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Knut H. Nordstad and Tor K. Kristiansen, Statoil, Stavanger Norway David Dortmundt, UOP Des Plaines US
This paper presents hybrid concepts for the separation of CO2 from ethane involving the combination of cryogenic distillation and UOP Separex™ membranes. Statoil and UOP have together carried out pilot testing at Kårstø gas processing plant in Norway. A gas mixture of CO2 and ethane from a CO2 stripper overhead stream has been successfully separated with cellulose acetate membranes to produce CO2 of specified purity. The pilot testing has been carried out in a demonstration unit at approx. 38 barg (570 psia) pressure under varying temperatures.
Ethane became a new product from the Kårstø plant in October 2000, with the start-up of the Ethane plant. Ethane is exported from the plant by ship, and is used as a feedstock for ethylene production. There is an incentive to maximize production in the plant, and studies have been undertaken with this objective. With increasing CO2 content in the ethane feed stream to the plant, ethane recovery from the existing plant has been a concern. Methods for more effective separation of ethane and CO2 have therefore been studied. There has also been interest in a CO2 feed stream from the ethane plant, for further processing to a commercial CO2 product. For this reason, a process providing a high purity CO2 stream has also been studied.
Existing ethane plant at Kårstø
The Kårstø gas processing plant at Kårstø, in the Western part of Norway, was first put into operation in 1985. The plant has since been extended several times, with the latest in October 2000. The Kårstø ethane treatment plant was also put into operation in October 2000. Figure 1 shows a picture of the Kårstø gas plant after expansion in 2000. Figure 2 shows how the Ethane treatment plant is integrated into the total facilities at Kårstø. The Kårstø Ethane treatment plant, built by Etanor DA, receives raw ethane from the Statpipe processing trains 100 / 200 and Sleipner train 300. The Capacity of the plant is 620 mt/y produced ethane. The raw ethane consists of some methane and carbon dioxide together with ethane. The CO2 and the methane are stripped out of the ethane in a 64 tray cryogenic distillation column operating at 34 barg (510 psia) and –3°C (27°F) reflux conditions. Due to the CO2 / C2 azeotrope, the ethane recovery is limited in this process. The heating and cooling duty is served by a steam turbine-driven propane heat pump. In figure 3, a PFD for the existing Ethane plant is presented.
Figure 1: Picture of Kårstø gas plant in Norway Figure 2: Block Flow Diagram of Kårstø gas processing plant including the Ethane treatment plant .
producing high purity CO2 product suitable for commercial sale 2.6 bar -8.5 t/h 29-HV-1045 FC 1037 PC 1038 A Til turtalls regulering av dampturbinen 25 PC 0031 29-QSV-1003 FC 1016 CO2 stripper refluks seperator 34.00 Figure 3: Process Flow Diagram of the Kårstø Ethane treatment plant Conceptual alternatives for enhanced ethane recovery and CO2 removal The CO2 content in gas arriving at the Kårstø gas plant is expected to increase in the future.32 bar -34.2 C / 73 t/h 29-HG-103 Etan rundown kjøler Til fakkel Til fakkel 25-HV-0064 Propan kondenser 25-HA-011 29-HV-1065 Sjøvann Sjøvann Akkumulator 25-VA-013 Etan fra C2 kompressor 46-system 73 t/h Antisurge FFIC 039 