IBP2144_10 SUCCESSFUL INTEGRATION OF MEMBRANES FOR CO2 REMOVAL INTO AN FPSO TOPSIDES PROCESS SCHEME Gunasekaran Palanivel1, Brian

Monty2, and William Echt3

This Technical Paper was prepared for presentation at the Rio Oil & Gas Expo and Conference 2010, held between September, 1316, 2010, in Rio de Janeiro. This Technical Paper was selected for presentation by the Technical Committee of the event according to the information contained in the abstract submitted by the author(s). The contents of the Technical Paper, as presented, were not reviewed by IBP. The organizers are not supposed to translate or correct the submitted papers. The material, as it is presented, does not necessarily represent Brazilian Petroleum, Gas and Biofuels Institutes opinion, nor that of its Members or Representatives. Authors consent to the publication of this Technical Paper in the Rio Oil & Gas Expo and Conference 2010 Proceedings.

Abstract
Many new oil reserves are being developed offshore in deep water where producing platforms are not practical. Producing oil offshore on a Floating Production, Storage and Offloading vessel (FPSO) requires processing the associated natural gas, which always contains water and valuable hydrocarbons. The gas may also contain significant amounts of carbon dioxide (CO2) as well as trace contaminants such as hydrogen sulfide (H2S) and mercury (Hg). Gas conditioning offshore is not new, but the challenges of integrating technologies for a comprehensive economical process can be significant. This paper describes a venture in creating an optimized solution for a range of gas processing conditions on an FPSO. For the first of their pre-salt fields they intend to develop, Petrobras requested potential contractors bid an FPSO capable of producing oil and associated natural gas which could have a wide range of CO2 content. While the gas processing section was to incorporate the option to use membranes for CO2 removal, the final configuration of the topsides process was left to the vessel contractors. MODEC International, Inc., the eventual winner of the tender, evaluated various membrane suppliers as well as processing options using membranes to remove CO2 from the associated natural gas. CO2 levels ranged from 8 to 25 mole% in the associated gas and the product gas specification was less than 5 mole%. Stringent specifications applied to all of the design cases. At the same time, dehydration, H2S removal, and dew point control had to be worked into the processing scheme. In recent offshore project awards, UOP LLC, A Honeywell Company had integrated UOP Separex membrane systems into the overall process flow scheme in various ways to create optimum solutions for their customers. This paper describes how an economical process scheme was developed for the Tupi Pilot FPSO.

Project Schedule
Petrobras requested that the FPSO vessel be operational not later than December 2010. The project was awarded to MODEC in August 2008. MODEC immediately began to award sub-suppliers for delivery of the compressors and process modules. Award of the CO2 removal membranes was made at the end of October 2008 to UOP with a project schedule of 61 weeks. UOP delivered the membrane module two weeks early, in December 2009. At this writing, the membrane module is installed and the FPSO is undergoing pre-commissioning tie-ins. The ship is due to arrive in Brazilian waters ahead of schedule in September 2010 with oil production commencing by the end of October. First gas to the processing section is targeted for November 2010.

_________________________________________________ 1 Facilities Engineering Manager, MODEC International Inc. 2 Lead Process Engineer, MODEC International Inc. 3 Technology Manager, UOP LLC, A Honeywell Company

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FPSO Processing Requirements

