CA1340001C - Process for separating components of a gas stream - Google Patents
Process for separating components of a gas streamInfo
- Publication number
- CA1340001C CA1340001C CA000550376A CA550376A CA1340001C CA 1340001 C CA1340001 C CA 1340001C CA 000550376 A CA000550376 A CA 000550376A CA 550376 A CA550376 A CA 550376A CA 1340001 C CA1340001 C CA 1340001C
- Authority
- CA
- Canada
- Prior art keywords
- stream
- accordance
- component
- feed gas
- components
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- C01B23/00—Noble gases; Compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/225—Multiple stage diffusion
- B01D53/226—Multiple stage diffusion in serial connexion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/229—Integrated processes (Diffusion and at least one other process, e.g. adsorption, absorption)
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0229—Purification or separation processes
- C01B13/0248—Physical processing only
- C01B13/0251—Physical processing only by making use of membranes
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- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0229—Purification or separation processes
- C01B13/0248—Physical processing only
- C01B13/0259—Physical processing only by adsorption on solids
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/04—Purification or separation of nitrogen
- C01B21/0405—Purification or separation processes
- C01B21/0433—Physical processing only
- C01B21/0438—Physical processing only by making use of membranes
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/04—Purification or separation of nitrogen
- C01B21/0405—Purification or separation processes
- C01B21/0433—Physical processing only
- C01B21/045—Physical processing only by adsorption in solids
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/144—Purification; Separation; Use of additives using membranes, e.g. selective permeation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/106—Silica or silicates
- B01D2253/108—Zeolites
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- B01D2253/116—Molecular sieves other than zeolites
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- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/25—Coated, impregnated or composite adsorbents
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/10—Nitrogen
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- B01D2256/16—Hydrogen
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- B01D2256/18—Noble gases
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- B01D2256/22—Carbon dioxide
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- B01D2256/24—Hydrocarbons
- B01D2256/245—Methane
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2257/00—Components to be removed
- B01D2257/10—Single element gases other than halogens
- B01D2257/102—Nitrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2257/10—Single element gases other than halogens
- B01D2257/104—Oxygen
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7022—Aliphatic hydrocarbons
- B01D2257/7025—Methane
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/0462—Temperature swing adsorption
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/047—Pressure swing adsorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/047—Pressure swing adsorption
- B01D53/0476—Vacuum pressure swing adsorption
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0405—Purification by membrane separation
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- C01B2203/042—Purification by adsorption on solids
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- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/047—Composition of the impurity the impurity being carbon monoxide
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- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/048—Composition of the impurity the impurity being an organic compound
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- C01B2210/0046—Nitrogen
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- C01B2210/0078—Noble gases
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/20—Capture or disposal of greenhouse gases of methane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Water Supply & Treatment (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Separation Of Gases By Adsorption (AREA)
Abstract
The present invention is a process for separating and recovering a component from a multi-component feed gas mixture. The feed gas mixture is initially separated in a membrane separation unit or units to produce a gas stream concentrated in the desired component. The concentrated gas stream is subsequently further separated in an adsorption unit having an adsorbent which selectively adsorbs non-desired gaseous components thereby producing a purified product stream. The non-desired gaseous components are subsequently desorbed and a purge stream from the adsorption unit containing the desorbed non-desired gaseous components along with a portion of the desired components is recycled to the feed gas mixture.
Description
~ 3 !3~ l PROCESS FOR SEPARATING COMPONENTS
OF A GAS STREAM
TECHNICAL FIELD OF THE INVENTION
The present invention relates to the separation and recovery of a component from a multi-component gas stream.
BACKGROUND OF THE INVENTION
In the past, processes designed to produce a high purity product stream at high recovery from feed streams containing up to 90 mole ~ of the desired component required multiple staged membrane systems or multi-bed Pressure Swing Adsorption ("PSA") units. The use of stand-alone membrane units to produce a very high purity stream; i.e.
greater than 99%, was found to be inefficient since large me~brane areas and power de -nds were required in order to achieve this high purity at a high recovery. PSA units, on the other hand, proved to be very efficient in producing a high purity stream from feed streams containing the desired gas at concentrations greater than 70 mole %, but become less l!i efficient for treating relatively low pur~ty; i.e. less than 70% streams to yield a high purity product at high recovery.
