data of the desulphurisation processes
Applicability
Desulphurisation technique
Seawater scrubbing
SNOX
Walther
Wellman Lord
Iron chelating, solvent
extraction, NaOH adsorption or
molecular adsorption
Mineral Oil and Gas Refineries
Chapter 4
Operation data
Being a dry process, corrosion conditions are less severe than is the case with
WS. Hence, the scrubber is usually made of (uncoated) carbon steel. Calcium
chlorides may yet prompt acid corrosion as they precipitate on the absorber
walls and attract moisture. Recycling by-product with wet flue gas to the
sorbent make-up tank may suffer from plugging; regular cleaning is required.
The system is less effective as regards the removal of HCl, hence the fuel
should not have a higher Cl content than approximately 0.3 % for corrosion
prevention.
The process offers simplicity, thus high availability,
Chloride aerosols and a visible waste gas plume may occur when fuels are
used with a high chlorine content. Aerosol formation can be mitigated by
increased liquid to gas ratio in the absorber and the use of multiple tube
filters. Deposits of sulphates can be removed by blowing with hot flue gas or
by water washing. NOx has no influence on the FGD process as it does not
react with ammonia.
Operational aspects include problems with respect to fouling, corrosion and
erosion. In the pre-scrubber deposits of ammonium sulphate can occur. The
evaporator is susceptible to wear by the abrasive salt slurry, corrosion during
shutdowns and mechanical strains related to the high speed centrifuge.
Through good engineering practice (liberal sizing of spray systems and
mixers, applying washing on demisters etc.) deposits and plugging of the
various components can largely be avoided.
For high-grade gypsum production, forced oxidation and good pH control is
required. Furthermore, good quality limestone (> 93 % purity in CaCO3)
must be used and dust and trace elements, in particular chlorine, should be
removed by prescrubbing of the raw gas and dewatering and optional
washing of the product. Organic buffers (such as adipates and dibasic acid)
can be used for pH control, thereby substantially enhancing the SO2 removal
efficiency by typically 4 %. Early corrosion problems have been overcome;
often rubber lining is used in the absorber, requiring some care in view of
abrasion damage.
Applicability
Because particulates (may be containing heavy metals) are
tranferred to the seawater, a particulate abatement technique is
necessary previous the seawater scrubbing.
The three main treatment areas in refineries of applications of
this sytem are H2S gases, onsite regeneration of H2SO4 used in
the alkylation unit and FCCU regenerator off-gases.
The system is not suitable for fuels with elevated sulphur
content, as these results in increased ammonia slip due to the
formation of ammonia sulphates. The sulphates are
objectionable because of corrosion and aerosol emissions.
Despite of its excellent emission profile, the process complexity
has been an obstruction to wide-spread application.
Those techniques are typically used when the ammount of SO2
to recover are small because they produce waste. For example in
small specialised refineries or small natural gas plants.
349
Chapter 4
Economics
Desulphurisation technique
AI-process
Seawater scrubbing
Wellman Lord
Wet Limestone Scrubber
Iron chelating, solvent
extraction, NaOH adsorption or
molecular adsorption
Driving force for implementation
Desulphurisation technique
Wellman Lord
Iron chelating, solvent
extraction, NaOH adsorption or
molecular adsorption
Example plants
Desulphurisation technique
Seawater scrubbing
SNOX
Wellman Lord
Wet Limestone Scrubber
Iron chelating, solvent
extraction, NaOH adsorption or
molecular adsorption
Reference literature
[250, Winter, 2000], [257, Gilbert, 2000], [181, HP, 1998], [258, Manduzio, 2000]
350
Techniques to consider in the determination of BAT
Economics
35 - 55 EUR/kWth (unit size: 75 - 300 MWth). annual operating cost
roughly equals capital cost.
Low capital costs and low operating costs (no bulk chemicals
required, although sometimes magnesium hydroxide is used to
enhance the alkalinity).
The investment cost is estimated to be $50 million for a unit to handle
a flue-gas flow rate of 500000 Nm3/h and a SO2 concentration of
0.8 %. The cost includes licensing fees, engineering, equipment
delivery, construction, commissioning and startup services.
75 - 180 EUR/kWth (unit size: 75 - 300 MWth). Anual operating cost
roughly equals capital cost.
Capital cost: EUR 10 - 20 million. Operating cost EUR 1.6 - 4
million/yr (costs are mainly for caustic soda). Flue gas flows 200000
to 650000 Nm3/h
They are battery limit costs based on 1998 prices and include such
items as equipment, licence fees, foundations, construction 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 %.
They are tipically very cheap compared with other FGD techniques
Driving force for implementation
The process characteristics can suit the needs of particular industrial
sites using high-sulphur fuels (in the US, Japan and Austria the
process has been used in refineries).
Abatement of small quantities of SO2
Example plants
The process has been applied to some extent (in 1994: 2500 MWe /
47 units), also used for smelters, refineries and oil-firing (at 3 % S).
More than 25 units have been successfully installed worldwide.
Applied in Italy in a big oil refinery which produces and burns high
sulphur petcoke
More than 40 systems have been applied over the world.
Operational experience with WS is highly satisfactory,
demonstrated by high availability. This system is widely applied in
power plants.
Applied in some small refineries and natural gas plants
Mineral Oil and Gas Refineries