The following topside processing capacities were required: Produce up to 19,100 Sm3/day (120,000 bpd) of oil Process 24,000 Sm3/day (150,000 bpd) of liquids Process 5,000,000 Sm3/day (176 MMSCFD) of associated gas To accommodate oil storage and provide the required deck space for the processing equipment, MODEC identified a very large crude carrier (VLCC) for retrofitting. The vessel was cleaned and structurally modified to support a new deck area of approximately 11,000 m2. Onto this new deck, a series of modules were installed for crude separation, de-salting, produced water treatment, gas compression, dew point control, CO2 removal, H2S removal, export gas compression and high-CO2 permeate compression/pumping for re-injection. The modules were arranged with interconnecting piping, allowing room for operations and maintenance access. The selected ship has the following specifications: Shipyardintegration and conversion: Mooring System: Number of Risers: Water Depth: Storage Capacity: Oil Production: Gas Production Capacity: Water Injection: CO2 Injection: COSCO Dalian China Spread mooring wit 24 mooring legs 43 2,500 meters 1.6 MM bbl of net storage for stabilized crude 16,000 Sm3/day (100,000 bpd) 5,000,000 Sm3/day 16,000 Sm3/day (100,000 bpd) 500,000 Sm3/day

The vessel FPSO Cidade de Angra dos Reis MV22 is 330 meters in overall length, 58 meters in breadth and 29.7 meters in depth. A key feature of the FPSO topsides was processing the associated gas into two separate product streams for compression. Hydrocarbon gases were to be conditioned for pipeline transportation to shore. This required removal of water, CO2 and H2S to pipeline specifications. The CO2-rich permeate stream was to be re-injected to avoid release of green-house gases as well as to aid secondary oil recovery. While MODEC had extensive experience in many gas conditioning operations, the extent of this topside processing scheme was greater than typical. MODEC relied on technology suppliers to help with integration of the various processing steps.

Associated Gas Processing

The design of the gas treatment system needs to consider the following design ranges contained in the tender: Parameter Minimum Maximum Feed Flow Rate, Sm3/day (MMSCFD) 1,500,000 (53) 5,000,000 (176) Feed Gas CO2 Content, mole% 8 25 C6+ Content, ppm 2160 4430 Aromatics (BTEX) Content, ppm Unknown Unknown H2S Content, ppm not specified 170 Water Content Saturated Saturated The values in the Minimum and Maximum columns are not necessarily coincident with one another. It was also recognized that the gas recovered from the oil/gas separator is likely to have different compositions and flow rates than what was available in the tender documents based upon the actual properties of the produced well fluids. This uncertainty is attributed to: The wells that feed the FPSO were still being drilled, so only a partial representation was available for analysis. Producing wells would be added or taken off line, as required, for production control. Well fluids change over time as a reservoir is depleted.

This additional uncertainty warrants a robust design that is flexible to the potential variations within the operating envelope. 2

Rio Oil & Gas Expo and Conference 2010 The feed gas was to be separated into two product streams with the following specifications: Gas Property CO2 Content, mole% Water Content, ppm H2S Content, ppm Sales Gas <5 <1 <20 Acid Gas 90% (estimated) not specified N/A

Petrobras proposed as a base case an overall gas processing scheme, but allowed the FPSO provider to optimize the process, provided the required product specifications were met or exceeded. Based on their investigation of existing, standard processing units, the following flow scheme was proposed in the tender:
Vapor Recovery Unit From Subsea Wells Oil/Water Separator 20 kg/cm with heat + oil and water treatment Oil tanks H2O Molecular Sieve Dryers to <1 ppmv H2O H2O Disposal HC to Oil Hydrocarbon Dew Point Control Unit 97 to 68 kg/cm2 H2O TEG Bulk Dehydration H2S Removal 170 ppmv to <5 H2S Main (a) Compressors 20 to 98 kg/cmg

Membrane Unit 64 kg/cm2

<5% CO2

Main (b) Compressors 61 to 250 kg/cm2g Fuel Gas

Reinjection Compressors 250 to 550 kg/cmg To Pipeline To Re-injection Wells To Re-injection Wells

