# Patent

## Title
Method of separating CO2 from hydrocarbon gas

## Abstract

A method of separating CO2 from a hydrocarbon gas inlet stream that is within predetermined pressure and temperature ranges including the steps of subjecting the inlet stream to fractional distillation providing a bottom product stream and a distillation overhead stream, passing the distillation overhead stream to a membrane unit producing a CO2 by-product stream and a hydrocarbon stream and chilling the hydrocarbon stream to produce a reflux liquid stream and a hydrocarbon gas product.

## Background
REFERENCE TO PENDING APPLICATIONS
This is a continuation-in-part application based on pending U.S. application Ser. No. 10/697,380, Filed 30 Oct. 2003 entitled


FIELD OF THE INVENTION
The present invention relates to a method for treating a hydrocarbon gas stream to remove CO2 using fractional distillation, membrane separation and reflux technology.
BACKGROUND OF THE INVENTION
Much of the world's natural gas supply is contaminated with unacceptably high levels of carbon dioxide (CO2). In some cases, in addition to excessive CO2, the natural gas may also contain excessive levels of sulfur compounds. Such sulfur compounds include hydrogen sulfide and carbonyl sulfide. In many cases, the carbon dioxide and sulfur contaminants lower the BTU value of natural gas making such gas unsuitable for use as a fuel or unsuitable to be transported in a pipeline carrier. Various commercial technologies including low temperature distillation, amine scrubbing and membrane separation, have been developed to upgrade natural gas containing excessive CO2 or sulfur compounds. All of the above-mentioned technologies typically produce a useable natural gas stream and a carbon dioxide/sulfur compound stream. The distillation separation of CO2 from hydrocarbon gas is a very energy and capital-intensive process. The present invention is an improvement on distillation technology that reduces the energy and capital requirement, producing a hydrocarbon product more efficiently.
Background information relating to the extraction of CO2, with or without accompanying sulfur compounds, from hydrocarbon gas may be found in the following publications:

    (1) Process Can Efficiently Treat Gases Associated With CO2 Miscible Flood—Oil & Gas Journal, Jul. 18, 1983.
    (2) U.S. Pat. No. 4,936,887—Distillation Plus Membrane Processing of Gas Streams, Waldo et al., Jun. 26, 1990.
    (3) Canadian Patent No. 1,253,430—Process and Apparatus for Fractionation of a Gaseous Mixture, Burr, May 2, 1989.
    (4) U.S. Pat. No. 4,417,449—Process for Separating Carbon Dioxide and Acid Gases From a Carbonaceous Off-Gas, Hagarty et al., Nov. 29, 1983.
    (5) U.S. Pat. No. 4,602,477—Membrane-Aided Distillation for Carbon Dioxide and Hydrocarbon Separation, Lucadamo, Jul. 29, 1986.
    (6) U.S. Pat. No. 4,444,571—Energy Efficient Process for the Stripping of Gases from Liquids, Matson, Apr. 24, 1984.
    (7) U.S. Pat. No. 4,374,657—Process of Separating Acid Gases from Hydrocarbons, Feb. 22, 1983.


