SulphurRecovery PDF
SulphurRecovery PDF
SulphurRecovery PDF
Technology
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Technology Portfolio
Table of Contents
TABLE OF CONTENTS
1.0
2.0
TOC
Technology Portfolio
Technology Leaflets & Pictures
1.0
Section 1
Page 1 of 5
Page 2 of 5
Line Burner
SUPERCLAUS Catalyst
Main Burner
Page 5 of 5
APPLICATIONS
The ADIP process is a regenerative process
developed to reduce H2S in gas to very low
concentrations, while a good selectivity for H2S in the
presence of CO2 can be achieved. The ADIP process
covers the use of the aqueous solution of diisopropanol amine (DIPA) and the aqueous solution of
methyldiethanol amine (MDEA). MDEA is used for
those applications in which high selectivity for H2S is
required. Depending on operating conditions 20 - 60%
of the CO2 is co-absorbed if DIPA is used as the ADIP
solvent, while this can be reduced to 10 - 30% if
MDEA is applied as the solvent. The ADIP process
can also be used for enrichment of acid gas feed to a
sulfur recovery plant, to achieve a higher H2S content.
Integration of gas treating with the SCOT solvent
system is an option.
DESCRIPTION
The H2S containing gas is contacted counter-currently
in an absorption column with ADIP solvent. The
regenerated solvent is introduced at the top of the
absorber. The H2S loaded solvent (rich solvent) from
the absorber is heated by heat exchange with
regenerated solvent and is fed back to the
regenerator, where it is further heated and freed of the
acid gases with steam.
UTILITIES
The estimated consumption varies widely with feed
composition and product specification. LP steam
consumption amounts to 0.4 to 2.8 ton/ton acid gas
removed.
FEATURES
Reduction of H2S to very low concentrations.
Low steam consumption and solvent circulation.
Carbon steel equipment.
Resistant against degradation (DIPA).
No reclaimer required.
Good selectivity for H2S in the presence of CO2.
Reduced investment and operating costs with
selective designs.
REFERENCES
More than 450 ADIP units ranging in capacity from
1.900 Nm3/d to 12.200.000 Nm3/d and 19 t/sd to 7700
t/sd liquid hydrocarbons are in operation throughout
the world, demonstrating the reliability of the process
LICENSOR
Jacobs Nederland B.V., Leiden, The Netherlands, is
one of the three authorized licensors on behalf of
Shell Research Ltd. since 1981.
Streams to be treated
Refinery gases: e.g. from HDS and cracking units
Natural gases
Reduced Claus tail gas (SCOT process)
Gas from oil or coal gasification in combined-cycle power stations
Claus feed gas enrichment
Contaminants removed
H2S
H2S, CO2 (partly)
H2S, CO2 (partly)
H2S, CO2 (partly)
H2S, CO2 (partly)
APPLICATIONS
The ADIP process is also used for the reduction of
H2S and COS to very low levels in liquid hydrocarbons
such as propane-propylene (PP), LPG and NGL. The
process is based on regenerative absorption with an
amine solvent in contact with the acidic feed. Removal
of CO2 is also possible. Removal of H2S from LPG or
NGL down to 20 ppmwt or lower, COS removal down
to 5 ppm wt as S.
REFERENCES
More than 450 ADIP units ranging in capacity from
1.900 Nm3/d to 12.200.000 Nm3/d and 19 t/sd to
7.700 t/sd liquid hydrocarbons are in operation
throughout the world, demonstrating the reliability of
the process.
LICENSOR
Jacobs Nederland B.V., Leiden, The Netherlands, is
one of the three authorized licensors on behalf of
Shell Research Ltd. since 1981.
DESCRIPTION
In liquid hydrocarbon treating, for example LPG, feed
LPG is contacted counter-currently with lean ADIP in
a packed liquid-liquid extractor column.
If COS is present in the LPG, removal of COS is
achieved by a mixer/settler system. The lean ADIP
solvent passes first through the mixer/settler system
before entering the extractor. Co-current and countercurrent mixer/settlers are used for COS removal.
Streams to be treated
Contaminants removed
H2S, COS
H2S, COS
SULFUR RECOVERY
CLAUS PROCESS
be designed for turndown ratios of 100-15%. Product
sulfur has a purity of more than 99.9% -bright yellow- ;
and contains less than 10 ppmwt H2S after degassing.