U.S. Patent 4,229,188 teaches a process for recovering hydrogen from a gas mixture containing hydrogen and normally liquid hydrocarbons. The feed stream is passed to a selective adsorption unit to initially 2~ separate the feed, and the purge stream from the adsorption unit is subsequently treated in a membrane separator to recover an additional amount of the desired component. The process design disclosed in this patent, however, is only an efficient scheme for feed streams that are highly concentrated in the desired components; i.e. have a concentration 2!j of greater than 70 mole % of the desired component.
~.S. Patent 4,238,204 discloses a process for recovering a light gas in both high purity and high yield from a gas mixture containing said light gas and other c ,~o~ents. The gas mixture is initially directed to a selective adsorption unit which produces a high purity light gas and a 3() .
- 2 - ~ t~ (3 :~.
purged gas containing at least a portion of the liqht gas. The purged gas from the adsorption unit is subsequently passed to a membrane permeator selectively permeable to the light gas in order to recover the permeated gas comprising light gas of improved purity from said permeator cj and recycling said permeated gas to the selective adsorption unit. As with U.S. Patent 4,229,188, this process scheme is also only suitable for feed streams which are relatively highly concentrated in the desired feed component; i.e. greater than 70 mole %.
U.S. Patent 4,398,926 discloses a process for recovering hydrogen from a high pressure stream having a hydrogen content of up to about 90 mole ~. The feed stream is passed to a separator containing a permeable membrane capable of selectively permeating hydrogen. The separator is used to achieve a bulk separation of the desired hydrogen component from impurities contained in the gas stream. The separated hydrogen is recovered at reduced pressure and passed to a pressure swing adsorption system adapted for operation at reduced pressure.
Additionally, the off gas from the separator is recovered essentially at the higher pressure of the feed gas stream, and at least a portion of this stream is throttled to a lower pressure and passed to the pressure swing adsorption system as a co-feed gas in order to increase the recovery of the desired component.
BRIEF SUMMARY OF THE INVENTION
The present invention is a process for separating and recovering a desired c~ onent at high purity and high recovery from a multi-component gas stream comprising components which have different permeabilities through a semi-permeable membrane.
The process comprises passing the multi-component feed gas stream to a plurality of membrane separation units to produce a gas stream concentrated in one or more desired components. The concentrated stream is passed to an adsorption unit which contains an adsorbent which selectively adsorbs the non-desired gaseous components to produce a product stream which can have a concentration of up to 9S mole ~ or greater of the desired c-~L~or?nt. The gaseous c~ ,- ents which were adsorbed in the adsorption unit are subsequently desorbed and recycled and combined with the feed gas stream entering the membrane separation unit. In some instances, a portion of the desorbed gas may be suffic:iently concentrated in a particular component to be withdrawn as a purge or a co-product stream.
5, The present process provides an efficient means to recover one component from a gas mixture containing at least one otner c-n"onent.
The interactions between the membrane and adsorption units compliment each other's operation to provide an efficient process for producing a high purity product stream at recoveries greater than can be achieved by either unit operated individually.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a schematic flow diaqram of one embodiment of the present invention wherein the desired product is a more permeable component of the feed gas mixture.
Figure 2 is a schematic flow diagram of one embodiment of the present invention wherein the desired product is a less permeable component of the feed gas mixture.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is a process for recovering one or more components from a gas mixture. The process involves hybridizing a semi-permeable membrane-based unit or units with an adsorption unit. A
multi-component feed gas mixture containing at least two major components wherein the permeation rate through a membrane unit of one major component is different from the other major components is passed to a plurality of membrane separation units to produce a gas stream concentrated in the desired component. A major component in a feed gas mixture is one whose concentration exceeds 1 volume %, and typically 310 exceeds 4 volume %.