25-HV-0063 29-HV -1095 11. two industrial concept applications were developed and studied: 1. With increasing CO2 content in the raw ethane feed.3 C 29-HG-101 Koker 1 29-HV-1042 24-HV -1060 29-HV-1055 0.34. Cryogenic–Membrane–Cryogenic CO2/C2 separation.9 C / 216 t/h Etan rundown HT dampturbin Antisurge FFIC 028 MM 11.2 C 29-PA-101A/B 29-HV -1028 FC 1068 CO2 kompressor 29-KA-101 34.5 t/h Til salgsgass sugedrum 29-HV-1096 FC 1004 Fra T-100 29-HV-1097 FC 1036 85. The existing Ethane plant rejects the CO2 and lost ethane back into sales gas. producing 95% CO2 Concept for increased ethane recovery and the production of high purity CO2 A Flow Diagram of the concept is shown in fig 4.5 t/h FF 1016 57 HC 1017 B PC 1038 B 2.5 bar / 5. For this reason.7 C LT seperator 25-VA-012 25 LC 0078 Til fakkel 25-HV-0081 LC 1008 29-QSV-1022 25 PC 0027 17. Hence the commercial need for removing CO2 from the export sales gas and improve ethane recovery became obvious. the ethane recovery was predicted to drop below 80%.6 C HT seperator 25-VA-011 25 LC 0071 Fra T-200 29-HV-1098 FC 1025 Fra T-300 CO2 stripper LC 1046 FC 1021 106. The capability of distilling close to the azeotrope in the overhead is determined by the number of separation stages in the rectifying section of the column.0 bar / -3. The product specifications applied to this concept are shown in table 1 .4 bar / 52. Cryogenic–Membrane CO2 /C2 separation.5 C / 119 t/h PC 1017 64 29-HG-102 Kondenser Til fakkel 29-HV-1066 12. The recovery of ethane will be reduced as CO2 content increases due to the distillation process in the CO2-stripper column being limited by the azeotropic mixture of ethane and carbon dioxide.7 bar / 17.
• • In order to recover as much ethane as possible from the ethane rich residue gas. Overhead gas from the column consisting of methane. with 50 theoretical trays.7 and the number of separation stages in the rectifying section.5 wt% Min 95 wt% Max 4. The separation principle is presented in graphically on a T-X-Y Plot of CO2 and C2 mixture in figure 5. carbon dioxide and some ethane is used as low btu fuel. the residue can either be re-circulated back to the existing CO2 stripper.98 mol% The unit operations in the concept consist of: • The existing CO2 stripper column producing an overhead gas limited by the CO2/C2 azeotrope of 0. or processed in a new secondary CO2 stripper dependant on available capacity. The permeate is further compressed and passed to a CO2 purification column. The membrane separator will break the C2/CO2 azeotrope and produce a permeate stream with approximately 93% CO2. The CO2 purification column.000 ppm hydrocarbons. operating at 18 barg and -30°C overhead temperature will produce a bottom CO2 product with less than 1. The membrane separator receiving gas from the existing CO2 -stripping column at approx 34 barg separates the gas into a low pressure permeate stream and a high pressure residue stream.5 wt% Max 100 wt ppm CO2 product Max 1 ppbV Max 1000 ppmV Max 1 ppbV Min 99.Table 1: Product specifications high purity CO2 applied Components Methane Ethane Propane + Carbon dioxide Ethane product Max 1. The reject stream is passed to a secondary CO2 stripper. Figure 4: Flow Diagram for increased ethane recovery and the production of high purity CO2 . The CO2 purification column separates the CO2/C2 mixture from the “other” side of the azeotrope than the CO2 stripper.