H2S (stack) emission: 5-10 ppm vol. with thermal
incinerator depending on the incinerator temperature
and 10 ppm vol. with a catalytic incinerator.
UTILITIES
Basis: 100 t/d sulfur recovery unit, 93 vol.% H2S in
feed gas and catalytic incineration.
APPLICATIONS
The Claus process has been developed to recover
elemental sulfur from H2S containing gases originating
from gas treating plants such as alkanolamine units or
physical solvent plants. Modern Claus plants should
be able to process H2S/NH3 containing gases as well,
originating from Sour Water Strippers.
DESCRIPTION
The Claus process is based on the combustion of part
of the H2S to SO2 and the subsequent reaction
between the remaining H2S and the SO2 produced,
forming sulfur. There are two main varieties of the
Claus process: straight through and split flow. The
straight through process is used for feed gas
containing more than 50% H2S while split flow is
applied for gases containing 50 to 15% H2S. The
sulfur recovery process consists of a thermal stage
(combustion chamber, waste heat boiler) and two or
three catalytic reaction stages (reheater, reactor and
condenser). In the thermal stage, the Claus reaction
takes place at a high temperature level (950-1350C).
The sulfur produced in this stage is condensed either
in the waste heat boiler or in the condenser.
Subsequently, the gas is reheated to a temperature of
200-300C before introduction into each reactor
stage. The heat generated from the reactions is used
for steam production. In the thermal stage, a choice
can be made between the production of LP, MP or HP
steam. In the sulfur condensers LP steam is
generated. The tail gas is sent to an incinerator or tail
gas treater.
OPERATING CONDITIONS
NH3 in the total Claus feed gas can be processed up
to 30 vol.%. Some feed gases may contain small
amounts of heavy hydrocarbons and aromatics,
operating experience up to 2 vol.%. Claus plants can
LP steam
MP steam
Electricity
Fuel gas
Boiler feed water
LP steam (plant heating)
t/h
t/h
kW
t/h
t/h
t/h
Consumption
--220
0.12
13.5
0.4
Production
3.3
10.2
-----
FEATURES
Sulfur recovery with
two reactors
: up to 96%
three reactors
: up to 98%
SULFUR HANDLING
SHELL SULFUR DEGASIFICATION PROCESS
The Shell Sulfur Degasification Process
to incinerator
LP steam
sulfur from
Claus plant
sulfur to
storage
air
sweep gas
stripping column
Figure 1
The Shell Sulfur Degasification Process
LP steam
sulfur from
Claus plant
to incinerator
air
air
sulfur to
storage
sweep gas
stripping
column with
separation
baffle
stripping
column with
separation
baffle
Figure 2
APPLICATIONS
The Shell Sulfur Degasification Process has been
developed to remove H2S and H2Sx from liquid sulfur
eliminating potential toxic and explosion hazards
associated with handling, transport and storage of
liquid sulfur. Elemental, sulfur produced by the Claus
process contains both physically dissolved H2S and
chemically bound H2S in the form of hydrogen
polysulfides (sulfanes): H2Sx. Liquid sulfur produced
typically contains 250-350 ppm wt H2S mainly in the
polysulfide form. The principle of sulfur degasification
is to accelerate decomposition of the polysulfides
according to H2Sx H2S + Sx-1 and to remove the
dissolved H2S from the liquid sulfur. In the Shell Sulfur
Degasification Process, the sulfur is degassed to less
than 10 ppm wt H2S/H2Sx.
DESCRIPTION
Degasification is carried out as a continuous process
in the degasification compartment of the Claus plant
sulfur pit or in a dedicated vessel. The actual
degasification takes place in the stripping column
where sulfur is vigorously agitated by bubbling air
: 5 kW
: 200 kg/h
: not required
FEATURES
Safer working conditions for handling liquid sulfur.
Less corrosion in transport and storage equipment.
Reduction of emission problems in the surrounding
of the sulfur pit.
No chemicals present in the gasified product
sulfur.
No moving parts.