~90% CO2 CO2 Compression / Pumping 0 to 300 to 550 kg/cmg

Figure 1 - Overall Associated Gas Processing Scheme

Inlet Compression
Membranes had been selected as the preferred CO2 removal technology by MODEC with acceptance from Petrobras. Membranes require elevated pressure for efficient separation, but need minimal plot space. An intermediate pressure of approximately 60 kg/cm2(g) was selected for the membrane unit. Inlet compression was then sized to provide one of two possible conditions (a) approximately 100 kg/cm2 if Joule-Thompson (J-T) cooling was used in the Dew Point Control Unit (DPCU) or (b) approximately 75 kg/cm2 if propane refrigeration was to be used in the DPCU. MODEC evaluated the options and concluded that J-T expansion was simpler, less costly and required less deck space compared to refrigeration. Therefore, inlet compression was designed to discharge at 98 kg/cm2. Closed loop, inhibited fresh water (indirect cooling with seawater) would be used to obtain a discharge temperature of about 40C. Even though the higher discharge pressure results in a higher horsepower requirement for the Main (a) Compressors (3 x 50%), elimination of the propane compressor along with its spare (and the resulting reduction in plot space) offset the added cost of this feed compressor.

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H2S Removal
MODEC opted to use an H2S scavenger process that removes the hydrogen sulfide from a gas stream via reaction with a solid absorbent. The process consists of a fixed-bed of granular reactant contained in a pressure vessel. Sour gas flows downward through the bed, where the hydrogen sulfide reacts with the scavenger to form a stable and safe byproduct. Spent material is periodically replaced with fresh absorbent. A two-bed lead-lag configuration guarantees full consumption of all of the reactant. The chosen absorbent requires a water-saturated feed gas, so the H2S removal bed was located upstream of the dehydration unit. Based on a tradeoff of vessel size versus vessel wall thickness, MODEC chose to locate the vessels at low pressure, upstream of the Main (a) Compressors.

Gas Drying
For the gas dryers, MODEC selected molecular sieve technology utilizing an UOP adsorbent. There were two key criteria that required special consideration: (1) the size of the adsorber vessels and the regeneration equipment had to be minimized and (2) the sieve needed to hold up in the acidic environment of high-CO2 gas processing. UOP was able to design for both of these conditions. First, a three-bed system using series regeneration (Memphis cycle) was recommended with internal adsorber insulation. Series regeneration reduces adsorber size by simultaneously heating and cooling regeneration beds during a shortened regeneration cycle. This also serves to reduce the demand for regeneration gas versus typical longcycle-time dryers used onshore. Heating and cooling requirements are reduced to their minimum by internally insulating the adsorbers. This is critical when electricity is used for heating the regeneration gas, as was the case for this FPSO. Internal refractory insulation increases vessel weight, but saves the energy normally absorbed by the vessel walls during the heating step compared to externally insulated vessels. Second, UOP recommended specialty adsorbent AW-500 for the molecular sieve dryers. AW-500 has been specially formulated both in zeolite molecular sieve type and binder such that it will be resistant to degradation in highly acidic process streams. At high levels of CO2 (above about 5 mole%), acidic gases will attack the structure of a conventional zeolite molecular sieve resulting in reduced sieve capacity. UOP AW-500 reduces vulnerability to acid attack. Tri-ethylene glycol (TEG) is commonly used for dehydration of natural gas to pipeline specifications. It is an inexpensive bulk dehydration process. However, it is not capable of meeting the final water specification of <1 ppm H2O. Screening-level cost analysis was performed to look at the effect of using a TEG unit in combination with a downstream molecular sieve unit. This is the original configuration suggested in the Petrobras tender documents. MODEC determined that the added space and weight requirements of the TEG system, along with additional complexity of a two-system water removal process, did not justify the reduction in size of the downstream dryer. By using series regeneration and internal insulation, as agreed between MODEC and UOP, the dryer fit within the size, weight and utility limits for the dehydration step without pre-drying in a TEG unit.

