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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.
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
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).
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
LEAN
AMINE
FLASH DRUM
OPTIONAL
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.
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.
Cross-media effects
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:
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:
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 %.
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]
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.
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
Figure 4.11: Simplified process flow diagram of a sulphur recovery unit (CLAUS) unit
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.
Cross-media effects
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.
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 %.
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]
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.
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.
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.
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 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.
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.
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.
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:
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.
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.
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:
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.
Example plants
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]
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]
Description
The system works with a fixed-bed or batch-type granular reactant.
Applicability
Applications to waste water sytems, land oil tanker vent, oil storage and transportation, and
bitumen plants.
Example plants
More than 1000 applications worldwide.
Reference literature
[181, HP, 1998]
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.
Cross-media effects
Operational data
Applicability
Economics
Example plants
Reference literature
[250, Winter, 2000], [257, Gilbert, 2000], [181, HP, 1998], [258, Manduzio, 2000]