BRIEF SUMMARY OF THE INVENTION
The present invention relates to a membrane/distillation system for producing a CO2 product, or a sour CO2 product and a hydrocarbon product. The system is comprised of: (a) ancillary equipment for dehydrating, cooling, and temperature conditioning the inlet gas; (b) a distillation system for separating the conditioned inlet gas into a CO2 liquid stream and a distillation overhead stream; (c) a primary condenser and reflux drum for separating the distillation overhead into a primary reflux stream and a hydrocarbon vapor stream, (d) a membrane system for separating the vapor stream into a hydrocarbon product and a permeate stream that is compressed, cooled and condensed to form additional reflux for the distillation column. The inlet hydrocarbon stream may be a natural gas stream or associated gas stream and may have liquid hydrocarbon components and which contains carbon dioxide and/or sulfur compounds. The hydrocarbon product may be a stream consisting predominantly of light hydrocarbons. The hydrocarbon product may include insignificant amounts of CO2, sulfur containing species and other components. The CO2 product may include insignificant amounts of hydrocarbon and other components, or the CO2 product may be pure CO2.
In one embodiment of the invention, the inlet gas stream is preconditioned for the separation by ancillary equipment. If required, inlet temperature, and pressure of the dehydrated hydrocarbon mixture are adjusted. After conditioning, the conditioned inlet stream is subjected to distillation. The distillation column produces an overhead stream and a CO2 bottom product. The distillation overhead is further processed by a primary reflux system. The primary reflux system partially condenses the stream in a condenser. The partially condensed stream is separated by the primary reflux drum into a liquid reflux and hydrocarbon overhead. The liquid reflux is returned to the column. The hydrocarbon-enriched overhead vapor from the primary reflux drum is further separated by the membrane system. The membrane system separates the reflux drum vapor into a hydrocarbon vapor stream and permeate stream. The permeate stream is compressed to a pressure greater than the distillation overhead. The compressed permeate stream is combined with the distillation overhead. This combined stream (distillation overhead and permeate stream) comprises the primary condenser inlet stream. This combined condenser inlet is fed to the primary reflux system which ultimately provides liquid reflux and membrane feed as described above.
In a separate embodiment of the invention, the inlet hydrocarbon fluid mixture is initially preconditioned and separated by the distillation system. If required, the inlet temperature and pressure of the dehydrated hydrocarbon mixture are adjusted. After conditioning, the inlet stream is subjected to fractional distillation. The distillation column produces an overhead stream and a CO2 bottom product. The distillation overhead is further processed by a primary reflux system. The primary reflux system partially condenses the condenser inlet stream in the primary condenser. The partially condensed stream is separated by the primary reflux drum into a liquid reflux and hydrocarbon overhead. The overhead hydrocarbon vapor from the primary reflux drum provides a partial feed to the membrane system. The membrane system separates the membrane inlet stream into a hydrocarbon product and a permeate stream. The permeate stream is compressed to a pressure greater than the primary reflux. The permeate stream is partially condensed in a secondary condenser and a secondary reflux drum is used to separate the two phase fluid. The pressurized liquid from the secondary reflux drum is added to the primary reflux downstream of the primary condenser. The hydrocarbon vapor from the secondary reflux drum is combined with the hydrocarbon vapor stream from the primary reflux drum. This combined stream comprises the membrane inlet stream.
In either of the above embodiments of the invention, the CO2 bottom product from the fractional distillation is processed identically. The stream is partially vaporized in a reboiler heater. A reboiler separator produces a vapor for re-introduction into the column and a CO2 liquid product. A portion of the CO2 liquid product may optionally be used to satisfy the cooling requirements of the process. In this mode of operation, a CO2 gas product is also produced.
The conditioned inlet gas required as feed to this invention may be obtained by a variety of methods well-known to those skilled in the art. The dehydrating system may be a glycol absorption system, a desiccant absorption system or a membrane dehydration system. For purposes of this invention, a dehydrating system is defined as a system that removes water from the stream to a dew point of less than the lowest temperature observed in the system.
A cooling system for the purposes of this invention may be a heat exchange system, a gas expansion system, a turbo expander system, a valve expansion system, or a mechanical refrigeration system. The heat exchange system is defined as one or more heat exchangers which utilize ambient temperature, or temperature of internal process streams, to decrease the temperature of the specified stream. A heat exchange system may consist of aerial-type exchangers, shell and tube, or plate and frame-type exchangers, which transfer heat from one process stream to another. An expansion system, either gas or liquid, is the expansion of a process stream to a condition of lower pressure. A turbo expander system is the expansion of this process stream through a turbo expander. In a turbo expander system, the expansion or pressure reduction of the gas stream is used to generate mechanical energy and effect a cooling of the process stream. A valve expansion system is the expansion or pressure reduction of this process stream through a valve or an orifice. The pressure reduction causes the gas stream to cool. A mechanical refrigeration system is the reduction of a process temperature by use of cooling derived from a refrigeration source that is ancillary to the process streams. In a mechanical refrigeration system, a refrigerant is contained in a closed loop. The refrigerant is subjected to pressurization, expansion and condensation. On expansion, the pressurized refrigerant vaporizes and cools. This cooling is utilized in a cross exchanger to reduce the temperature of the process stream. The heat loss from the cross exchange causes condensation of the refrigerant stream. The condensed refrigerant is again pressurized and the cycle repeated.