REFERENCES
More than 150 Shell Sulfur Degasification systems
ranging in capacity from 10 to 4000 t/d sulfur
production are in operation or are under design/
construction throughout the world demonstrating the
reliability, simplicity and flexibility of the process.
LICENSOR
Jacobs Nederland B.V., Leiden, The Netherlands, is
the exclusive worldwide licensor of behalf of Shell
Research Ltd. since 1981.
SULFUR RECOVERY
EUROCLAUS PROCESS
The EUROCLAUS process
combustion
chamber
steam
selective
oxidation
reactor
Claus
reactor
reheater
incinerator
stack
waste heat
boiler
steam
H2S
0.8-1.5 vol.%
condenser
feed gas
O2
0.5-2 vol.%
S
air
APPLICATIONS
The EUROCLAUS process has been developed to
recover elemental sulfur from H2S containing gases
originating from gas treating plants such as
alkanolamine units or physical solvent plants. The
EUROCLAUS process is an improvement of the
SUPERCLAUS process. Yields up to 99.7% overall
sulfur recovery without any further tail gas clean up
are possible.
UTILITIES
Basis: 100 t/d sulfur recovery unit, 93 vol.% H2S feed
gas and catalytic incineration.
DESCRIPTION
The EUROCLAUS process consists of a thermal
stage followed by three catalytic reaction stages with
sulfur removed between stages by condensers. Two
reactors are filled with standard Claus catalyst while
the last reactor is filled with the selective oxidation
catalyst. In the thermal stage, the acid gas is burned
with a substoichiometric amount of controlled
combustion air such that the tail gas leaving the
second reactor contains typically 0.8 to 1.0 vol.% of
H2S and 100-200 ppmv SO2. This low SO2 content is
obtained with a hydrogenation catalyst which converts
SO2 to H2S in the bottom of the second reactor. The
catalyst in the last reactor oxidizes the H2S to sulfur at
an efficiency of more than 85%. However, because
this catalyst neither oxidizes H2S to SO2 nor reverses
the reaction of sulfur and water to H2S and SO2, a
total sulfur recovery efficiency up to 99.3% can be
obtained. If a sulfur recovery efficiency of more than
99.3% is required, one additional Claus reactor stage
may be installed upstream of the selective oxidation
reactor.
FEATURES
Application in both new and existing plants.
The SUPERCLAUS catalyst as applied in the
SUPERCLAUS process.
Improved process controls of the SUPERCLAUS
stage.
A final Claus reactor also containing hydrogenation
catalyst.
Long catalyst lifetime up to 10 years.
Sulfur recovery up to 99.7%.
Reduction of current SO2 emissions up to 90%.
Simple continuous operation.
Low additional investment costs.
NH3 destruction.
Capability to combust heavy hydrocarbon and
aromatics.
High turndown.
High reliability - less than 1% unscheduled
shutdown time.
OPERATING CONDITIONS
Three main principles are applied in operating the
EUROCLAUS process:
Operating the Claus plant with excess H2S to
suppress the SO2 content in the Claus tail gas.
LP steam
MP steam
Electricity
Fuel gas
Boiler feed water
LP steam (plant heating)
t/h
t/h
kW
t/h
t/h
t/h
Consumption
--220
0.12
13.5
0.4
Production
3.3
10.2
-----
REFERENCES
Since the first commercial demonstration of the
EUROCLAUS process in 2000, more than 12 plants
are in operation or under construction in the first
quarter of 2003.
LICENSOR
Jacobs Nederland B.V., Leiden, The Netherlands.
OPERATING CONDITIONS
Operating test data of LS-SCOT at three different
locations
H2S in feed gas to absorber
CO2 in feed gas to absorber
Total S in treated gas
Solvent temperature
Solvent type
Regenerable free base
Actual total base
Specific steam rate
Number of absorber trays
vol.%
vol.%
ppmv
C
wt.%
wt.%
kg/m3
Test 1
2.4
7.1
<50
35
DIPA
41
42
120
11
Test 2
2.1
4.0
<50
39
MDEA
52
53
135
11
Test 3
1.4
3.0
<50
32
DIPA
44
48
132
9
vol.%
vol.%
ppmv
C
kg/m3
Test run
no. 1
1.3
3.0
<50
45
320
Test run
no. 2
1.7
2.5
<50
44
350
wt.%
wt.%
24
24.5
26
27
REFERENCES
Since 1991 six LS-SCOT and six Super-SCOT units
are in operation behind the Claus unit with a capacity
between 30 t/d and 950 t/d. Three of the six SuperSCOT units have been designed to lower the steam
consumption.