0 azeotrope CO2/(CO2+C2)=0.0 B D feed D B 0 B B D D B B B D D B D D B D B -4.5 wt% Max 100 wt ppm CO2 product Min 95 mol% The unit operations in the concept consists of: • The existing CO2 stripper column producing an overhead gas limited by the CO2/C2 azeotrope of 0. The membrane separator will break the C2/CO2 azeotrope and produce a permeate stream with approximately 95% CO2.6 0.4 0.0 Pure C2 0 0. In order to recover as much ethane as possible from the ethane rich residue gas. the residue can be re-circulated back to the existing CO2 stripper. e r u t a r e p m e T Distil 1 (CO2-splitter) B Distil 2 (CO2-purification) 8.0 D B C 12. A flow diagram of the alternative concept is shown in figure 6.7 and modified with additional separation stages in the rectifying section.0 B D Bubble Point Dew Point B D .5 wt% Min 95 wt% Max 4. Mole Fraction CO2.0 Composition.Principles for Cryo/Membrane-hybride Process T-X-Y Plot for CO2 and C2 16.000 BAR) Pure CO2 Figure 5: Separation principles for the cryogenic–membrane hybrid separation process Concept for increased ethane recovery and production of low purity CO2 The product specifications applied to this concept are shown in table 2: Table 2: Product specification for production of low purity CO2 applied Components Methane Ethane Propane + Carbon dioxide Ethane product Max 1.7 D D B D D B D B D B D D B B B -8. • • . (P = 34.2 0. The membrane separator receiving gas from the existing CO2-stripping column at approx 34 barg separates the gas into a low pressure permeate stream and a high pressure residue stream. The residue gas is used as low calorific fuel.8 1.0 bottoms feed B D D overhead overhead feed Membrane separator permeate bottoms 4.
Our concept required a membrane separating carbon dioxide from an ethane-rich gas. As the CO2 content in the overhead gas from the CO2 stripper was fluctuating. and are shown in table 3. An existing membrane separation rig was revamped. The hybrid concepts are lower in capital expenditure and more environmental friendly as no chemicals are used. Statoil and UOP’s Gas Processing Group. two feed compositions were defined. Prior to starting the demonstration testing. where methane is the dominant component. fitted with pilot-size Separex Spiral Wound elements. a demonstration program was set-up at the Kårstø Ethane plant in cooperation between Etanor DA. In order to demonstrate the membrane capability and performance in performing this task. and connected to the Ethane plant. acceptance criteria were established by Statoil and its Etanor DA partners. Residue gas was returned to the suction side of the blower.Figure 6: Flow Diagram for increased ethane recovery and the production of low purity CO2 The hybrid concepts presented are comparable to the more traditional amine type processes. and found favorable in several aspects. . The equipment lay-out and tie-ins to existing facilities are shown in figure 7. where methane is a minor component. The acceptance criteria are shown in figure 8. Gas from the existing CO2-stripper overhead blower was passed to the membrane pilot unit. In this way. a real plant operation demonstration could be achieved. The acceptance criteria are set by the calculated selectivity of the selected membrane material to be used. Pilot demonstration tests Industrial references for CO2 membranes are mainly for the separation of CO2 from a natural gas.
more than 140 data points were collected.4 and 3 barg (5 to 45 psig). and permeate pressure between 0. the feed CO2 content varied during testing between 15 and 23 mole percent. Due to operational fluctuations in the CO2 stripper and in upstream processes. .Figure 7: Pilot test rig and tie-in to existing plant Table 3: Demonstration case definitions Figure 8: Demonstration testing acceptance criteria The testing involved varying feed temperature between 30 and 12°C (86 to 54°F). In the 5 weeks demonstration program.
Acknowledgements also to Etanor DA. A/S Norske Shell. Acknowledgements The authors gratefully acknowledge the contributions from Russel H. the test data was collected.s. indicates better performance than predicted. Norsk Hydro Produksjon a. and Norske Conoco AS. the data had to be adjusted for these variations in order to compare achieved performance to the projected performance. The results are shown in figure 9. Because of operational variations in feed temperature. Statoil ASA. Oelfke with Exxon Mobil in the planning and analyses of the pilot demonstration. feed composition and permeate pressure. Achieved performance lying on the “right hand” side of the acceptance criteria curve. and a vital part of the cryogenic-membrane hybrid separation concept was verified. Figure 9: Achieved performance compared to acceptance criteria Conclusion The adjusted data shows that Cellulose Acetate Spiral Wound membranes were easily able to meet expected performance for separating carbon dioxide from ethane. for allowing us to publish this paper. (Etanor DA is a company owned by the Norwegian state.. Mobil Exploration Norway Inc. analyzed and compared to the established acceptance criteria.After the demonstration was finished.) .
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