A preferred temperature range of the cooling procedure of step (a) is from about −30° F. to about 150° F. and more preferably between −20° F. and 60° F.
The system of the present invention may comprise a depressurizing device for optimizing the properties of inlet streams for separation by components of this invention. Distillation and membrane separation are the primary components. Typical depressurizing devices are a compressor, a turbo expander, and an expansion valve. The separation system of the present invention may also comprise a pump and a compressor. The pressure of the pressuring adjusting step (b) is from about 200 psia to about 1200 psia, and preferably from 350 psia to 800 psia and most preferably between 550 and 650 psia.
The distillation system is defined as a separation device that utilizes differences in boiling point and relative volatility to effect separation of components. The distillation system may have a plurality of distillation columns and the columns may be in a series or recycle configuration. Typical distillation columns employ trays and weirs to effect the successive steps of rectification and equilibration required for distillation. The column has a reflux produced by an overhead reflux system (condenser and separator drum) and reboiler vapor produced by a bottom fluid boiler and separator drum.
The membrane system is defined as a system which utilizes a selective barrier that is capable of separating components on the basis of size, shape or solubility. The membrane system separates a high-pressure feed stream into a high-pressure non-permeate stream and a lower pressure permeate stream. Membranes that preferentially permeate CO2 faster than hydrocarbons are useful for this invention. Membranes of this type are typically comprised of a glassy polymer. A glassy polymer is a polymer that is applied at a temperature lower than the glass transition. Examples of polymer families that are typically employed as glassy polymer membranes include: cellulose acetate, polyaramides, polybenzoxazoles, polycarbonates, polyimides, and polysulfones. Structural modification of the base polymer backbone is often used to enhance the gas separation performance of a given polymer family. These structural variants are also useful in this invention.
The membrane system has at least one membrane unit. The membrane system can have a plurality of membrane units. Often, the plurality of membrane units are arranged in a series configuration. The series configuration leads to improved performance when the membrane module performance is less than predictions based on an ideal membrane unit. A recycle configuration of the membrane modules can also be used to reduce hydrocarbon losses.
In one embodiment, the process comprises the step of recovering energy from the stream of CO2 liquid from the bottom of the distillation column. By flashing all or a part of the liquid across an expansion valve, sufficient refrigeration can be achieved to meet or exceed the cooling requirements of the system. Furthermore, this mode of operation eliminates the necessity of ancillary mechanical refrigeration.
In another embodiment, the present invention relates to a process for producing high levels of CO2 liquid and a hydrocarbon product. The process comprises the steps of: (a) cooling dehydrated hydrocarbon fluid mixture; (b) adjusting the pressure of the hydrocarbon fluid mixture; (c) distilling the hydrocarbon fluid mixture to produce a CO2 liquid and a hydrocarbon byproduct containing CO2 and/or sour gas; and (d) utilizing a membrane system to further separate the hydrocarbon byproduct to produce a recoverable hydrocarbon product and an additive for distillation column reflux. In this embodiment, mechanical refrigeration is used for the cooling step (c) and, the CO2 liquid from the bottom of the distillation column (c) is collected as product.
An additional embodiment of the invention provides a method of separating CO2 from a hydrocarbon inlet gas stream that is within predetermined pressure and temperature ranges. The inlet gas stream is first subjected to fractional distillation in a distillation column providing a bottom product stream and a distillation overhead stream. The distillation overhead stream is then passed to a membrane unit that selectively separates CO2 and hydrocarbon gas molecules producing a hydrocarbon stream and a CO2 by-product stream. The hydrocarbon stream from the membrane unit is passed to a hydrocarbon separator that divides the streams into a hydrocarbon liquid stream and a hydrocarbon vapor stream. The hydrocarbon vapor stream is then cooled in a temperature reduction device. Next the cooled hydrocarbon vapor stream is passed to a reflux drum producing a reflux liquid stream and a hydrocarbon gas product stream. The reflux liquid stream is returned to a top tray of the distillation column. The system thereby provides a hydrocarbon gas product stream and a CO2 by-product stream.
By appropriate temperature control of the system, the hydrocarbon product stream may be in the form of a hydrocarbon condensate or liquid product stream and a separate hydrocarbon gas product stream.
This alternate embodiment of the invention may be practiced in a way that includes the steps of subjecting the hydrocarbon gas inlet stream to fractional distillation providing a bottom product stream and a distillation overhead stream; subjecting the distillation overhead stream to membrane separation providing a hydrocarbon stream and a CO2 by-product stream; cooling the hydrocarbon stream to produce a cold hydrocarbon stream and refluxing the cold hydrocarbon stream back into the distillation column, the bottom product stream of the distillation column being employed to produce a hydrocarbon condensate liquid product stream.



DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic flow diagram of a first embodiment of the present invention.
FIG. 2 is a schematic flow diagram of a second embodiment of the invention wherein a permeate stream from a membrane system is condensed in a separate condenser and added to vapor from a distillation column condenser to provide feed for a membrane system.
FIG. 3 is a schematic diagram of a third embodiment of the invention in which a hydrocarbon product from a membrane system is partially condensed to provide reflux that is fed back to a distillation column.



DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Major elements of the invention are indicated in the drawings by numerals as follows:













14
Inlet gas stream


16
Inlet cross heat exchanger


18
Cooled inlet stream


20
Reboiler cross heater


22
Conditioned inlet stream


24
Distillation column


26
CO2 bottom product stream


28
Distillation overhead stream


30
Permeate stream


32
Combined condenser inlet stream


34
Primary condenser


36
Primary condenser outlet stream


38
Primary reflux drum


40
Hydrocarbon vapor stream


42
Primary reflux liquid stream


44
Primary reflux pump


46
Pumped primary reflux liquid stream


48
Membrane unit


49
Membrane inlet


50
Permeate cross heat exchanger


52
Hydrocarbon gas product stream


54
Permeate stream


56
Compressor


58
Compressed permeate stream


60
First permeate cross heat exchanger feed stream


62
Second permeate cross heat exchanger feed stream


64
Permeate cross heat exchanger outlet stream


66
Hydrocarbon product cross heat exchanger


68
Hydrocarbon product cross heat exchanger outlet stream


70
CO2 bottom product pump


72
Pumped CO2 bottom product stream


74
Reboil/separator


76
Reboiler separator inlet stream


78
Reboiler separation vapor stream


80
Reboiler separation liquid stream


82
Primary CO2 refrigerant stream


84
CO2 liquid product


86
Primary refrigerant pressure reduction device


88
Primary condenser refrigerant inlet stream


90
Primary condenser refrigerant outlet stream


92
CO2 gas product


94
Hydrocarbon gas product


96
Secondary reflux drum


98
Secondary condenser


102
Secondary condenser outlet stream


104
Secondary reflux liquid stream


106
Combined reflux liquid stream


108
Secondary CO2 refrigerant stream


110
Secondary refrigerant pressure reduction device


112
Secondary condenser refrigerant inlet stream


114
Secondary condenser refrigerant outlet stream


116
Combined refrigerant outlet stream


118
Secondary hydrocarbon vapor stream


120
Inlet gas stream


122
Inlet cross heat exchanger


124
Conditioned inlet stream


126
Distillation column


128
Bottom product stream


130
Distillation overhead stream


132
Membrane unit


134
Hydrocarbon stream


136
CO2 by-product


138
Hydrocarbon separator


140
Hydrocarbon vapor stream


142
Temperature reduction device


144
Cold hydrocarbon stream


146
Reflux drum


148
Cold hydrocarbon product stream


149
Hydrocarbon liquid stream


150
Reflux liquid stream


152
Reflux pump


154
Pumped reflux liquid stream


156
Hydrocarbon gas product


158
Bottom product pump


160
Pumped bottom product stream


162
Reboiler heater


162
Reboiler heater


164
Reboiler separator inlet stream


166
Reboil/separator


168
Reboiler separation vapor stream


170
Hydrocarbon condensate liquid









Referring now to the drawings wherein like reference numerals designate identical or corresponding parts throughout the several views and more particularly to FIG. 1 wherein the system and method of the present invention are illustrated. A dehydrated hydrocarbon fluid mixture gas stream inlet which contains high levels of carbon dioxide flows by way of inlet gas stream 14 and enters an inlet cross heat exchanger 16 for conditioning. The resulting cooled inlet stream 18 enters a reboiler cross heater 20 for further conditioning, producing a conditioned inlet stream 22. Stream 22 may be further cooled using a chiller. If the pressure of conditioned inlet stream 22 exceeds the critical pressure, either a Joule-Thomson expander or a turbo-expander can be used to reduce the pressure of conditioned inlet stream 22. The energy from the expander can be used for compression or for generating electricity.
