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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.
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Document History
Date 20/9/2008 Issue A Reason Change Issued for internal appoval for Auhors Blas, Wilfredo Koh, Boon Eng Srivathsan, Bharath Bajpai, Vishrut Reviewed/Verified by de Oude, Matthijs Sakthivel, Ramachandran Srinivasan, Rajiv van Heeringen, Gijs Paques B.V. Approved by Van Hooijdonk, Jeroen
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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
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. 1. Background Information Background Information 1.1 1.2 2. Overview of the Project Scope of Proposal 4 5 6 8 8 8 8 9 9 11 12 12 12 12
The Integrated Treating Line-up 2.1 Feed Gas Specifications 2.2 Product Specifications 2.3 AGTU Plant Capacity 2.4 Design Considerations & Assumptions 2.4.1 2.4.2 Mercaptan Speciation & Handling Feed Gas Condition
2.4.3 Use of Shell Proprietary Contacting Internals in the AGRU Absorber 12 2.4.4 2.4.5 Use of Solvent Flash Vessel AGRU Feed Gas and Treated Gas Knock Out Drums 12 13
2.4.6 Integration with the Molecular Sieve Regeneration Gas Recovery 13 2.4.7 2.4.8 2.4.9 2.4.10 3. Use of a Mechanical Refrigeration Loop in the MSU Mercaptans Conversion in the BSRU Heat Integration Opportunities Re-use of Water Streams 13 14 14 14 15 15 15 16 16 16 16
6
The Sulfinol - X Process 3.1 3.2 3.3 Process Overview Process Description AGRU Process Flow Diagram
3.4 Heat & Material Balance 3.5 Equipment 3.6 Utility, Catalyst & Chemical Requirements
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4.
The Shell-Paques Process Biological Sulfur Recovery Process 4.1 Process Overview 4.2 Process Chemistry 4.3 Process Description 4.4 BSRU Process Flow Diagram 4.5 Heat & Material Balance 4.6 Equipment 4.7 Stream Summary 4.8 Utility, Catalyst & Chemical Requirements
17 17 19 19 20 20 20 20 21 22 22 24 25 25 25
5.
The Molecur Sieve Process 5.1 Process Overview 5.2 Process Description 5.3 MSU Process Flow Diagram 5.4 Heat & Material Balance 5.5 Equipment 25 5.6 Utility, Catalyst & Chemical Requirements
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1.
1.1
Background Information
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:
Equipment Items Filter coalescer, F-0205 on feed to AGRU Filter coalescer, F-0301 A/B on feed to MSU
*Refer to Section 2.4.6 with respect to the recommeded removal of the caustic unit from the AGTU.
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2.1
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 Flow rate Temperature Pressure Carbon Dioxide Nitrogen Oxygen Methane Ethane Propane i-Butane n-Butane i-Pentane n-Pentane n-Hexane n-Heptane n-Octane n-Nonane n-Decane H2S Mercaptans Carbonyl Sulphide Feed Gas Conditions 75 MMSCFD 108 400 F psig
Composition (dry basis) %-mole 23.00 0.47 0.00 70.78 2.23 0.8 0.17 0.19 0.08 0.06 0.08 0.09 0.04 0.01 0 7000 1700 50 %-mole %-mole %-mole %-mole %-mole %-mole %-mole %-mole %-mole %-mole %-mole %-mole %-mole %-mole ppmv ppmv ppmv
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 Nitrogen Methane Ethane Propane i-Butane n-Butane i-Pentane n-Pentane n-Hexane n-Heptane n-Octane n-Nonane H2S M-Mercaptan COS H2O Condensate Total Feed Gas Conditions 0.01 0.045 120 40 127 91 MMSCFD F psig %-mole %-mole %-mole %-mole %-mole %-mole %-mole %-mole %-mole %-mole %-mole %-mole %-mole ppmv ppmv ppmv %-mole %-mole
Composition (dry basis) 4.390 32.66000 0.600 90.286 2.841 1.017 0.215 0.240 0.100 0.074 0.096 0.099 0.037 0.007 45 13 0.4 0 0 100.00 0.19700 0.00000 57.33700 3.74200 1.68500 0.37300 0.41800 0.17000 0.12600 0.15100 0.14300 0.04800 0.00800 0.00000 137 39 0 100.00
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 Stream Sales Gas Recovered Sulfur Incinerator Stack Gas Stream Flash Gas Fuel Gas Bleed Stream Final Products Unit From MSU BSRU BSRU Intemediate Products Unit From AGRU MSU BSRU To
Custody Transfer Metering Site Storage Environment To Fuel Gas System Fuel Gas System Effluent Treatment Plant
Table 5: Recovered Sulphur Specification Parameter Sulfur Purity, min. Inorganic Ash, max. Carbon Content, max. H2S Content, max. Water Content, max. Color Flake Size Odour Value 99.5 0.05 0.05 10 1 Bright Yellow 10-15 Odourless cm Unit %wt %wt %wt ppmwt %wt
Notes:
(1) 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.