Dew Point Control

As discussed above, J-T expansion was chosen for the DPCU. The flow scheme shown below was proposed in the tender:

From Dehydration 40C 97 kg/cm2 JT Vave Gas-Gas Exchanger

Low Temperature Separator ~11C ~68 kg/cm2

Condensate to Oil / Water Separator To CO2 Removal System 30C Max 1000 ppm C6 +

Figure 2 Hydrocarbon Dew Point Control Unit 4

Rio Oil & Gas Expo and Conference 2010 Due to the range in inlet compositions (with 8 to 25% CO2), there is not a common combination of pressures and temperatures at the Low Temperature Separator. It was considered more prudent to regulate the J-T downstream pressure, as this would have direct impact to upstream compressors as well as compressors on both the permeate and residue sides of the downstream CO2 removal membranes. MODEC consulted with the various membrane suppliers who were bidding for this project to fix an operating pressure that would be acceptable to each of them. The resulting Low Temperature Separator operating temperature and resulting C6+ content in the dew-pointed gas was subsequently checked for each of the design cases to ensure that these parameters were within the membrane design capabilities. If any adjustments were required, it could be achieved by increasing the discharge pressure of the upstream Main (a) Compressors. Ultimately, MODEC selected UOP Separex membranes for CO2 removal and further optimization could be achieved. A condensing pressure of 67 kg/cm2 was found by MODEC to be optimal at the Low Temperature Separator. The resulting condensing temperature ranged from 17 to 19C and some cases did exceed the recommended 1000 ppm of C6+. UOP confirmed that these conditions were adequate for pretreatment, provided the addition of superheat at the membrane preheaters. The need for membrane pretreatment is based on increasing membrane life. Membrane life is directly affected by the system operating philosophy. The gas entering a membrane system is cooled due to the J-T effect during permeation of CO2 from the high-pressure feed to the low-pressure permeate side of the membrane. The residue gas is always lower in temperature than the feed. At the same time, the hydrocarbon dew point of the gas is increasing due to the removal of CO2, which concentrates the hydrocarbon fractions. As the dew point rises and the gas temperature falls, condensation is a very real possibility when processing associated natural gas streams. The operating philosophy for UOP Separex membranes is to prolong membrane life by remaining in the vapor phase because condensation of hydrocarbons may have serious effects on membrane performance and membrane life. These include: Light hydrocarbons on the surface form a barrier to mass transfer, thus reducing flux though the membrane. These may not damage the membrane surface, but they reduce processing capacity until they are evaporated from the surface. Aromatic compounds commonly found in associated gas streams (benzene, toluene, ethyl-benzene and xylenes BTEX) are harmless to cellulose acetate polymers in the vapor phase, but can permanently damage the membrane surface in the liquid phase. Heavy hydrocarbons on the membrane surface (C10+) form a barrier to mass transfer and permanently reduce processing capacity.

Residue gas dew point margin at the exit of the membranes can be controlled via feed gas dew point control and the addition of superheat in the upstream membrane pretreatment. In the scheme shown in Figure 2, some superheat is provided by the cross exchanger in front of the J-T valve. The gas/gas exchanger also cools the feed gas, thus reducing the amount of pressure drop required to reach the condensing temperature. This aspect is important in minimizing the discharge pressure of the Main (a) Compressors and/or maximizing the feed gas pressure to the membrane system. MODEC selected a printed-circuit heat exchanger to obtain the smallest possible temperature approach. One last adjustment was made to the DPCU flow scheme. UOP required the installation of a filter coalescer on the vapor stream leaving the cold separator. The filter coalescer captures entrained droplets and aerosols that escape the mesh pad at the outlet of the cold separator. This added level of capture ensures that the dew point of the gas entering the membrane system is equal to the condensing temperature in the cold separator. It only takes a few drops of liquid carryover to increase the dew point of the membrane feed gas and increase the chance of condensing hydrocarbons (perhaps BTEX) within the membrane elements. The DPCU produces condensates that are returned to the oil stabilization section of the processing facility. This ultimately results in a net increase of product crude for the same incoming flow rate to the facility. The increased oil recovery provides a direct economic benefit to Petrobras. Altogether, the membrane pretreatment system prolongs membrane life, reduces operating costs and increases revenue for the FPSO. MODEC found that membrane replacement cost was a major factor in their economic evaluation and the money spent on adequate pretreatment is returned in lower operating costs. The final flow scheme for the DPCU is shown below in Figure 3.