Upon completion of the cooling process and pressure reduction processes, the hydrocarbon fluid mixture gas stream is properly conditioned for distillation separation. A distillation separation system that produces a high yield of liquid CO2 is preferred. The primary reason for selecting distillation for the bulk removal of CO2 is its ability to remove the CO2 as a liquid. Conditioned inlet stream 22 is distilled in distillation column 24 producing a liquefied CO2 bottom product stream 26 and a distillation overhead stream 28 (containing significant amounts of CO2). The distillation overhead stream 28 is combined with permeate stream 30 from the membrane unit 48 producing combined condenser inlet stream 32. This stream 32 is cooled by primary condenser 34 producing a primary condenser outlet stream 36. This stream 36 enters a primary reflux drum 38 producing a hydrocarbon vapor stream 40 and a primary reflux liquid stream 42. This liquid stream 42 flows back to distillation column 24 by gravity or is pumped by primary reflux pump 44 to enter a top tray of distillation column 24 as reflux. The hydrocarbon vapor stream 40 is sent to membrane unit 48 for further CO2 removal. Hydrocarbon vapor stream 40 enters permeate cross heat exchange 50 and is warmed prior to entering membrane unit 48. The membrane unit may be a single stage or multiple stages depending on the application, in addition, the permeate pressure of the membrane stages can be different to optimize compressing the permeate gas. Membrane separation produces a hydrocarbon product stream 52 and permeate stream 54. For this example, permeate stream 54 is compressed in a compressor 56 producing a compressed permeate stream 58. This stream 58 is divided into first and second permeate cross heat exchanger feed streams 60 and 62. These streams are cooled by permeate cross heat exchanger 50 and hydrocarbon product cross heat exchanger 66 producing permeate cross heat exchanger outlet stream 64 and hydrocarbon product cross heat exchanger outlet stream 68 that combine to form permeate stream 30.
Permeate stream 30 is then combined with distillation overhead stream 28 from the distillation column overhead to form combined condenser inlet stream 32. Permeate stream 54 could also be removed for disposal or for further processing instead of being utilized for reflux enhancement.
The CO2 bottom product stream 26 may be pumped to an elevated pressure using pump 70 into stream 72. Thermal energy from the pumped CO2 bottom product stream 72 is then recovered using reboiler cross heater 20 to cool inlet stream 18. The reboiler separator inlet stream 76 enters a reboiler/separator 74. The vapor from reboiler/separator 74, stream 78, is returned to the bottom of distillation column 24. The liquid from reboiler/separator 74, stream 80, is split into a primary CO2 refrigerant stream 82 for chilling, with the balance, stream 84 remaining as a CO2 liquid product stream. Primary CO2 refrigerant stream 82 is reduced in pressure with a primary refrigerant pressure reduction device 86 producing primary condensed refrigerant inlet stream 88. This stream 88 enters primary condenser 34 providing cooling sufficient to produce the required reflux liquid stream 42. Primary condenser refrigerant outlet stream 90 leaving primary condenser 34 enters inlet cross heat exchange 16 as an economizer to cool the inlet gas. The CO2 gas stream leaving inlet cross heat exchange 16 as a gas stream 92 can be compressed to combine with liquid CO2 product stream 84 or can be used as a CO2 gas product stream.
For a typical application with an inlet gas of 58% CO2 at 610 psia, the process, as shown in FIG. 1, produces a hydrocarbon product containing 10% CO2 at 565 psia and recovers 89.9% of the hydrocarbon in the inlet gas stream. The CO2 gas product stream contains 92.8% CO2 and recovers 89.1% of the CO2 at 200 psia. The CO2 liquid product stream contains 92.8% CO2 and recovers 3.7% of the CO2 at 610 psia. This gives a total recovery of CO2 for this example of 92.8%. A significant demand for energy in any CO2 removal process producing gaseous CO2 is compression of the CO2. CO2 compression can be the limiting factor for projects requiring CO2 at elevated pressures such as enhanced oil recovery, or re-injection of the CO2 to eliminate venting to the atmosphere. The compression requirements for this process are less than that for traditional distillation processes, since the CO2 product streams are produced at a relatively high pressure, and no external refrigeration is required.
Referring now to FIG. 2, wherein like reference numerals designate identical or corresponding parts, a dehydrated hydrocarbon fluid mixture inlet gas stream 14 that contains carbon dioxide enters inlet cross heat exchanger 16 for cooling. The resulting cooled inlet stream 18 enters a reboiler cross heater 20 for further cooling, producing conditioned inlet stream 22 which may be further cooled using a chiller. If the pressure of conditioned inlet stream 22 exceeds the critical pressure, either a Joule-Thomson expander or a turbo expander can be used to reduce the pressure thereof. Energy from an expander can be used for compression of the permeate gas or for generating electricity.
