Sulfinol PDF

Shell Global Solutions
Confidential Technical Proposal PPGJ Project : CPP Gundih AGTU
This Confidential Technical Proposal for a Sulfinol-M/X Process Acid Gas Removal Unit (AGRU),
Molecular Sieve Dehydration and Mercaptan Removal unit (MSU) and a Shell-Paques Process Sulphur
Recovery Unit (BSRU) has been prepared based on the an updated information received from PT PT
Tripatra Engineering & Construction (herein after refered to as TRIPATRA) on 18th of July 2008
entitled SPECIFICATION FOR SHELL GLOBAL COMPANY , hereinafter referred to as the
Request For Proposal (RFP).
This proposal also incorporates inputs from the meetings and discussions held throughout the period of
the proposal development.
This Proposal provides preliminary AGRU, MSU and SRU design information based on the feed
conditions as specified in the RFP. As the project entails a complex gas treating challenges, we believe that
the solution provided best meets the project requirements as outlined by Pertamina EP PPGJ project team.
This technical proposal is provided under the Secrecy and Restricted Use Agreemet between Shell and
TRIPATRA for the purpose of enabling TRIPATRA to consider the Shell Licensed Processes for
application in the PPGJ Project.
The corresponding commercial offer shall submitted as a separate document from this technical proposal.
Sulfinol
is a trademark of Shell
DISCLAIMER
The purpose of this proposal is to assist Customer, as recipient, in deciding whether or not to proceed with discussions with Shell concerning an engagement of Shell for the
license and services stated herein. This proposal is not intended to constitute an offer or acceptance or to give rise to any binding obligation unless and until a formal contract is
signed by both parties. Nothing contained herein shall constitute otherwise. Until a final contract is signed, either party may close discussions for any reason with no liability to
the other.
Shell disclaims any and all liability for representations or warranties, express or implied, contained in the proposal or in any other written or oral communications with Customer
concerning this subject matter. Only those particular representations and warranties which may be made in a written contract shall, subject to such limitations and restrictions as
may be specified in the contract, have any legal effect.
This proposal is confidential and subject to the terms of the Confidentiality Agreement between the parties dated as of 31st July 2008. This Proposal is being delivered for
informational purposes only and upon the express understanding that it will be used only for the purposes set forth above.
Confidential

Document History
Date
Issue
Reason
Change
20/9/2008
Issued for
internal
appoval
for
Auhors
Reviewed/Verified by
Approved by
Blas, Wilfredo
de Oude, Matthijs
Van Hooijdonk, Jeroen
Koh, Boon Eng
Sakthivel, Ramachandran
Srivathsan, Bharath
Srinivasan, Rajiv
Bajpai, Vishrut
van Heeringen, Gijs

Paques B.V.
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Block Flow Diagram of Acid Gas Treating Unit (AGTU)

The general process line-up for the Acid Gas Treating Unit for the CPP Gundih Station is as follows (only
main process streams shown):
Sales Gas from AGTU
HP Fuel Gas to Distribution
MOLECULAR
SIEVE UNIT (MSU)
Water Make-Up
Incinerator Gases
Feed Gas to
AGTU
ACID GAS
REMOVAL UNIT
(AGRU)
LP Separator,
Condensate
Stabiliser and
Produced Water
Injection Unit
Offgas Streams
Bleed Stream to Effluent

Treatment Plant
BIOLOGICAL SULFUR
RECOVERY UNIT
(BSRU)
Recovered Sulfur
By EPC Contractor By SHELL
By SHELL
By EPC Contractor
Figure I: Acid Gas Treating Unit up Simplified Block Flow Diagram (CPP Gundih)
Most of the contaminants (CO2, H2S, COS, and Mercaptans) in the Feed Gas to the AGTU are removed
by the Acid Gas Remval Unit (AGRU) with the remainder of mercaptans recovered in the Molecular Sieve
Unit (MSU). The MSU also dries the gas to sales specification. Fuel Gas is partially taken from the sales gas
to provide the requirements of the CPP.
The sulphur species in the acid gas stream out of the AGRU are then recovered in the Biological Sulphur
Removal Unit (BSRU) and the desulphurized CO2 stream is then routed to the incinerator.
Additional offgas feed stream from the upstream processing units in the CPP are routed to the thermal
oxidizer of the BSRU for disposal.
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Table of Contents
Document History
Block Flow Diagram of Acid Gas Treating Unit (AGTU)
Table of Contents
1.
Background Information
1.
1.1
Overview of the Project
1.2
Scope of Proposal
The Integrated Treating Line-up
2.1 Feed Gas Specifications
2.
2.2 Product Specifications
11
2.3 AGTU Plant Capacity
12
2.4 Design Considerations & Assumptions
12
2.4.1
Mercaptan Speciation & Handling
12
2.4.2
Feed Gas Condition
12
2.4.3 Use of Shell Proprietary Contacting Internals in the AGRU

Absorber
12
2.4.4
Use of Solvent Flash Vessel
12
2.4.5
AGRU Feed Gas and Treated Gas Knock Out Drums
13
2.4.6 Integration with the Molecular Sieve Regeneration Gas