The membrane unit used in this invention can be any membrane device with some selectivity for separating one major gaseous component from the other major - ,onents in the feed gas mixture when a pressure differential is maintained across the membrane. Each membrane unit may consist of a single membrane device or, alternatively, several membrane 13~3~0 l devices plumbed and operated so as to achieve the separation in the most efficient manner; e.g., a cascade of membranes with internal recycle streams between various stages of the membrane unit. Typically, the membrane devices are manufactured in modules, each having certain !j semi-permeable membrane areas for permeation. Semi-permeable membrane materials currently available which can be employed in this process include: polysulfone, cellulose acetate, polyimide, polyamide, silicone rubber, polyphenylene oxide, etc.
The resultant stream from the membrane separation unit concentrated in one or more desired components: i.e., the concentrated stream, is passed to an adsorption unit which contains an adsorbent capable of selectively adsorbing non-desired components, thereby producing a product stream having a high concentration of the desired component. A product stream having a total concentration of the desired components up to at 1.5 least 95 mole % and preferably greater than 99 mole % can be achieved.
In typical embodiments, the product stream will represent at least an 80 mole % and preferably at least a 90 mole % recovery based upon the feed.
The adsorption unit can be kinetic or equilibrium-based and operated as pressure swing, temperature swing, vacuum swing or any other suitable method or combination thereof. Examples of adsorbents typically used in these units include molecular sieves, such as carbon molecular sieves and zeolit:ic materials such as cation exchanged zeolites from the faujasite and mordenite families.
While the term adsorption is used herein, it should be realized that, depending upon the totality of operating conditions and gaseous components, absorption or other similar type purification units may suitably be substituted without deviating from the spirit of the invention.
The non-desired components which were adsorbed in the adsorption unit are subsequently desorbed and recycled along with a portion of the desired r n~onents to the feed gas mixture entering the membrane separation units. A portion of the desired components can be employed as a rinse stream for the adsorption unit following the desorption step.
The rinse stream may then be recycled along with the desorbed ~n~
components. At some point during the desorption cycle, the concentration of one or more of the non-desired c~ nPnts may be sufficiently high to purge a portion of this stream from the process or make it available as a co-product.
5, Units or systems to remove very low levels of conta~i~ts such as ~2~ N2~ H2~ CO2, H2O, etc. can be added to further treat any of the process streams. Such systems are commercially available and can be added as needed to any of the hybrid schemes of the present invention.
Figure l represents one embodiment of the present invention wherein a more permeable component of the feed gas mixture is separated and recovered as a purified product. The gaseous feed mixture 10 containing, up to 90 mole % of the desired component, and preferably between 20-85 mole G5~ is mixed with the compressed recycle stream 95, to give a combir-ed feed stream 20. The combined feed stream 20 is passed to a first membrane unit 21 to form a first permeate stream 30 and a first reject: stream 40. The permeate stream 30, from the first membrane unit Zl is concentrated in the desired component and is fed to an adsorption unit 23 for a final purification to produce a purified product streann 50. Depending upon the pressure level of the permeate stream 30, 2'0 the st:ream can optionally be compressed before it is fed to the adsorption unit 23. The first reject stream 40 from the first membrane unit, 21, is fed to a second membrane unit 22 to produce a second permeate stream 70 and a second reject stream 80. The recovery level of the desired component in the second permeate stream 70 from the second membrane unit 22 is fixed depending upon the desired recovery level or optimum recovery level determined by economic analyses. If necessary, one can fix the recovery level at this stage to be very high such that the overall product recovery level is greater than 99%; a level which is generally very difficult to achieve with the prior art schemes. The 3,0 pressllre of the second permeate stream 70 is generally fixed to be equivalent to that of the purge stream 60 from the adsorption unit 23 so that t:hey can be mixed to form stream 90, compressed in compressor 93, and recycled as compressed stream 95 to the feed gas mixture 10.
Alternatively, the streams could be at different pressures and fed to indivïdual stages of compressor 93. The second reject stream 80 from the ~ x~
second membrane unit 22 may be recovered as a high pressure stream and either expanded separately to recover energy, or utilized for other operations or simply discarded. Depending upon concentration and compos'ition, a portion of the desorbed c~ Ants may optionally be recovered from the adsorption unit 23 as a co-product stream 52 and a separate portion 62 may optionally be passed through an intermediate membrane unit, such as unit 22, prior to being recycled. The key to this proceCs scheme is to fix the recovery of the desired compsnent at a moderate level ~30-90%, particularly 50-80~) at the first membrane unit 2;1, and at a high level; i.e., >50~ and preferably >80~, at the second membrane unit 22.