Upon completion of the cooling process and pressure reduction process, the hydrocarbon fluid mixture is properly conditioned for distillation separation. A distillation separation system that produces a high yield of liquid CO2 is preferred. The primary reason for selecting distillation for the bulk removal of CO2 is its ability to remove the CO2 as a liquid. Conditioned inlet stream 22 is then distilled in distillation column 24 producing a CO2 bottom product stream 26 and a distillation overhead stream 28, which contains significant amounts of CO2. The distillation overhead stream 28 is cooled by primary condenser 34 producing primary condenser outlet stream 36 that enters primary reflux drum 38 producing a hydrocarbon vapor stream 40 and a primary reflux liquid stream 42. This primary reflux liquid stream 42 is combined with secondary reflux liquid stream 104 from the secondary reflux drum 96. The combined reflux liquid stream 106 flows to a top tray of distillation column 24 as a reflux.
Hydrocarbon vapor stream 40 from primary reflux drum 38 is combined with secondary hydrocarbon vapor stream 118 and enters permeate cross heat exchanger 50 and is warmed prior to entering membrane unit 48. The membrane unit 48 may be single stage or multiple stages depending on the application. In addition, the permeate pressure of the membrane stages can be different to optimize compressing the permeate gas. Separation in membrane unit 48 produces a hydrocarbon product stream 52 and a permeate stream 54. Stream 54 is then compressed in compressor 56 producing compressed permeate stream 58 that is cooled by heat exchangers 50 and 66 producing permeate stream 30. The permeate stream 30 is then partially condensed using secondary condenser 98 producing secondary condenser outlet stream 102. Secondary reflux drum 96 produces secondary hydrocarbon vapor stream 118 and secondary reflux liquid stream 104. Vapor stream 118 is combined with vapor stream 40 from primary reflux drum 38. The combined stream is feed to membrane unit 48. Secondary reflux liquid stream 104 is combined with pumped primary reflux liquid stream from primary reflux drum 38 to provide the combined reflux liquid stream 106 that feeds onto an upper tray in distillation column 24.
The liquefied CO2 bottom product stream 26 may be pumped to an elevated pressure using pump 70. Thermal energy from the pumped bottom product stream 72 is then recovered using heat exchanger 20 to cool inlet stream 18. The high concentration reboiler separator inlet stream 76 leaving heat exchanger 20 enters reboiler/separator 74. The vapor from reboiler/separator 74, stream 78 is returned to the bottom of distillation column 24. Liquid from reboiled/separator 74 is split into secondary CO2 refrigerant stream 108 and reboiler separation liquid stream 80. Stream 108 is reduced in pressure with a secondary refrigerant pressure reduction device 110 providing secondary condenser refrigerant stream 112 that enters secondary condenser 98 providing cooling sufficient to produce the required reflux stream 104 that is fed to distillation column 24. The secondary refrigerant outlet stream 114 leaving secondary condenser 98 is combined with primary refrigerant outlet stream 90 and enters inlet cross heat exchange 16 as an economizer to cool the inlet gas to the process. CO2 gas leaving heat exchange 16 as product 92 can be compressed to combine with liquid CO2 stream 84 or retained as a CO2 gas product stream.
For a typical application with an inlet gas of 58% CO2 at 610 psia, the process as shown in the drawing produces a hydrocarbon gas product containing 10% CO2 at 565 psia and recovers 91% of the methane in the inlet. The CO2 product gas stream contains 92.8% CO2 and recovers 88.2% of the CO2 at 200 psia. The CO2 liquid product stream contains 92.8% CO2 and recovers 4.6% of the CO2 at 610 psia. This gives a total recovery of CO2 for this example of 92.8%. A significant demand for energy in any CO2 removal process producing gaseous CO2 is compression of the CO2. CO2 compression can be the limiting factor for projects requiring the CO2 at elevated pressure such as enhanced oil recovery, or re-injection of the CO2 to eliminate venting to the atmosphere. The compression requirements for this process are less than that for a traditional distillation process since the CO2 product streams are produced at a relatively high pressure and no external refrigeration is required.