Recovery
13
2.4.7
Use of a Mechanical Refrigeration Loop in the MSU
13
2.4.8
Mercaptans Conversion in the BSRU
14
2.4.9
Heat Integration Opportunities
14
2.4.10
3.
Re-use of Water Streams
14
The Sulfinol - X Process
15
3.1
Process Overview
15
3.2
Process Description
15
3.3
AGRU Process Flow Diagram
16
3.4 Heat & Material Balance
16
3.5 Equipment
16
3.6 Utility, Catalyst & Chemical Requirements
16
6
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4.
5.
The Shell-Paques Process Biological Sulfur Recovery Process
17
4.1
Process Overview
17
4.2 Process Chemistry
19
4.3 Process Description
19
4.4 BSRU Process Flow Diagram
20
20
4.6 Equipment
20
4.7 Stream Summary
20
21
The Molecur Sieve Process
22
5.1 Process Overview
22
5.2 Process Description
24
5.3 MSU Process Flow Diagram
25
25
5.5 Equipment 25
25
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1.
1.1
Overview of the Project
PT Pertamina E&P intends to produce the gas wells in various fields in the Gundih Area located in
Kabupaten Blora, Central Java, Indonesia. The sales gas is to be used for power generation.
The gas is characterized as difficult due to the high levels and the prescence of the various impurities in
the gas (CO2, mercaptans, H2S and COS) as further described in Section 2 of this proposal.
To meet the sales gas specifications, PT Pertamina EP plans to construct and operate a Central Processing
Plant (CPP) which will comprise of flowlines, inlet manifolds, gas separation units, condensate handling
unit, acid gas treating unit, produced water injection unit and other required supporting systems (e.g.
utilities).
TRIPATRA is participating in the tender of the PPGJ Project for the development of the Central
Processing Plant and as required by Pertamina, the process design of the AGTU shall be developed by
approved licensor.
1.2
Scope of Proposal
Shell Global Solutions has been asked to provide a confidential technical proposal for the processes
required for the Acid Gas Treating Unit for CPP, which includes the following units:
Acid Gas Removal Unit (AGRU)
Molecular Sieve Unit (MSU)
Biological Sulphur Recovery Unit (BSRU)
Caustic Unit*
Some equipment items within the AGTU have been excluded from Shell scope in clarification with
TRIPATRA and these include:
Unit
Equipment Items
Remarks
AGRU
Filter coalescer, F-0205 on feed to AGRU
As specified by TRIPATRA
MSU
Filter coalescer, F-0301 A/B on feed to MSU
As specified by TRIPATRA
*Refer to Section 2.4.6 with respect to the recommeded removal of the caustic unit from the AGTU.
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2. The Integrated Treating Line-up

The AGTU integrated design is based on the feed gas conditions and product specifications as outlined in
the RFP and as described further below.
2.1
Feed Gas Specifications
The main feed gas stream to the AGTU comes from the from the Filter Coalescer, F-0102 A/B. The
following table outlines the composition given:
Table 1: Feed Gas to AGTU
Feed Gas Conditions
75
MMSCFD
Flow rate
Temperature
108
Pressure
400
psig
Composition (dry basis)

%-mole
23.00
Carbon Dioxide
Nitrogen
0.47
%-mole
Oxygen
0.00
%-mole
Methane
70.78
%-mole
Ethane
2.23
%-mole
Propane
0.8
%-mole
i-Butane
0.17
%-mole
n-Butane
0.19
%-mole
i-Pentane
0.08
%-mole
n-Pentane
0.06
%-mole
n-Hexane
0.08
%-mole
n-Heptane
0.09
%-mole
n-Octane
0.04
%-mole
n-Nonane
0.01
%-mole
n-Decane
%-mole
H2S
7000
ppmv
Mercaptans
1700
ppmv
50
ppmv
Carbonyl Sulphide
Notes:
(1) Contaminant levels of CO2, H2S, RSH and COS have been taken with a
+/- 10% variance as advised by TRIPATRA
(2) Feed Gas compositions have been normalized with water exception of
water content
(3) Mercaptan speciation was taken as 100% methyl mercaptan
Offgases from the LP Separator and Condensate Stabiliser are combined and with the offgas from the
Produced Water Injection Unit are routed to the BSRU. The following tables outline the composition
given for each of the streams.
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Table 2: Off Gas Feed to BSRU

Flow rate
Temperature
Pressure
CO2
Feed Gas Conditions

0.01
0.045
120
40
127
91
psig
Composition (dry basis)

4.390
32.66000
Nitrogen
0.600
Methane
MMSCFD
%-mole
0.19700
%-mole
90.286
0.00000
%-mole
Ethane
2.841
57.33700
%-mole
Propane
1.017
3.74200
%-mole
i-Butane
0.215
1.68500
%-mole
n-Butane
0.240
0.37300
%-mole
i-Pentane
0.100
0.41800
%-mole
n-Pentane
0.074
0.17000
%-mole
n-Hexane
0.096
0.12600
%-mole
n-Heptane
0.099
0.15100
%-mole
n-Octane
0.037
0.14300
%-mole
n-Nonane
0.007
0.04800
%-mole
H2S
45
0.00800
ppmv
M-Mercaptan
13
0.00000
ppmv
0.4
137
ppmv
H2O
39
%-mole
Condensate
%-mole
100.00
100.00
COS
Total
Notes:
(1) Feed Gas compositions have been normalized with water exception of
water content;
(2) Mercaptan speciation was taken as 100% methyl mercaptan;
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2.2
Product Specifications
The AGTU has a total of 3 final products and 3 intermediate products as described below.
Table 3: List of Product Streams from AGTU
Final Products
Unit From
Stream
Sales Gas
MSU
To
Custody Transfer Metering
Recovered Sulfur
BSRU
Site Storage
Incinerator Stack Gas
BSRU
Environment
Intemediate Products
Unit From
Stream
To
Flash Gas
AGRU
Fuel Gas System
Fuel Gas
MSU
Fuel Gas System
Bleed Stream
BSRU
Effluent Treatment Plant
The following product specifications have been applied:

Table 4: Sales Gas Specification
Parameter
Value
Unit
Temperature, max
120
oF
Pressure, min
330
psig
lbs/MMscf
5-10
micron
CO2 content , max.
%-mole
H2S , max.
ppmv
Total sulphur, max.
30
ppmv
Water content, max

Particles, size
Table 5: Recovered Sulphur Specification

Parameter
Value
Unit
Sulfur Purity, min.
99.5
%wt
Inorganic Ash, max.
0.05
%wt
Carbon Content, max.
0.05
%wt
H2S Content, max.
10
ppmwt
Water Content, max.
%wt
Color
Flake Size
Odour
Bright Yellow
10-15
cm
Odourless
Notes:
(1)
(2)
The biosulphur product, out of the Shell Paques Unit has proven use in the
agricultural industry and will result in savings on investment of the sulphur workup section.
The sulphur work-up section (melter and flaking system) is not a Shell licensed
process and thus performance guarantees shall have to be made with the
respective vendors.
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Table 6: Incincerator Stack Gas Specification

Parameter
Value
Unit
Sulfur Dioxide, SO2
2600
mg/Nm3
Notes:
(1)
(2)
2.3
Based on 25oC and 1 atm.