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From Dehydration 40C 97 kg/cm2 JT Vave Gas-Gas Exchanger

Low Temperature Separator 17-19C ~67 kg/cm2

Condensate to Oil / Water Separator To Membrane Preheater 33C No Maximum C6+

Figure 3 Hydrocarbon Dew Point Control Unit As Built

CO2 Removal
MODEC developed the following design cases for the feed to the CO2 removal membranes: Table 1 Design Feed Streams for the UOP Separex Membrane System Case Pressure, bar Temperature, C Std Gas Flow, MMSm3/d Composition, Mole% Carbon dioxide Nitrogen Methane Ethane Propane i-Butane n-Butane i-Pentane n-Pentane n-Hexane+, ppm Water, ppm Hydrogen sulfide, ppm 1 64 33 3.50 10.93 0.50 69.25 9.50 6.22 0.98 1.75 0.34 0.39 1500 1 5 2 64 33 2.60 9.57 0.84 71.33 8.54 6.18 0.95 1.66 0.30 0.52 1100 1 5 3 64 33 2.00 25.31 0.76 59.19 6.93 4.93 0.73 1.32 0.24 0.50 900 1 5 4 64 33 4.80 9.30 0.51 70.60 9.71 6.35 0.98 1.74 0.32 0.36 1400 1 5 5 64 33 4.60 8.01 0.86 72.81 8.71 6.25 0.94 1.61 0.27 0.45 1000 1 5 6 64 33 4.80 13.85 0.91 68.24 8.28 5.81 0.80 1.40 0.21 0.43 700 1 5

Membrane systems are typically designed to run steady-state within a fairly narrow design basis. The range of feed gas flow rates and CO2 concentrations posed an interesting challenge: how to design a single system that will function at any point within this operating envelope without having to remove or add membrane elements? All of the cases have to produce less than 5% CO2 in the sales gas and still produce at least 80% CO2 in the permeate stream. One way to achieve a permeate CO2 concentration that high when starting with a feed gas as low as 8% CO2 is by using a two-stage membrane configuration as shown below:

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Residue Feed Permeate

Figure 4 Two-stage Separex Membrane System After pretreatment, the feed gas enters the primary stage of the Separex membrane system. The membrane separates the gas into a CO2-rich permeate stream and a CO2-depleted residue stream. The residue gas will contain 5 mol% CO2 and is routed to the export compressors. The permeate gas from the primary stage is compressed and routed to the second stage membrane. Second stage pretreatment for lube oil removal is not required due to the use of a centrifugal compressor with dry gas seals. In addition, controls are provided at the permeate compressor final stage discharge cooler, which allow temperature adjustment of the feed gas to the second stage membranes. The second stage membranes separate the gas into a CO2-rich permeate stream and a CO2-depleted residue stream. Residue gas from the second stage is recycled to the inlet of the primary membranes. This configuration recovers methane that would be lost in the primary stage permeate and concentrates the CO2 into the second stage permeate stream. The permeate stream from the second stage is available at 2.8 kg/cm2(g) at the Separex membrane skid edge. UOP was able to meet the design requirements using a combination of membrane isolation (sub-sections arranged in thirds) and variations in operating temperature and permeate pressure. Adjusting the amount of membrane area online is a gross adjustment to align operations with the actual gas flow rate. Once that is accomplished, the feed gas temperature can be adjusted using the membrane pre-heater. Also available for adjustment is the primary membrane permeate pressure, as long as the conditions are within the capability of the permeate compressor. It should be noted that only one permeate compressor is installed. If the compressor trips or is down for preventive maintenance, the second stage membranes are also offline but the primary membranes continue to make onspecification sales gas. Hydrocarbon recovery is lower when the compressor is down and the CO2 content of permeate stream will be lower. The permeate stream is automatically dumped to flare when the permeate compressor has tripped. There are two features of the membrane system that make it ideal for processing associated gas on the Petrobras FPSO when compared to conventional amine treating. First, the system can efficiently operate over a wider range of feed gas conditions. Amine units operate on a linear relationship to the moles of acid gas in the feed stream. As CO2 concentration increases, the circulation rate of the amine unit increases linearly so that sufficient solvent is available to react with the acid gases. Membranes actually become more efficient at higher concentration of acid gas because the driving force for permeation is the partial pressure of acid gas in the feed stream. Therefore, membrane systems only require a small increase in available surface area with increasing acid gas concentrations. The result is less over building to accommodate the high-CO2 stream compositions. The second important feature is that membranes are a dry process. Amine treating saturates both the treated gas and the acid gas with water. For this project, both the acid gas and sales gas stream would require dehydration downstream of an amine unit. The sales gas must be dry to meet pipeline water specifications intended to eliminate corrosion. The CO2 stream is required to be very low in water content for high pressure re-injection. It was not critical for this application, but membranes are also capable of delivering the acid gas stream at elevated pressure. Amine units produce an acid gas stream at a maximum pressure of about 2 kg/cm2(g). The pressure is limited by the degradation temperature of the solvent at the reboiler temperature. In some CO2 re-injection cases, the membrane permeate is produced at a pressure of 4 kg/cm2(g) or higher. The higher delivery pressure may reduce reinjection compression cost. MODEC did evaluate amines as an alternative process for CO2 removal and concluded that the membrane option was best for this application.

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Conclusion
The final topsides associate gas processing scheme developed by MODEC is shown below in Figure 5.

Vapor Recovery Unit From Subsea Wells Oil/Water Separator 20 kg/cm with heat + oil and water treatment Oil tanks HC to Oil Hydrocarbon Dew Point Control Unit 97 to 67 kg/cm2 H2O Disposal H2O Molecular Sieve Dryers <1 ppmv H2O Main (a) Compressors 20 to 98 kg/cm2g H2S Removal <5 to 170 ppmv H2S

Membrane Unit 64 kg/cm2 ~80% CO2

<5% CO2

Main (b) Compressors 61 to 250 kg/cm2g Fuel Gas

Reinjection Compressors 250 to 550 kg/cmg To Pipeline To Re-injection Wells To Re-injection Wells

CO2 Compression / Pumping 0 to 300 to 550 kg/cmg

Figure 5 Topsides Associated Gas Process Scheme As Built Via collaboration with the technology providers, MODEC was able to optimize the FPSO gas processing scheme. The improvements versus the initial proposed scheme included: Elimination of the TEG bulk dehydration unit. Optimization of the gas dryers to reduce electricity consumption. Relocation of H2S removal system upstream of Main (a) Compressors. Keeping with a traditional DPCU versus external refrigeration system. Optimization of the DPCU, reducing pressure loss at this step. Supply of a membrane system using minimal weight and space while providing flexible operation over a wide-range operating envelope. Supply of a membrane pretreatment scheme that ensures long membrane life with minimal operating cost.

As with any capital-intensive project, excellence in design and execution are required to meet customer requirements. MODEC accepted the challenge of integrating gas processing into the FPSO and partnered with suppliers and sub-contractors who could deliver technology and equipment on time and on budget. For the critical step of CO2 removal, UOP Separex membranes were chosen to create the two product gas streams required by Petrobras. Through a collaborative engineering effort, a robust and economical solution was found to meet all of the technical requirements for processing of a wide range of associated gas streams. At the same time, plot space and utilities were minimized to fit within the available space. The combination of MODECs experience in fabrication of the vessel and integration of topside processing equipment and UOPs experience in gas treating using a combination of proven technologies has created a design capable of meeting all the gas processing goals of the Tupi Pilot FPSO project.