HYBRID SEPARATION OF CO2 FROM ETHANE USING MEMBRANES

Knut H. Nordstad and Tor K. Kristiansen, Statoil, Stavanger Norway David Dortmundt, UOP Des Plaines US

Abstract
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 Krst 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.

Introduction
Ethane became a new product from the Krst 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 Krst

The Krst gas processing plant at Krst, 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 Krst ethane treatment plant was also put into operation in October 2000. Figure 1 shows a picture of the Krst gas plant after expansion in 2000. Figure 2 shows how the Ethane treatment plant is integrated into the total facilities at Krst. The Krst 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 3C (27F) 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 Krst gas plant in Norway

Figure 2: Block Flow Diagram of Krst gas processing plant including the Ethane treatment plant

34,5 bar / 5,5 C / 119 t/h

PC 1017
64

29-HG-102 Kondenser

Til fakkel
29-HV-1066

12,5 t/h Til salgsgass

sugedrum

29-HV-1096

FC 1004

Fra T-100
29-HV-1097 FC 1036

85,5 t/h
FF 1016
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HC 1017 B

PC 1038 B

2,6 bar -8,6 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
106,5 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

34,0 bar / -3,3 C

29-HG-101 Koker

29-HV-1042 24-HV -1060 29-HV-1055

0,32 bar -34,7 C LT seperator 25-VA-012 25 LC 0078

Til fakkel
25-HV-0081

LC 1008 29-QSV-1022 25 PC 0027

17,2 C

29-PA-101A/B
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CO2 kompressor 29-KA-101

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29-HG-103 Etan rundown kjler

Til fakkel

Til fakkel
25-HV-0064

Propan kondenser
25-HA-011

29-HV-1065

Sjvann

Sjvann

Akkumulator 25-VA-013
Etan fra C2 kompressor 46-system
73 t/h Antisurge FFIC 039 25-HV-0063

29-HV -1095 11,4 bar / 52,9 C / 216 t/h

Etan rundown

HT dampturbin

Antisurge FFIC 028

MM 11.00

Figure 3: Process Flow Diagram of the Krst Ethane treatment plant

Conceptual alternatives for enhanced ethane recovery and CO2 removal

The CO2 content in gas arriving at the Krst gas plant is expected to increase in the future. The existing Ethane plant rejects the CO2 and lost ethane back into sales gas. 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. 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. With increasing CO2 content in the raw ethane feed, the ethane recovery was predicted to drop below 80%. Hence the commercial need for removing CO2 from the export sales gas and improve ethane recovery became obvious. For this reason, two industrial concept applications were developed and studied: 1. CryogenicMembraneCryogenic CO2/C2 separation, producing high purity CO2 product suitable for commercial sale 2. CryogenicMembrane CO2 /C2 separation, 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. The product specifications applied to this concept are shown in table 1

Table 1: Product specifications high purity CO2 applied Components Methane Ethane Propane + Carbon dioxide Ethane product Max 1,5 wt% Min 95 wt% Max 4,5 wt% Max 100 wt ppm CO2 product Max 1 ppbV Max 1000 ppmV Max 1 ppbV Min 99,98 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 0.7 and the number of separation stages in the rectifying section. 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 membrane separator will break the C2/CO2 azeotrope and produce a permeate stream with approximately 93% CO2. The permeate is further compressed and passed to a CO2 purification column. The reject stream is passed to a secondary CO2 stripper. The CO2 purification column, with 50 theoretical trays, operating at 18 barg and -30C overhead temperature will produce a bottom CO2 product with less than 1,000 ppm hydrocarbons. Overhead gas from the column consisting of methane, carbon dioxide and some ethane is used as low btu fuel. The CO2 purification column separates the CO2/C2 mixture from the other side of the azeotrope than the CO2 stripper. The separation principle is presented in graphically on a T-X-Y Plot of CO2 and C2 mixture in figure 5.

In order to recover as much ethane as possible from the ethane rich residue gas, the residue can either be re-circulated back to the existing CO2 stripper, or processed in a new secondary CO2 stripper dependant on available capacity.

Figure 4: Flow Diagram for increased ethane recovery and the production of high purity CO2

Principles for Cryo/Membrane-hybride Process

T-X-Y Plot for CO2 and C2

16.0
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Distil 2 (CO2-purification)

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feed
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overhead feed Membrane separator permeate

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azeotrope CO2/(CO2+C2)=0.7
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-8.0

Pure C2

0.2

0.4

0.6

0.8

1.0

Composition, Mole Fraction CO2, (P = 34.000 BAR)

Pure CO2

Figure 5: Separation principles for the cryogenicmembrane 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 1.5 wt% Min 95 wt% Max 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 0.7 and modified with additional separation stages in the rectifying section. 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 membrane separator will break the C2/CO2 azeotrope and produce a permeate stream with approximately 95% CO2. The residue gas is used as low calorific fuel. 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. A flow diagram of the alternative concept is shown in figure 6.

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 hybrid concepts are lower in capital expenditure and more environmental friendly as no chemicals are used.

Pilot demonstration tests

Industrial references for CO2 membranes are mainly for the separation of CO2 from a natural gas, where methane is the dominant component. Our concept required a membrane separating carbon dioxide from an ethane-rich gas, where methane is a minor component. In order to demonstrate the membrane capability and performance in performing this task, a demonstration program was set-up at the Krst Ethane plant in cooperation between Etanor DA, Statoil and UOPs Gas Processing Group. An existing membrane separation rig was revamped, fitted with pilot-size Separex Spiral Wound elements, and connected to the Ethane plant. The equipment lay-out and tie-ins to existing facilities are shown in figure 7. Gas from the existing CO2-stripper overhead blower was passed to the membrane pilot unit. Residue gas was returned to the suction side of the blower. In this way, a real plant operation demonstration could be achieved. Prior to starting the demonstration testing, acceptance criteria were established by Statoil and its Etanor DA partners. The acceptance criteria are shown in figure 8. As the CO2 content in the overhead gas from the CO2 stripper was fluctuating, two feed compositions were defined, and are shown in table 3. The acceptance criteria are set by the calculated selectivity of the selected membrane material to be used.

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 12C (86 to 54F), and permeate pressure between 0.4 and 3 barg (5 to 45 psig). Due to operational fluctuations in the CO2 stripper and in upstream processes, the feed CO2 content varied during testing between 15 and 23 mole percent. In the 5 weeks demonstration program, more than 140 data points were collected.

After the demonstration was finished, the test data was collected, analyzed and compared to the established acceptance criteria. The results are shown in figure 9. Because of operational variations in feed temperature, feed composition and permeate pressure, the data had to be adjusted for these variations in order to compare achieved performance to the projected performance. Achieved performance lying on the right hand side of the acceptance criteria curve, indicates better performance than predicted.

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, and a vital part of the cryogenic-membrane hybrid separation concept was verified.

Acknowledgements
The authors gratefully acknowledge the contributions from Russel H. Oelfke with Exxon Mobil in the planning and analyses of the pilot demonstration. Acknowledgements also to Etanor DA, for allowing us to publish this paper. (Etanor DA is a company owned by the Norwegian state, Statoil ASA, Norsk Hydro Produksjon a.s, A/S Norske Shell, Mobil Exploration Norway Inc., and Norske Conoco AS.)