Maximum O2 content of stack gas is 3% vol.
AGTU Plant Capacity
The AGTU has been sized for a maximum capacity of 75 MMSCFD of the Feed Gas to the AGRU. No
further overcapacity has been incorporated at this stage of the project.
2.4
Design Considerations & Assumptions
Reference is made to the Block Diagram of the AGTU.
2.4.1
Mercaptan Speciation & Handling

The mercaptan speciation plays an important role in determining how the desired total sulphur
specification can be achieved out of the AGTU. In discussion with TRIPATRA the speciation
adopted for the feed gas was advised as 100% methyl-mercaptan.
The amount of mercapatans in the feed gas to the AGTU is high and on the basis that
mercapatans removal in the AGRU is to be achieved using an enhanced MDEA process (i.e.
Shells ADIP-X), the amount of mercaptan removal to be performed by the MSU is too high
and will result in a bed size which is beyond the practical limitations of Molecular Sieves
technology. For this reason, the use of an MDEA hybrid solvent Shells Sulfinol-X, has been
applied, such that bulk of the mercaptans (~97%) can be removed in the AGRU and sent for
Sulphur recovery.
Appendix VIII contains a reference list of Sulfinol applications wherein similar combination of
contaminants have been addressed.
2.4.2
Feed Gas Condition

For the purpose of the current design, the following assumptions have been made for the feed
gas to the AGRU:
2.4.3
It is free of any solid particles

It is free of liquid hydrocarbons
The gas is at its (water) dewpoint
Use of Shell Proprietary Contacting Internals in the AGRU Absorber

The RFP mentions the use of a packed column for the AGRU absorber, however upon
comparison the use of Shell Proprietary Calming Section/Hi-Fi trays in the AGRU absorber is
expected to reduced the column height by about 2-4 meters as use of packing will require
additional space internal liquid redistributors.
Calming
2.4.4
Section, Hi-Fi, ADIP-X and Sulfinol are trademarks of Shell
Use of Solvent Flash Vessel

Though the amount of hydrocarbon entrainment can be minimized through the use of special
internals at the bottom of the main absorber, the use of a solvent flash vessel was reviewed and
retained for the following reasons:
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(a) The solvent flash vessel provides a buffer/surge capacity which contributes to the
operational stability of the system as it protects the regeneration section of the AGRU from
being directly affected by any upset in the absorber;
(b) A Flash Gas Absorber (FGA) has been included to produce a desulfurized flash gas stream,
which will be available for use as fuel gas.
2.4.5
AGRU Feed Gas and Treated Gas Knock Out Drums

TRIPATRA has confirmed the inclusion of a filter colaescer vessel in the following locations:
1)
upstream the AGRU Feed Gas Knock out Drum
2)
downstream the AGRU Treated Gas Knock Out Drum
which are expected to perform the same if not better removal efficiency of liquids from the gas
stream. Hence it can be considered to remove the assocaited AGRU Feed and Treated Gas
Knock Out Drums under the conditions that:
The filter coalescer is located inside the AGRU plot or such that omission of the AGRU
Sweet/Treated Gas Knock Out Drum does not create a portion of piping that can have
condensation of free liquids, which could lead to corrosion.
The design of the filter coalescer is the responsibility of TRIPATRA.
2.4.6
Integration with the Molecular Sieve Regeneration Gas Recovery

The option of the proposed Caustic Unit for the recovery of the MSU Regen Gas was compared
to the use of an amine scrubber as an alternative option.
The initial conclusion from a +/- 35% FOB cost comparison of main equipment items was that
there is no significant difference but the main benefits of employing an amine absorber for regen
gas treating in the MSU are:
Lower plot space requirements due to lower equipment count as well as associated
auxillary and caustic storage facilities which will impact the overall installed cost;
1 less toxic waste stream (Di-Sulphide Oil, DSO) to store/dispose;
1 less unit to operate as the amine scrubber can be treated as part of the AGRU and does
not require a different skill/competence to operate;
Less regret cost should there be a lower mercaptan content during actual operating
conditions;
Presence of about 5 % CO2 in the regen gas will lead to very high consumption / loss of
caustic. This is not an issue with an amine scrubber because the used up amine is
completely regenerated.
Hence it is recommended to use an Amine Scrubber to recover the MSU Regen Gas.
2.4.7
Use of a Mechanical Refrigeration Loop in the MSU

The RFP specifies the use of an Air Cooled Exchanger to cool and AGRU Sweet/Treated Gas
stream prior to entering the Sweet/Treated Gas Knock Out Drum. This will bring the gas
temperature down to approximately 116oF (46oC), which is much above the typical inlet
temperature to a mol sieve unit based on LNG applcations. It is typically not recommended to
design a MSU unit a high inlet temperature.
The following are the key benefits seen in the design of the Molecular Sieve Unit if designed on
the basis of an inlet temperature of 21oC as compared to a design at a high inlet temperature
(about 46oC):
The height of the water removal mol-sieves is halved
Around 5% decrease in the height of Sulphur removal mol-sieves.
About 17% decrease in the mol-sieve vessel diameter.

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Regen gas flow decreases by about 50%.
The effect on the regen gas flow is crucial as this also affects the sizing of the Regen Gas
Scrubber and the associated solvent circulation rate and thus the final sizing of the AGRU.
The estimated duty requirement is approximately 1.5 MW and is recommended to be included as
part of the utilities system. Propane can be used as the refrigerant for this purpose.
Further benefit of the refrigeration system can be utilized by cooling the main sour gas feed to the
AGTU, which will subsequently improve the sizing of the AGTU.
2.4.8
Mercaptans Conversion in the BSRU

With most of the mercaptans removed in the AGRU and sent to the BSRU in the acid gas stream
exiting the AGRU regenerator column, it is required to include a feed pre-treatment unit as part
of the BSRU to enable mercaptan conversion into H2S. This is further described in Section 4 and
is based on existing and well proven process technologies.
2.4.9
Heat Integration Opportunities

Heating and Cooling duties have been specified in Appendix III Equipment Summary Sheets,
for consideration by TRIPATRA to be able to quantify the benefits of heat integration
opportunities and its effect to the rest of the plant that is outside the Shell scope of licensed
processes (e.g. Hot Oil System).
This can be further explored and developed in the BDP/FEED stage of the project.
2.4.10 Re-use of Water Streams