A third basic embodiment of the invention is illustrated in FIG. 3. In this embodiment dehydrated hydrocarbon gas inlet stream which contains high levels of carbon dioxide, flows by way of inlet gas stream 120 through an inlet cross heat exchanger 122 for conditioning. The resulting conditioned inlet stream 124 may be further cooled using a chiller (not shown). If the pressure of conditioned inlet stream 124 exceeds the critical pressure, either a Joule-Thomson expander or a turbo-expander (neither of which are shown) can be used to reduce the pressure. Energy from such expander if produced, can be used for compression purposes or for generating electricity.
Upon completion of the cooling process and pressure reduction processes, the hydrocarbon fluid mixture gas stream 124 is properly conditioned for distillation separation and is fed into distillation column 126 producing a liquefied bottom product stream 128 (containing significant amounts of heavy hydrocarbons) and a distillation overhead stream 130 (containing significant amount of CO2). The distillation overhead stream 130 is sent to a membrane unit 132 for CO2 removal. The membrane unit may be a single stage or multiple stages depending on the application. In addition, the permeate pressure of the membrane stages can be different to optimize compressing the permeate gas if desired. Membrane separation produces a hydrocarbon stream 134 and a CO2 by-product stream 136. For this example, CO2 by-product stream 136 is removed for disposal, but it can be further processed to produce a more pure CO2 stream if desired.
Hydrocarbon stream 134 may be two phase due to the removal of CO2 in the membrane unit and if so the condensed liquid may be processed in a hydrocarbon liquid/vapor separator 138. Vapor is taken from separator 138 as a hydrocarbon vapor stream 140 that is cooled by a temperature reducing device 142. Temperature reducing device 142 can be, as examples, a refrigeration chiller, a Joule Thomson expander or a turboexpander. Cold hydrocarbon stream 144 from temperature reducing device 142 enters a reflux drum 146. Hydrocarbon liquid leaves separator 138 as a hydrocarbon liquid stream 148 and flows into reflux drum 146. Reflux drum 146 produces a hydrocarbon gas stream 149 and a reflux liquid stream 150. Hydrocarbon liquid stream 150 flows back to distillation column 126 by gravity or is pumped by reflux pump 152 that provides a pumped reflux liquid stream 154 to enter a top tray of distillation column 126. Hydrocarbon gas stream 149 enters inlet cross heat exchanger 122 as an economizer to cool the inlet gas stream. The hydrocarbon gas stream leaves cross heat exchanger 122 as a hydrocarbon gas product stream 156.
The bottom product stream 128 from distillation column 126 may be pumped to an elevated pressure using bottom product pump 158 providing pumped bottom product stream 160. Heat is added to pumped bottom product stream 160 by a reboiler heater 162 providing a reboiler/separator inlet stream 164. Vapor from a reboiler/separator 166, as reboiler separation vapor stream 168, is returned to the bottom of distillation column 126. Liquid from reboiler/separator 166 forms a hydrocarbon condensate liquid stream 170 which is one of the outlet streams from the method illustrated in FIG. 3. Hydrocarbon condensate liquid stream can be further processed to produce a saleable product.
For a typical application with an inlet gas of 41% CO2 at 604 psia, the process, as shown in FIG. 3, produces a hydrocarbon product containing 22% of CO2 and recovers 91.5% of the light hydrocarbons (methane, ethane and propane) in the inlet gas stream. The condensate stream recovers 33.9% of the propane and heaver components and 99.9% of the hexane and heavier components contained in the inlet stream. The CO2 by-product stream contains 86% CO2 and recovers 64.2% of the CO2 contained in the inlet stream. This method of providing a distillation column feed for membrane unit reduces the reflux loading on the distillation column and reduces the condenser load that would be required for a distillation only process producing the same products.
While the invention has been described with a certain degree of particularity, it is manifest that many changes may be made in the details of construction and the arrangement of components of the equipment and systems used in the invention, as well as the steps and sequence thereof, of practicing the methods of the invention without departing from the spirit and scope of this disclosure. It is understood that the invention is not limited to the embodiments set forth herein for purposes of exemplification, but is to be limited only by the scope of the attached claim or claims, including the full range of equivalency to which each element or step thereof is entitled.