E'articular gas mixtures which are well suited for separation via this process scheme include: hydrogen-carbon monoxide; hydrogen-hydrocarbon; helium-hydrocarbon; helium-hydrocarbon-nitrogen; and metharle-nitrogen.
Figure 2 represents a process scheme that enriches one or more less permea,ble components as a reject stream in a series of membrane units and purifies the stream in an adsorption unit to recover the desired components as purified product. The major difference between this scheme from the one shown in Figure 1 is that the adsorption unit 230, is used to purify the reject stream 800 from a second membrane unit 220.
The gaseous feed mixture lO0, containing up to a total of 90 mole and preferably between 20-85 mole % of the desired components is mixed with the compressed recycle stream 950 to produce a combined feed stream 200. The combined feed stream 200 is passed to a first membrane unit %lO to produce a first permeate stream 300 and a first reject stream 400. Depending upsn the recovery level desired in the product stream 500, the first membrane unit 210 can be configured into a multi-stage membrane unit. The first permeate stream 300 is collected for subsequent use or simply discarded. The first reject stream 400 is passed to a second membrane unit 220 to produce a second permeate stream 700 and a second reject stream ~00. The second reject stream 800, enriched in the de5ired c~ _onentS~ is passed to an adsorption unit 230 1 3 ~
containing an adsorption medium selective for adsorbing non-desired components, thereby producing a purified product stream 500, having a high concentration of the desired c~ pC entS.
The non-desired components are subsequently desorbed from the adsor~tion unit 230 as stream 600 and mixed with the second permeate stream 700 from membrane unit 220, which are generally at similar pressures, to form stream 900. Stream 900 is compressed to about feed pressure in compressor 930 to form compressed stream 950 which is subse~uently combined with the feed gas mixture 100. Alternatively, streams 600 and 700 may be at different pressures and can be fed to individual sta~es of the compressor 930. Depending upon concentration and composition, a portion of the desorbed components may optionally be recovered from the adsorption unit 230 as a co-product stream 520 and a separate portion 620 may optionally be passed through an intermediate ~5 membrane unit, such as unit 220, prior to being recycled. Gas mixtures which are well suited for separation using this process scheme include:
argon-oxygen; inert gas (nitrogen and argon)-oxygen, hydrocarbon-carbon dioxide; ar~on-NH3 purge gas; and nitrogen-methane.
rn all of the process schemes of the present invention, optional ;20 compressors or expanders may be utilized to vary the pressure of any of the gas streams, depending upon the gas mixture, treatment and product pressure, and pressure difference between any two streams which are subsequently combined. Compressors 93 and 930 in Figures 1 and 2 respectively are only representative of particular embodiments and may be ;!5 repos:itioned or eliminated as other process conditions are altered~
The examples presented below are presented only to illustrate the invenl:ion and are not meant to limit the scope of the invention.
Example 1 The objective of this example is to produce a purified helium (99.9~ mole %) stream at 210 psia from a 665 psia gas mixture containing 58.2 mole % helium. The properties of the feed gas stream are set out in Table 1 below.
- 8 - 1 3~ 0 Table 1 Feed Rate = 240 lb. moles/hr.
Pressure = 665 psia Temperature = 110~F
,j ElEED GAS COMPOSITION:
Component Mole Percent Helium 58.2 Nitrogen 40.5 Methane 1.3 1.0 E'rocess calculations were done for a membrane/PSA process in accorclance with the present invention a~ depicted in Figure 1 ~case 1) and also for several prior art membrane/PSA processes (cases 2 and 3).
1.5 Case 1 I'he feed stream 10, is first mixed with the recycle stream 95 to form a mixed stream 20 having a helium concentration of 66.6 mole ~.