At several points of the process free water is knocked out of the system and can be considered
for re-use in the system as water make-up. The main considerations will be the presence of
hydrocarbons in the water stream, which can cause foaming in the amine system.
This can be further explored and developed in the BDP/FEED stage of the project.
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3. The Sulfinol - X Process

3.1
Process Overview
The Shell Sulfinol Process is a regenerative amine-based solvent technology for the removal of CO2, H2S,
and organic sulfur compounds such as mercaptans, COS, and CS2 from natural gas feed streams. The
Sulfinol Process AGRU solvent utilizes a non-proprietary formulation of amine, Sulfolane and water. The
molecular structure of Sulfolane is shown below.
Sulfolane (2,3,4,5-tetrahydrothiopene-1, 1-dioxide)
CH2
CH2
CH2
CH2
S
The presence of Sulfolane in the solvent enables the Sulfinol Process to achieve highly efficient absorption
and removal of organic sulfur compounds such as mercaptans and COS from natural gas feed.
The Sulfinol Process AGRU design for the PPGJ Project is based on application of a solvent formulation
containing 50 wt% amine (43%wt MDEA with 7% wt Piperazine), 25 wt% Sulfolane, and 25 wt% water.
3.2
Process Description
The Sulfinol Process AGRU description and equipment tag numbers referenced below correspond to the
Process Flow Diagram in Appendix 1
The natural gas feed first passes through a knockout vessel V-1001 to prevent gas gathering system
contaminants such as well treating chemicals, pipeline corrosion inhibitors, compressor oils and pipeline
scale, etc, from entering the gas absorber C-1001. These contaminants can accumulate in the amine system
and potentially lead to operating problems such as foaming and fouling. Oxygen should also be excluded
from the natural gas feed to the AGRU to minimize the potential for oxidative degradation of the solvent.
The feed gas is then contacted counter-currently in the absorber (C-1001) over Shell proprietary Calming
Section/Hi-Fi trays with lean solvent, which is supplied under flow and temperature control. The lean
solvent feed temperature to C-1001 is maintained at 5 C higher than the feed gas temperature to avoid
condensation of hydrocarbons in the absorber, which can increase the potential for foaming in the AGRU
and operational difficulties in the downstream SRU.
The treated gas is then cooled by the treated gas cooler E-1005 to 21oC and free liquids are knocked out in
the filter coalescer, V-1002 before the gas is sent to the MSU.
Rich solvent leaves the absorber column under level control and is routed to a rich solvent flash vessel V1003, in which the pressure is reduced. Dissolved and entrained hydrocarbons are separated from the rich
solvent in the flash vessel. The lighter hydrocarbons form flash gas, which is treated with a small
slip-stream of lean solvent in the flash gas absorber column (C-1003) positioned on top of V-1003 to
reduce the H2S and organic sulfur content. The treated flash gas is routed to the plant fuel gas system.
The solvent from the MSU Regan Gas Absorber is added downstream the Flash Vessel to minimize the
effects of the amount of mercaptans going to the flash gas stream and thus the corresponding height of the
Flash Gas Absorber. Entrained heavier hydrocarbons, which are insoluble in the rich solvent, are skimmed
from the upper layer of the liquid phase in V-1003.
The solvent regeneration system consists of a regenerator column C-1002 with a water wash section, an
overhead condenser E-1003, and a reboiler E-1004. The regenerator operates at low pressure and high
temperature. The pre-heated rich solvent is stripped counter-currently in the regenerator column over a
medium of trays with steam generated in the reboiler. The reboiler is heated by a hot oil loop. The
bottom section of the regenerator column holds some volume which can be used as the system's buffer
storage and surge facility by allowing the liquid level to float freely.
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Regenerated lean solvent leaves the bottom of the regenerator column and is pumped by the solvent
booster pump P-1002 through the lean/rich solvent heat exchanger E-1002 and the lean solvent cooler E1001. The solvent charge pump P-1001 further increases the lean solvent stream pressure prior to being
fed to the top of the absorber
The overhead vapour stream from the regenerator column, which contains water, CO2, H2S, COS and
mercaptans, is cooled in the regenerator overhead condenser E-1003 to condense and recover water. The
condensed water is collected in the reflux/acid gas separator vessel V-1004 and pumped by P-1003 back to
the top of the regenerator column under level control. The acid gas from V-1004 is routed to the SRU
under pressure control.
A 10% slip-stream of the circulating lean solvent is routed through a mechanical filter and an activated
carbon filter. The mechanical filter removes suspended solids and particulates from the lean solvent,
which are a potential source of foaming in the AGRU. The activated carbon filter removes non-ionic
surface-active contaminants from the lean solvent, which can also promote foaming in the system. The
activated carbon filter is followed by a mechanical post-filter to prevent breakthrough of carbon fines from
the activated carbon filter into the AGRU.
There is a net loss of water in the AGRU and to maintain the appropriate solvent concentration, makeup
water (demineralized quality) is added to the system.
3.3
AGRU Process Flow Diagram
Refer to Appendix I
3.4
Heat & Material Balance
Refer to Appendix II
3.5
Equipment
Equipment Summary Sheets with preliminary sizing of the main equipment items shown above are in
Appendix III
3.6
Utility, Catalyst & Chemical Requirements
The following utilities are required for the AGRU

Demin Water Requried as water make-up for losses in the system;
Electricity for motor drives of air cooler and any associated pumps;
Nitrogen for Solvent storage & drain vessel blanketting;
The estimated utility consumption is shown in Table 7.
Table 7 Operating & Equipment Parameters
Utility
Unit
Consumption
Electricity
kW
1150
Heating Duty
MW
26358
Water Make-up
tpd
22.5
Nitrogen
Intermittent use
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4. The Shell-Paques Process Biological Sulfur Recovery