LICENSOR
Jacobs Nederland B.V., Leiden, The Netherlands, is
one of the three authorized licensors on behalf of
Shell Research Ltd. since 1981.
Figure 1
APPLICATIONS
The Shell Claus Off-gas Treating (SCOT) process has
been developed to remove sulfur compounds from
Claus tail gas to comply with air stringent emission
regulations. The standard SCOT process is able to
easily meet less than 250 ppmv total sulfur in the
SCOT off-gas, which corresponds to an overall sulfur
recovery efficiency of 99.9% on intake.
DESCRIPTION
The SCOT process essentially consists of a reduction
section and an ADIP absorption section of special
design. In the reduction section all the sulfur
compounds (other than H2S) present in the nonincinerated Claus tail gas (SO2, COS, CS2 and
elemental S) are completely converted into H2S over a
cobalt/molybdenum catalyst at 300C in the presence
of H2 or a mixture of H2 and CO.
The Claus tail gas feed to the SCOT process is
heated to 300C with an inline burner or heat
exchanger with optionally added H2 or a mix of H2/CO.
If reducing gas, H2 or CO, is unavailable, an inline
burner is operated substoichiometrically to produce
reducing gas. The heated gases than flow through a
catalyst bed where sulfur compounds, including CS2
and COS, are reduced to H2S. Process steam is
generated in by cooling the gas to about 165C in a
heat recovery boiler and subsequently by direct
contact cooling with water to 40C. Water vapor in the
process gas is condensed and the condensate is sent
to a sour water stripper. The cooled gas, which
normally contains up to 3% vol. H2S and up to 20%
vol. CO2 or more is countercurrently washed with an
alkanolamine solvent in an absorption column
designed to absorb almost all H2S but relatively little
CO2. The treated gas from the absorption column
contains only traces of H2S and is burned in a
standard Claus incinerator. The concentrated H2S is
recovered from the rich solvent in a conventional
stripper and is recycled to the Claus unit. The SCOT
units are designed for minimum pressure drop so that
they can be added easily to existing Claus units.
If insufficient pressure is available, a gas booster can
be installed, preferably between the cooling tower and
the absorption tower.
: 94% vol.
: 28 kWh
: 0.46 t (for add-on SCOT)
: 0.33 t (for integrated SCOT)
: 0.016 t
: 0.36 t
FEATURES
High degree of desulfurization over a wide range of
operating conditions.
Recovery of sulfur as a single, homogeneous
product via the Claus unit.
No secondary air of water pollution.
Minimum operator attention.
Easy integration with existing Claus units.
Application of familiar equipment and process
operations.
High reliability - less than 1% unscheduled
shutdown time.
REFERENCES
More than 185 SCOT units for the treatment of tail
gas from Claus plants ranging in capacity from 3 t/d
up to 4000 t/d sulfur production are in operation
throughout the world, demonstrating the reliability and
flexibility of the process.
LICENSOR
Jacobs Nederland B.V., Leiden, The Netherlands, is
one of the three authorized licensors on behalf of
Shell Research Ltd. since 1981.
SULFUR RECOVERY
SPECIALITIES
1. JACOBS NH3 DESTRUCTION SYSTEM
Application
To recover elemental sulfur from acid gas containing
H2S, CO2 and NH3 in Claus plants. In JNL's ammonia
destruction system all gases containing H2S and NH3
are burnt in one burner, offering the following
advantages:
Complete destruction of NH3.
No deposits of ammonia salts.
No NOx formation due to reducing flame conditions.
Simple operation and control.
Since 1969 this Jacobs Nederland system has been
installed in more than 150 Claus plants
2. HEAVY HYDROCARBON DESTRUCTION SYSTEM
Application
Some feed gas streams may contain small amounts
of heavy hydrocarbons and aromatics. In Jacobs
burning system, these components are completely
burnt, preventing soot formation and the production of
off-spec sulfur.