(2)
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Table 6: Incincerator Stack Gas Specification Parameter Sulfur Dioxide, SO2 Value 2600 Unit mg/Nm3
Notes:
(1) (2) Based on 25oC and 1 atm. Maximum O2 content of stack gas is 3% vol.
2.3
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
2.4.1
2.4.2
2.4.3
2.4.4
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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
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.
2.4.6
2.4.7
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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
2.4.9
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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
Refer to Appendix I
3.4
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
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 Electricity Heating Duty Water Make-up Nitrogen Unit kW MW tpd Consumption 1150 26358 22.5 Intermittent use
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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.
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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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:
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
Refer to Appendix I
4.5
Refer to Appendix II
4.6
Equipment
Equipment Summary Sheets with preliminary sizing of the main equipment items shown above are in 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 Stream Stack Gas from Incinerator Sour Water Bleed Sulfur Cake @ 60 wt% Solids Flow 43,064 Nm3/hr 1.0 m3/hr 5.4 m3/hr C Pressure bara pH SO2 750 35 40 1.01 1.40 TBD < 2600Nm3/hr NA 8.0-9.3 Effluent Treatment Plant Effluent Treatment Plant Sulphur Processing Section Downstream Unit (1) Environment
1656 kg/hr
40
NA
8.0-9.3
Table 9 Vapor Stream Compositions Stream Treated Gas H2S Absorber Vent Air Bioreactor H2S, ppmv < 25 <1 H2O, vol% saturated saturated 20
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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 Electricity (1) Cooling Duty Caustic (100 wt%) Nutrients-Nutrimix Make-Up Water Fuel Gas (2) Notes: 34/32 Utility & Consumable Estimates kW MW kg/hr li/hr m3/hr kg/ hr 981.7 11.2 648 34.3 5.26 1260
(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.
5.1
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. Direction of the flow Feed Concentration
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.
Figure V
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
350.0 300.0 temperature [ C] 250.0 200.0 150.0 100.0 50.0 0.0 0 1 2 3 4 5
cooling
stand-by
10
11
Figure 3
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.
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
Refer to Appendix I
5.4
Refer to Appendix II
5.5
Equipment
Equipment Summary Sheets with preliminary sizing of the main equipment items shown above are in 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 4A Adsorbent 5A/13X Adsorbent Heating Duty Electrcity Nitrogen Unit m3 m3 kW kW Consumption 29.5 18.5 875 520 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 Appendix II Appendix III Appendix IV Appendix V Appendix VI Appendix VII Appendix VIII Simplified Process Flow Diagrams Heat & Material Balances Equipment Summary Sheets General Information on Biosulphur Biosulphur Workup Options Sulphur Melter Information Material Safety Data Sheets Reference Lists
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