Process
The significant advantages of utilizing Shell-Paques technology in this project include:
A lower CAPEX compared to a Claus-based solution
Ability to handle high levels of CO2 produced in the acid gas from the AGRU
System operates at a lower pressure
4.1
Process Overview
The Shell-Paques Process is an environmentally friendly biological process for H2S removal and recovery
as elemental sulfur (S) from sour gas streams. The most unique aspect of the process is that it utilizes a
living biocatalyst to oxidize H2S to elemental S. The biocatalyst belongs to the group of naturally occurring
colourless sulfur oxidizing organisms known as Thiobacilli. These are autotrophic organisms, which means
that CO2 is required as their sole carbon source. The Thiobacilli catalyst is fast growing and highly resistant
to varying process conditions. The energy needed for growth is obtained from the sulphide oxidation
process. These organisms are naturally occurring and are not genetically manipulated nor modified.
The Shell-Paques Process has the following performance features:
Achieves essentially complete H2S removal and recovery as elemental S.
Simple process configuration and control with stable operation.
Low operating and chemical costs.
Wide and flexible operating range with short system start-up and shut down times.
Environmentally friendly process based on a naturally occurring Thiobacilli biocatalyst.
Recovered sulfur is hydrophilic and directly usable for fertilizer/agriculture applications.
Inherently safe operation
The Shell-Paques process can be applied to sour feed gases with H2S concentrations ranging from 50 ppmv
to 100 vol%. Regeneration of the scrubbing solution, rather than its disposal, is a key feature of the ShellPaques Process. Regeneration of the scrubbing solution is possible because the caustic consumption due to
the absorption of H2S is compensated by the oxidation of H2S to elemental sulfur and hydroxide.
A simplified Shell-Paques Process block flow diagram is shown below.
Sour feed gas enters the bottom of a packed absorber column. H2S is removed from the sour gas in the
absorber by the alkaline Shell-Paques solvent. The treated gas passes through a demister to minimize
entrainment of solvent and exits the absorber.
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The H2S rich solvent from the bottom of the absorber is routed to the bioreactor. The bioreactor is sparged
with air to enable the biocatalyst to convert the dissolved sulfide into elemental sulfur (S), thereby
regenerating caustic soda. The sulfur slurry is then sent to the sulfur recovery section, where it is processed in
a sulphur settler and then the decanter and centrifuge, with the recovered water recycled back to the process
via the bioreactor.
The regenerated solvent is recycled from the bioreactor back to the absorber. A small slipstream of solvent is
typically bled from the system to prevent any build-up of salts.
The Shell-Paques Process consists, in principle, of three integrated process sections: an absorber, an aerobic
biological reactor, and a sulfur separator and/or recovery unit.
Feed Pre-treatment Unit

Mercaptans have been identified as a contaminant that, above a certain concentration, will have
an impact on the process performance due to its tendency to foam. Mercaptans (especially
methyl-mercaptan) are expected to be fully oxidised to dimethyl disulphide (DMDS) in the
bioreactor. DMDS oil will interfere with the sulfur particles, and consequently foam. To
maintain operability of the Shell-Paques unit, a pre-treatment is specified.
The pre-treatment unit includes a reduction section to enable conversion of all sulphur
compounds present in the feed gas (especially Mercaptans) into hydrogen sulphide. The acid gas
is first heated to ~350C with fuel gas prior entering the reactor. In the reactor, the Mercaptans
are reduced to produce H2S. The reduction process is exothermic and the gas needs to be cooled
to a suitable temperature (35C) before entering the Shell-Paques Absober.
Absorber
In the absorber, the sour feed gas is contacted counter-currently with the solvent, which is
sprayed downwards through the column by nozzles. From the absorber bottoms, the H2S rich
solvent is routed to the aerobic bioreactor, where the dissolved sulfides are oxidized into
elemental S. It is important to note that the elemental S is produced in the bioreactor and not in
the absorber. Because of this feature, plugging problems that frequently occur in conventional
caustic or liquid iron based scrubbing systems are minimized in the Shell-Paques Process. The
biologically produced elemental S actually increases the operational reliability of the system and
enhances the H2S absorption.
Bioreactor
The aerobic bioreactor contains Thiobacilli microorganisms that oxidize the dissolved sulfides
into elemental S. Appropriate bioreactor internals are used to ensure complete mixing. The
volume of the bioreactor is designed to achieve optimal activity of the biocatalyst. The exhaust air
from the reactor can normally be emitted to the atmosphere without further treatment.
The air supply to the bioreactor must be controlled to minimize the formation of sulfate, and is
automated by a control system.
The conversion of H2S into elemental S is a biological process, and the biocatalysts periodically
require nutrients to maintain good performance. The nutrients include certain salts for their
growth and maintenance. Extensive laboratory and field research has led to the optimisation of
the nutrient solution and dosing rate for this process. The nutrient solution is called Nutrimix
34/32 Solution and contains up to 12 different salts.
Material Safety Datasheet (MSDS) for the biocatalyst is as attached in Appendix VII
Sulfur Recovery
The produced elemental S is separated from the solvent in a settler. A portion of the bioreactor
contents is recycled over the settler to maintain the desired dry solid content in the system. The
elemental S slurry is then further processed in a decanter-centrifuge to obtain an S concentration
of ~50 60 wt%. The elemental sulfur typically has a purity of ~95-98% on dry basis. The
recovered water is recycled back to the process via the bioreactor.
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Sulfur Work-Up Section

Optional equipment for upgrading of the biosulphur out of the Shell-Paques Unit to create
industrial (molten) sulphur quality is added to comply with the requirements of the RFP.
This is not part of the licensed process and further information is given in Appendix V.
Thermal Oxidizer (TOx)/Incinerator