3. ABC ADVANCED BURNER CONTROL
Application
To control the air to acid gas ratio, the ABC system
has to be developed for controlling the H2S content in
the gas to the SUPERCLAUS reactor stage, but the
ABC system can also be applied to control the
H2S/SO2 ratio in a conventional Claus plant.
Description
To cope with the flow rate disturbances, both the
conventional control system and the Advanced
Control System (ABC) use a feed-forward (ratio)
control scheme. The conventional control system
controls the air through the main air valve in ratio to
the acid gas flow. It has the disadvantage that the
main air valve is big and therefore slow. A step
change in acid gas does not result in a step change in
the main air flow, and leads to an incorrect ratio
during the (long) response time of the main air valve.
The ABC system reacts faster to changes in the acid
gas
flow
rate.
OPERATING CONDITIONS
Very wide ranges of treating pressures and
contaminant concentrations can be accommodated.
Natural gas pipeline specifications are easily met.
Removal of organic sulfur compounds is usually
accomplished by the solvent circulations as set by
H2S and CO2. In LNG plants a specification of 50 ppm
CO2 prior to liquefaction is attained without difficulty.
UTILITIES
The utility consumption varies widely with feed gas
composition and product gas specification.
FEATURES
Removal of H2S, COS and organic sulfur to natural
gas pipeline specification.
Low steam consumption and solvent circulation.
Low corrosion rates.
Selective removal of H2S in some natural gas
applications.
Smaller equipment due to low foaming tendency.
High on-stream factor.
REFERENCES
More than 200 Sulfinol units ranging in capacity from
10.000 Nm3/d to 32.000.000 Nm3/d are in operation
throughout the world, demonstrating the reliability of
the process.
DESCRIPTION
The feed gas is contacted counter-currently in an
absorption column with the Sulfinol solvent. The
regenerated solvent is introduced at the top of the
absorber.
The sulfur compounds loaded solvent (rich solvent) is
heated by heat exchange with the regenerated
solvent and is fed back to the regenerator where it is
LICENSOR
Jacobs Nederland B.V., Leiden, The Netherlands, is
one of the three authorized licensors on behalf of
Shell Research Ltd. since 1981.
Streams to be treated
Contaminants removed
Natural gases
Natural gases
CO2
Capacity
utilization
BENCHMARK
The benchmark is executed via defined performance
indicators, which are combined in the benchmarking
index. The performance indicators for this study are:
Availability
Maintenance expenses
Energy consumption
Operational expenses
Reliability
Sulfur recovery
Failures
Capacity utilization
Maintex
C a p a c ity
u tiliza tion
M a in te x
Energy
consumption
Failures
E ne rg y
c o n s um p tio n
F a ilu re s
Sulfur
Recovery
Opex
S u lfu r
R e c o v e ry
Reliability
O pex
R e lia b ility
PROCEDURE
After a positive reaction on the invitation letter, the
clients receive a questionnaire concerning the above
described topics, followed by a plant visit with
discussions during 2-3 days. The results are
described in a benchmarking report, followed by a
client specific report. The presentation of the benchmark as well as the exchange of experiences of the
clients will be facilitated during a workshop in our
office.
BI-1
BI-1 specific
DESCRIPTION
The topics, which are addressed, are:
Organizational aspects: shifts, training.
Plant data: performances of equipment, catalyst,
areas of modification, utility consumption,
operating costs, feed data, recovery, analysis.
Operational
aspects:
operation
modes,
reliability/availability, capacity usage, problem
areas, procedures, safety.
Instrumentation: plant automation systems,
critical instrumentation, analyzers.
Inspection/maintenance:
techniques,
costs,
organization of turnarounds, critical
maintenance areas, corrosion.
Environmental aspects: authority requirements,
SO2 emissions, penalties, waste disposal.
Future developments: operation modes, plant
capacity, environmental requirements.
Plants
EXPERIENCE EXCHANGE
An indication of the topics that were discussed
during the last study: corrosion, waste heat boiler
tube sheet corrosion, inspection techniques for HIC
detection, capacity increase, problems with tail gas
analyzers, foaming, hydrocarbon carry-over, gas
sampling techniques, shutdown procedure.
REFERENCES
In the past studies major West European refineries
have participated.