Mixed stream 20 is then fed to the first membrane unit 21 to form a first 2 permeate stream 30 and a first reject stream 40. The permeate stream 30, containing 95% helium, is recovered at 220 psia and is fed to a PSA unit 23 to recover a purified helium product stream 50 at greater than 99 mole % purity at 99.4 mole % recovery. The purified helium product stream 50 is then either sold as a gaseous product or sent to a liquefying process. The reject stream 40 from the first membrane unit 21 is at almost the same pressure as the fresh feed 10 and is fed to the second membrane unit 22 to recover an additional amount of helium. The helium recovery level at the second membrane unit 22 is fixed depending upon the overall desired helium recovery. The pressure of the permeate stream 70 from this membrane stage is the same as the purge stream 60 containing non-desired components, i.e. nitrogen and methane, desorbed from the PSA
unit. Streams 60 and 70 are combined and compressed in compressor 93 to the pressure of the feed 10 and recycled to form a combined feed streaml 20. The reject stream 80 from the second membrane unit 22 which consists mainly of nitrogen and methane c~ ,~on~nts can be directly expanded to recover its energy or can be sent to a helium liguefaction area to provide makeup nitrogen and~or to recover its energy.
I'he details of the key process streams for this process are given in Table 2 below.
A summary of the total helium recovered, relative power consumed, and relative membrane area required for this case is presented in Table 3 below. Although the helium recovery is very high, modifications of the operating conditions of the me~rane and PSA units can further increase recovery.
Table 2 Key Process Streams for the Membrane~PSA Hybrid Process of Figure 1, Example 1, Case 1 Stream Number 10 100 20 30 40 80 70 50 Pressure (psia) 665 665 665 220 660 655 25 210 Total Flow (lb.moles/hr) 240 127.4 367.4 208.6 158.8 101.3 57.5 138.8 Compositior. ~mole ~~' Helium 58.2 82.3 66.6 95.0 29.2 0.9 79.0 100.0 Nitrogen 40.5 17.1 32.4 4.8 68.6 96.0 20.4 --Methane 1.3 0.6 1.0 0.2 2.2 3.1 0.6 --Case 2 In this case a membrane unit is primarily used as a preprocessor to upgrade the feed stream to a desired level of helium purity before the stream is fed to the adsorption unit. The feed gas mixture set out in Table 1 was first treated in a membrane unit to give a permeate stream containing 95% helium at 220 psia as was done in Case 1. This helium-enriched stream is then sent to the PSA unit to produce a purified helium stream at a 210 psia pressure. Although this scheme uses less membrane area and power, it suffers from a significantly lower helium recovery as depicted as case 2 in Table 3 below.
Case 3 The feed gas mixture of Table 1 was treated in a scheme wherein a first membrane unit is used to recover the desired level of helium from the feed stream and a second membrane unit is used to produce a helium strea~m sufficiently enriched so that it can be fed to a PSA unit.
The feed stream is first mixed with the helium enriched stream from the second membrane unit. This mixed stream is then fed to the first membrane unit. The helium recovery level at this stage is fixed such ;~0 that the overall helium recovery level is consistent with Case 1. The permeate stream from the first membrane unit is then mixed with the purge stream from the PSA unit, compressed and subsequently fed to the second membr.~ne unit. The permeate stream from ~he second membrane unit is recovered at a 220 psia pressure and fed to the PSA unit to produce a ;!5 helium product stream.
~ n general, this scheme differs from the new concept in that the first membrane unit, which processes a large stream, is required to operalte at a very high recovery level. As shown in Table 3, this scheme ~case 3) uses more power and me~brane area than the new suggested 3~ concept.
3,5 - 12 - ~ c'~
Table 3 Comparison of the Cases Presented in Example 1 Case Heli~n Recovery (%) 99.4 43.5 99.4 Relative Power 1.0 0.0 1.76 Relative Area 1.0 0.26 1.10 .0 In summary, Example 1 clearly illustrates that the process scheme of the present invention (case 1) gives a purified product stream at very high recovery and is also very efficient compared to other schemes previously used to separate gas mixtures.
Example 2 ~'he following example illustrates the embodiment shown in Figure 2.
This concept is an attractive process scheme when the desired product is a less permeable component through the membrane units, which can be purified and recovered as a raffinate stream from the adsorption unit.