The purpose of the Thermal Oxidizer/Incinerator is to combust the remaining sulphur species
from the main processes of the BSRU
The treated gas from the Shell Paques absorber and the Bioreactors are sent directly to the TOx,
where it is combusted along with the offgas streams from units outside the AGTU. The TOx
oxidizes all sulphur compounds and hydrogen in the gas at ~850 C in the presence of a surplus
of air to SO2 and CO2.
The gas streams are heated to ~ 850C in the TOx mixing chamber. Fuel gas is combusted with
air to provide the high temperature required. There are two air lines to the TOX, the primary air
to the TOX burner to combust all of the fuel gas and the secondary air to the TOX mixing
chamber to ensure that there is sufficient O2 at the outlet (greater than 2 %v) to oxidise all of the
sulphur compounds.
The SO2 off-gas from the TOx is routed to the vent stack.
4.2
Process Chemistry
In the Shell-Paques Process absorber, H2S is removed from the sour gas by the alkaline scrubbing solution
in the absorber, which is maintained at a pH of ~8-9. The absorption of H2S proceeds according to the
following reaction:
H 2 S + NaOH NaHS + H 2 O
In the above reaction, alkalinity is consumed. This alkalinity consumption is compensated by the oxidation
of H2S to elemental sulfur, which proceeds under oxygen controlled conditions according to the following
reaction:
NaHS + O2 S o + NaOH
In the Shell-Paques Process, the Thiobaccilli biocatalyst oxidizes the H2S to elemental sulfur. The
biocatalyst is highly resistant to varying process conditions.
A small part of the dissolved sulfide will be oxidized to sulfate according to the following side-reaction:
2 NaHS + 4O2 2 NaHSO 4 Na 2 SO4 + H 2 SO4

A small amount of thiosulfate is also formed. As a result of this side-reaction, caustic is required to
neutralize the sulfuric acid formed. A small bleed stream is typically withdrawn from the system to prevent
the build-up of sodium sulfate, sodium thiosulfate, and other salts. The bleed stream, which contains
sodium salts and some elemental S particles, is harmless and can typically be discharged without further
treatment, depending on local environmental regulations.
4.3
Process Description
The Shell-Paques Process SRU was designed to remove and recover ~25.7 MT/D of sulfur from the acid
gas produced by the AGRU unit.
The Shell-Paques Process unit shall be a single train with one absorber, in which the AGRU Acid Gas is
treated counter-currently over a three-packed bed configuration. The absorber has liquid and gas
distribution devices in the top and bottom and liquid and gas redistribution devices between the packed
beds. The absorber operates at low pressure so no flash vessel is required upstream of the bioreactor.
The bioreactor is a CIRCOX-type air-lift loop reactor, which consists of a tall cylindrical reactor containing
multiple internal cylinders to create distinct aerated and non-aerated zones. Lean scrubbing solution is
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collected in the top of the bioreactor in a degassing module. The bioreactor internals are proprietary and is
supplied by Paques B.V.
The sulfur settler is a Tilted Plate Settler (TPS) type, which operates continuously. Sulfur is recovered from
the solution by gravitational settling, which produces a sulfur slurry containing ~10 wt% of solids. The
liquid overflow from the settler is low in solids content and is collected in the settler effluent tank and
recycled to the bioreactor. The TPS module in the sulfur settler is a proprietary internal that is supplied by
Paques B.V.
The sulfur dewatering unit is designed to remove the maximum sulfur load in a 24 hr/day runtime. When
not operating at maximum load, either the feed rate to the sulfur dewatering unit can be reduced or the
runtime can be shortened, the latter typically being the preferred option. The standard sulfur dewatering
unit used in this technical estimate is a decanter-centrifuge type, which produces a sulfur cake with a dry
solids content of ~50-60 wt%.
The bioreactor, sulfur settler, and tanks are operated at atmospheric pressure. A Vent Air Treatment
system can be installed if required to remove any residual H2S present in the bioreactor exhaust air
(typically < 1-2 ppmv H2S), however, it has not been included in the scope of this technical estimate.
4.4
BSRU Process Flow Diagram
Refer to Appendix I
4.5
4.6
Equipment
Appendix III.
4.7
Stream Summary
The estimated stream conditions and compositions based on the design conditions (per Shell-Paques
Process train) are shown in the following tables:
Table 8
Stream Conditions (per train)

Temperature
Pressure
bara
Flow
Stream
Stack Gas from
Incinerator
pH
SO2
Downstream
Unit (1)
Environment
43,064
Nm3/hr
750
1.01
< 2600Nm3/hr
Sour Water
1.0 m3/hr
35
1.40
NA
Effluent
Treatment Plant
Bleed
5.4 m3/hr
40
TBD
8.0-9.3
Effluent
Treatment Plant
8.0-9.3
Sulphur
Processing
Section
Sulfur Cake @
60 wt% Solids
1656 kg/hr
40
NA
Notes: (1) To be confirmed during the BDP / FEED design phase.
Table 9 Vapor Stream Compositions

Stream
Treated Gas H2S Absorber
Vent Air Bioreactor
H2S, ppmv
< 25
<1
H2O, vol%
saturated
saturated
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Table 10 Liquid Stream & Sulfur Cake Compositions

Stream
S
Bleed
< 2 g/l
Sulfur Cake @ 60 wt% Solids
60 wt%
Notes: (1) Aqueous phase composition.
HSmg/l
<1
< 1 (1)
Na+
kg/m3
25-35
25-35 (1)
SO42- + S2O32
kg/m3
20-40
20-40 (1)
HCO3-+ CO32kg/m3
30-50
30-50 (1)
The bleed stream is primarily water containing some salts (sodium sulfate, sodium thiosulfate),
anions (carbonate, bicarbonate) and small amounts of biocatalyst and sulfur.
The recovered sulfur is in the form of a wet cake or paste. The sulfur product is hydrophilic with
a small particle size and can be re-diluted if necessary for easier handling, which makes it very
suitable for agricultural purposes.
4.8
The following utilities and consumables are required for the Shell-Paques Process:
Electricity - Electricity is required for the pumps and the decanter-centrifuge.
Make-Up Water - Make-up water is added to the Shell-Paques Process to compensate for losses via
the bled stream, evaporation in the absorber and bioreactor, and with the sulfur product. The water
should have a maximum hardness of 10 0DH (= total Ca + Mg < 70 mg/l). It should be free of
chlorine and have no suspended particular matter. Drinking quality water quality can typically be used as
make-up water.
Cooling Duty - The biological oxidation of H2S to elemental sulfur is an exothermic reaction. Cooling
water is used to cool the rich solution and maintain the bioreactor temperature in an optimum
temperature range.
Caustic Caustic (NaOH) is added to the Shell-Paques Process to provide solvent alkalinity and
facilitate H2S absorption, and to compensate for the loss of sodium ions with the bleed stream. Caustic
is typically added as a 20 or 50 wt% solution.
Nutrient Solution - Nutrient solution (Nutrimix 34/32) is required for the maintenance of the
Thiobacilli biocatalyst. Nutrimix 34/32 is supplied by Paques B.V. The estimated price is Euros
1.20/liter.
Air Air is required for sparging the bioreactor. Plant air is available at 6 barg and ambient
temperature, which is deemed suitable for this service and eliminates the need for an air blower.
Fuel Gas Fuel gas is required for both the pre-treatment unit and the incinerator to meet the
heating requirement of the process gas. Treated gas from the MSU unit is used as the basis of
design and further optimisation of fuel gas consumption can be performed at the next design phase.
The utility, catalyst and chemical consumption estimates are shown in Table 14.
Table 11
Utility & Consumable Estimates
Electricity (1)
kW
981.7
Cooling Duty
MW
11.2
Caustic (100 wt%)
kg/hr
648
li/hr
34.3
Make-Up Water
m3/hr
5.26
Fuel Gas (2)
kg/ hr
1260
Nutrients-Nutrimix
Notes:
34/32
(1) Based on an overall efficiency of 70%.