SULFUR RECOVERY
SUPERCLAUS PROCESS
efficiently converts the remaining H2S in the
presence of water vapor and excess oxygen to
elemental sulfur only.
Other operating features, which apply to Jacobs
Claus process, are applicable for the
SUPERCLAUS process as well, such as NH3
destruction up to 30 vol.%, the capability to
process small amounts of heavy hydrocarbons
and aromatics up to 2 vol.%, turndown ratios of
100-15% and production of 99.9% pure bright
yellow sulfur.
APPLICATIONS
The SUPERCLAUS process has been developed
to recover elemental sulfur from H2S containing
gases originating from gas treating plants such as
alkanolamine units or physical solvent plants.
Modern SUPERCLAUS plants should be able to
process H2S/NH3 containing gases as well,
originating from Sour Water Strippers, with the
objection to yield up to 99.4% overall sulfur recovery
without any further tail gas clean-up.
DESCRIPTION
The SUPERCLAUS process consists of a thermal
stage followed by three catalytic reaction stages with
sulfur removed between stages by condensers. Two
reactors are filled with standard Claus catalyst while
the last reactor is filled with the new selective
oxidation catalyst. In the thermal stage, the acid gas
is burned with a substoichiometric amount of
controlled combustion air such that the tail gas
leaving the second reactor contains typically 0.8 to
1.0 vol.% of H2S. The new catalyst in the third
reactor oxidizes the H2S to sulfur at an efficiency of
more than 85%. However, because the new catalyst
neither oxidizes H2S to SO2 and H2O nor reverses
the reaction of sulfur and water to H2S and SO2, a
total sulfur recovery efficiency up to 99% can be
obtained. If a sulfur recovery rate of more than 99%
is required, one additional Claus reactor stage will
be installed upstream of the selective oxidation
reactor.
OPERATING CONDITIONS
Two main principles are applied in operating the
SUPERCLAUS process:
Operating the Claus plant with excess H2S to
suppress the SO2 content in the Claus tail gas.
Selective oxidation of the remaining H2S in the
Claus tail gas by means of special catalyst which
UTILITIES
Basis: 100 t/d sulfur recovery unit, 93 vol.% H2S
feed gas and catalytic incineration.
LP steam
MP steam
Electricity
Fuel gas
Boiler feed water
LP steam (plant heating)
t/h
t/h
kW
t/h
t/h
t/h
Consumption
--220
0.12
13.5
0.4
Production
3.3
10.2
-----
FEATURES
Application in both new and existing plants.
The newly developed SUPERCLAUS catalyst
possesses some unique properties:
- oxidation of H2S to sulfur is complete
- no sensitivity to water vapor
- further oxidation of SO2 is negligible even in the
presence of excess oxygen
- components such as H2, CO and other
combustibles are not affected
- the catalyst does not promote the Claus
equilibrium reaction
Long catalyst lifetime up to 10 years.
Sulfur recovery up to 99.4%.
Reduction of current SO2 emissions up to 90%.
Simple continuous operation.
Low additional investment costs.
NH3 destruction.
Capability to combust heavy hydrocarbon and
aromatics.
High turndown.
High reliability - less than 1% unscheduled
shutdown time.
REFERENCES
Since the first commercial demonstration of the
SUPERCLAUS process in 1988, more than 110
plants with a capacity up to 1165 t/d are in operation
or under construction in the first quarter of 2003.
LICENSOR
Jacobs Nederland B.V., Leiden, The Netherlands.
9
8
no. of licensed projects
7
JNL LIC
TPA LIC
Pritchard LIC
Parsons LIC
KTI/TECHNIP LIC
2
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TPA EPC
Pritchard EPC
Parsons EPC
KTI/TECHNIP EPC
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Section 2
Major licensors
KTI/Technip
9%
Parsons
13%
Pritchard
11%
JNL
56%
TPA
11%
JNL
17%
KTI/Technip
40%
TPA
22%
Parsons
4%
Pritchard
17%
All licensors
JNL
34%
Others
38%
TPA
7%
KTI/Technip
6%
Pritchard
7%
Parsons
8%
TPA
6%
Pritchard
4%
Parsons
1%
KTI/Technip
10%
Others
75%