## Claims

1. A method of separating CO2 from a hydrocarbon inlet gas stream that is within predetermined pressure and temperature ranges, comprising the steps of:
(a) subjecting the inlet gas stream to fractional distillation in a distillation column providing a bottom product stream and a distillation overhead stream;
(b) passing the distillation overhead stream from step (a) to a membrane unit producing a hydrocarbon stream and a by-product stream;
(c) passing the hydrocarbon stream from step (b) to a hydrocarbon separator to separate hydrocarbon liquid having been condensed in said membrane unit from hydrocarbon vapor; and
(d) subjecting the hydrocarbon vapor from step (c) to cooling providing a cooled hydrocarbon vapor stream that is fed to a reflux drum; and
(e) taking a reflux liquid stream from said reflux drum and a hydrocarbon gas product stream.

2. A method of separating CO2 from a hydrocarbon inlet gas stream according to claim 1 including:
passing said bottom product stream from step (a) to a reboiler/separator that provides a reboiler separator vapor stream directed to a bottom portion of said distillation column and a hydrocarbon condensate product stream.

3. A method of separating CO2 from a hydrocarbon gas inlet stream according to claim 2 wherein said bottom product stream from step (a) is pumped at increased pressure to said reboiler/separator.

4. A method of separating CO2 from a hydrocarbon gas inlet stream according to claim 1 wherein a reflux liquid stream from step (e) is pumped at increased pressure to a top tray of said distillation column.

5. A method of separating CO2 from a hydrocarbon gas inlet stream according to claim 2 wherein said bottom product stream from step (a) is heated prior to being passed to said reboiler/separator.

6. A method of separating CO2 from a hydrocarbon gas inlet stream according to claim 1 wherein said hydrocarbon liquid stream from said reflux drum is passed through a cross heat exchanger to heat said inlet gas stream prior to its fractional distillation.

7. A method of separating CO2 from a hydrocarbon gas inlet stream that is within predetermined pressure and temperature ranges comprising the steps of:
(a) subjecting the hydrocarbon gas inlet stream to fractional distillation in a distillation column providing a bottom product stream and a distillation overhead stream;
(b) subjecting said distillation overhead stream of step (a) to membrane separation, providing a hydrocarbon stream and a CO2 by-product stream;
(c) cooling the hydrocarbon stream of step (b) producing a cold hydrocarbon stream;
(d) refluxing said cold hydrocarbon stream from step (c) back into said distillation column; and
(e) pumping said bottom product stream from step (a) at increase pressure to a reboiler/separator that provides a reboiler separator vapor stream that is directed to a bottom portion of said distillation column and a hydrocarbon condensate liquid product stream.

8. A method of separating CO2 from a hydrocarbon gas inlet stream according to claim 7 wherein said cold hydrocarbon stream from step (d) is pumped at increased pressure to a top tray of said distillation column.

9. A method of separating CO2 from a hydrocarbon gas inlet stream according to claim 7 wherein said bottom product stream from step (a) is heated and then passed to said reboiler/separator.