(2) Fuel gas is assumed to be supplied from the treated gas ex MSU unit.
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5.
The Molecur Sieve Process
5.1
Process Overview
In natural gas dehydration and mercaptan removal applications with type 4A or 3A sieves, thermal swing
regenerative adsorption process is used. The water removal (4A or 3A) and mercaptan removal (5 A or 13
X ) molecular sieves are used in series to achieve simultaneous dehydration and mercaptan removal in a
common vessel. Dehydration and mercaptan removal of the process gas is achieved by its passage through
one or more fixed molecular sieve bed(s). A bed is removed from adsorption service and regenerated by
passage of hot gas which desorbs and carries away the adsorbed water and mercaptans from the sieves.
The regenerated bed containing small amounts of water and mercaptans (residual loading) is returned to
adsorption service after cooling. In the meantime the process gas dehydration is achieved by another other
bed(s). Thus the natural gas dehydration and mercaptan removal is continuously accomplished while the
beds themselves undergo cyclic batch operations of adsorption and regeneration.
Relevant adsorption and regeneration fundamentals are discussed in greater detail below with respect to
dehydration molecular sieves. These fundamentals are similar and are equivalently applicable to mercaptan
removal molecular sieves as well.
Adsorption
In adsorption, gas flows usually from top to bottom of a regenerated bed. During the course of
adsorption two zones will develop. The bed at the top will be saturated with water under the feed
conditions of temperature, pressure and water concentration and is called the Saturation Zone
(SZ). No water adsorption takes place in the saturation zone.
A finite part of the bed below the saturation zone is engaged in dehydrating the gas from feed
water concentration (wet) to effluent water concentration (dry), called the Mass Transfer Zone
(MTZ). Correspondingly, the sieve loading in the mass transfer zone progressively drops from
saturation level at top to rest loading at bottom.
With time, the saturation zone gets longer and moves downward. The length of the mass transfer
zone, on the other hand, remains constant for the given application. The mass transfer zone,
however, moves down with the same speed as the elongation of the saturation zone. This speed is
directly related to the rate of water removed from the feed gas. The bed below the mass transfer
zone is potentially active but takes no part in dehydration. In general, the length of the mass
transfer zone in natural gas dehydration is a function of the molecular sieve grade, gas superficial
velocity and water concentration in feed. In normal operating range, temperature and pressure
have little influence.
The adsorption step should be terminated before imminent breakthrough to allow a reliable
operation which will meet the required specification. In doing so, a non-utlized zone is created, as
presented in Figure V.
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Contaminant conc. in process stream

Product
Spec.
Feed
Concentration
Direction
of the flow
Saturated Zone (SZ)
a) The saturated zone (SZ) wherein the

adsorbent has achieved its maximum
loading and the concentration of the
contaminant in the process stream does not
change.
b) The m ass transfer or chem ical reaction

zone (M TZ/CZ) wherein the adsorbent is
only partially loaded and the contam inant
level drops from its feed concentration
down to the product level.
Mass transfer or
chemical reaction
zone (MTZ/CZ)
Non-utilised zone (NZ)
Figure V
c) The non-utilised zone (NZ) wherein both

concentration and adsorbent loading
changes are negligible.
Bed Zones
Regeneration
The objective of regeneration is to strip off the adsorbed impurities from the bed, after it has
been taken out of adsorption service. This is conveniently done by passage of hot gas and then
cold gas through the bed. Water stripped off by the hot gas is condensed and disposed of.
The hot regeneration gas serves two important purposes: provide heat to desorb water and act as
carrier gas to carry away the desorbed impurities, thus enabling deep regeneration. The
regeneration is carried out at the normal operating pressure, using a slip stream of the dried
product gas supplied counter-currently, based on the low water content specification.
Heating gas temperatures of 320C is required for 4A molecular sieves and is dictated by the
thermal stability limitations of these sieves. Lower temperatures are impractical from stripping
kinetics point of view and may lead to less efficient removal.
At the end of heating step and before the bed is returned into service, it is necessary to cool the
bed to restore its adsorption capacity. This is done by continuing the passage of regeneration gas
without the supply of heat. This counter-current dried gas cooling is adequate in dehydration
applications and has an advantage of valving simplicity and "thermal pulse", in which the initial
part of the cooling step also achieves some stripping due to hot cooling outlet gas.
For both the heating and cooling steps the rise and fall of gas temperature (at the start of heating
and cooling steps respectively) is controlled to minimise thermal fatigue stresses of the steel.
The gas outlet temperature is expected to come to within 15 - 20C of the inlet temperature at the
end of heating and cooling steps. While the shape of the outlet heating gas temperature varies
widely from application to application. The presence of a plateau (at approx. 150C) is sometimes
reported. This can be attributed to bulk desorption of water.
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400.0
heating
cooling
stand-by
350.0
temperature [ C ]
300.0
250.0
200.0
150.0
100.0
50.0
0.0
0
10
11
time from start of regen. [ hour ]
Figure 3
Typical temperature profile for a type 4A mol sieve dehydration unit
Water is typically desorbed in the "flat" peak and the peak flow rate is a rule of thumb 3 times
the average stripping rate . It is important to realise that during the initial part of the heating
step, free water can be formed in the upper section of the bed and on the inside of the top
dome of the vessel. This is because these parts offer relatively cold surfaces for moisture in
regeneration gas to condense. Later in the heating step the condensed water is re-vaporised, as
the temperature climbs up.
Ageing of Mol sieve

The deactivation rate of molecular sieves as a function of number of regenerations. And mol
seive units are generally sized for 3 years lifetime
5.2
Process Description
The treated gas from the Acid Gas Removal Unit (AGRU, U-1000) leaves at 21 C and is passed over
molecular sieve beds, removing the remaining mercaptan content and water to meet the sales gas
specification. The recommended adsorbent for dehydration is 4A molecular sieve and the additional bed
for mercaptan removal can use either 5A or 13X molecular sieves.
Each molecular sieve bed can be completely isolated from the process to allow molecular sieve change out
during operation.
Two beds operate in parallel in adsorption mode and one bed operates in regeneration mode. Each
molecular sieve bed cycles consecutively through adsorption, heating, and cooling modes under control of
a sequence control system. During the adsorption, gas flows downwards through the bed; during the
heating and cooling stages, gas flows upwards through the bed. The gas leaving the molecular sieve
adsorbers is split into three streams which are:
a) as sales gas
b) fuel gas supply
c) regeneration gas
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The regeneration gas, is routed to the regeneration-gas heater (E-1301), where it is heated and subsequently
used for regeneration of the regenerating bed. The slipstream is normally heated to 320C, with a
maximum of 350C in E-1301, using hot oil. The regeneration-gas flow rate is constant and temperature
control of this gas stream is achieved by bypassing E-1302. The heated gas stream passes upwards through
the molecular sieve bed, thereby driving the water and mercaptans from the molecular sieves.
After passing through the bed in heating mode, the regeneration gas is cooled by air cooler E-1302.
Condensed water, which also may contain co-adsorbed hydrocarbons, is knocked out in vessel V-1301 and
routed to water effluent treating/re-injection. The gas leaving V-1301 still contains the mercaptans
removed from the adsoprtion beds and is recovered by the regen Regen gas Gas absorberAbsorber, C1302, which is a Sulfinol-X absorber integrated with the rest of the AGRU. The desulphurized regen gas
passes through the regen gas knockout vessel, V-1302 and is then compressed by a centrifugal compressor
K-1301 and routed back to the inlet of the treated gas cooler (E-1005) in the AGRU where it combines
with the feed gas.
5.3
MSU Process Flow Diagram
Refer to Appendix I
5.4
5.5
Equipment
Appendix III.
5.6
The following utilities, catalyst/adsorbent and chemicals are required for the MSU
Electricity for motor drives of air cooler and any associated pumps;
Nitrogen for purging
Instrument Air for actuation of the valves
Heating Medium for actuation of the valves
The estimated utility consumption is shown in Table 12.
Table 12 Operating & Equipment Parameters
Utility
Unit
Consumption
4A Adsorbent
m3
29.5
5A/13X Adsorbent
m3
18.5
Heating Duty
kW
875
Electrcity
kW
520
Nitrogen
Intermittent use
Notes: (1) Adsorbent volumes are based on the total requirement for 3 beds, rounded up
to the nearest 0.5 m3 and does not contain any volume for contingency (e.g breakage
during shipping)
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Appendices
The following Appendices are supplied as attachements to this proposal
Appendix I
Simplified Process Flow Diagrams
Appendix II
Heat & Material Balances
Appendix III
Equipment Summary Sheets
Appendix IV
General Information on Biosulphur
Appendix V
Biosulphur Workup Options
Appendix VI
Sulphur Melter Information
Appendix VII
Material Safety Data Sheets
Appendix VIII
Reference Lists
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Shell Global Solutions

Confidential Technical Proposal PPGJ Project : CPP Gundih AGTU

Shell Global Solutions

Van Hooijdonk, Jeroen

Koh, Boon Eng

van Heeringen, Gijs

Shell Global Solutions

Block Flow Diagram of Acid Gas Treating Unit (AGTU)

Sales Gas from AGTU

HP Fuel Gas to Distribution

Bleed Stream to Effluent

Shell Global Solutions

Block Flow Diagram of Acid Gas Treating Unit (AGTU)

Overview of the Project

The Integrated Treating Line-up

2.1 Feed Gas Specifications

2.2 Product Specifications

2.3 AGTU Plant Capacity

2.4 Design Considerations & Assumptions

Mercaptan Speciation & Handling

Feed Gas Condition

2.4.3 Use of Shell Proprietary Contacting Internals in the AGRU

Use of Solvent Flash Vessel

AGRU Feed Gas and Treated Gas Knock Out Drums

2.4.6 Integration with the Molecular Sieve Regeneration Gas

Use of a Mechanical Refrigeration Loop in the MSU

Mercaptans Conversion in the BSRU

Heat Integration Opportunities

Re-use of Water Streams

The Sulfinol - X Process

AGRU Process Flow Diagram

3.4 Heat & Material Balance

3.6 Utility, Catalyst & Chemical Requirements

Shell Global Solutions

The Shell-Paques Process Biological Sulfur Recovery Process

4.2 Process Chemistry

4.3 Process Description

4.4 BSRU Process Flow Diagram

4.5 Heat & Material Balance

4.7 Stream Summary

4.8 Utility, Catalyst & Chemical Requirements

The Molecur Sieve Process

5.1 Process Overview

5.2 Process Description

5.3 MSU Process Flow Diagram

5.4 Heat & Material Balance

Shell Global Solutions

Filter coalescer, F-0205 on feed to AGRU

Filter coalescer, F-0301 A/B on feed to MSU

Shell Global Solutions

2. The Integrated Treating Line-up

Feed Gas Specifications

Composition (dry basis)

Shell Global Solutions

Table 2: Off Gas Feed to BSRU

Feed Gas Conditions

Composition (dry basis)

Shell Global Solutions

Custody Transfer Metering

Incinerator Stack Gas

Fuel Gas System

Fuel Gas System

Effluent Treatment Plant