This e!mbodiment has an added advantage in that the desired product can be recove!red as a high pressure stream without additional compression.
Calculations were done to produce a high purity argon stream from a gas mixture containing 50% oxygen and 50~ argon. The membrane characteristics used to simulate this example are for advanced membranes currently being developed; for example, U.S. patent 4,584,359 teaches a cobalt complex vinyl polymer membrane that possesses a very high permeability of oxygen with respect to other components such as nitrogen, argon, etc. The PSA unit used to simulate this case is a kinetic-based system which preferably adsorbs oxygen over argon; however, this particular PSA unit can be replaced with an equilibrium-based unit depending upon the specific separation desired in a process situation.
In this process, the feed stream, 100, is first mixed with the recycle stream, 950, before it is fed to the first membrane unit, 210 as - 13 ~ t~
stream 200 having a 52.1 mole% argon concentration. The permeate stream 300 from the first membrane unit 210 contains about 97% oxygen and is recovered at a 20 psia pressure. Again, the oxygen recovery at the feed stage membrane unit is fi~ed at a relatively low level ~~50%) in order to increase the oxygen purity and to minimize the argon losses in the permea,te stream 300. The reject stream 400 has a concentration of 68.2 mole ~; argon and is directly fed to the second membrane unit 220 to produce an argon-enriched reject stream 800, having an argon concer.~tration of 97.5 mole %, at a high pressure and to recover an argon-lean permeate strea~ 700 which is recycled after recompression.
The o~ygen recovery level at the second membrane unit can vary depending upon the argon purity and recovery desired for the second reject stream 800. The argon-enriched second reject stream 800 is then fed to the PSA unit to produce a purified argon product stream 500 at a concentration near 100% at high pressure. The eurge stream 600 from the PSA unit is at 20 psia pressure and is mixed with permeate stream 700 from the second membrane unit and recycled to the feed.
The details of the feed stream and the other key process streams for this process scheme are given in Table ~ below. These calculations were done based on the assumptions that all permeate streams from the membrane units and the purge stream from the PSA unit were maintained at 20 psia pressure, and the argon recovery at the PSA unit was fixed at 50%.
2l5 - 1 4 - ~- 3 ~
~ o o o CO , o o ~ ~ , o U ~ ,, o o ~ ,, o ~ U~
I' ~ In u~
.
o o a~
o o o~
~ er O t~
1~ o u r~ ~ C~
O O L~
.~ , .
,. . .
.q o o ~
o ~ u- a ~r .~ ~ O o a~
o ~ o a' o o a~
~ U- , o er U~
o a) ~ ~1 E
~ o o o o o U~ o _I o U~ U
~q a) S~
:C ~, o~~
~I a) I~J S E
~o --J~ 0~ r o .
F
O
~ U
v EO~ ~- ~
The data reported in Table 4 above show that the process scheme carried out in Example 2 above provides for the recovery of an argon product stream having a purity of about 100%. Total argon recovery is also very high since the only argon lost from the system is that 5, contained in the permeate from the first membrane unit which is regulated to keep the argon loss at a minimum.
Examp:Le 3 A second particular process scheme was carried in accordance with the general scheme illustrated in Figure 2. In this scheme, the permeate stream 300 from the first membrane unit 210 is further processed in a separate membrane unit ~not shown) to increase the purity of the more permeable component thus increasing the recovery of the desired less permeable component.
lS C'alculations were done to produce a high purity methane stream 500 from a gas mixture containing 55% methane, 41% carbon dioxide, and a remaining mixture containing nitrogen, oxygen and water vapor. This gas composition is typical of landfill gas. Characteristics of currently available membranes were used to simulate this process and the adsorption unit used was a PSA unit such as a kinetic-based or equilibrium-based system which preferably adsorbs carbon dioxide over methane.
ln this process, the feed stream 100 is first mixed with the purged stream from the PSA unit and the mixed stream is compressed to an intermediate pressure of about 100 psia. After compression, this mixed streaml is then mixed with the permeate stream from the second membrane separation unit 220. The resultant stream is then compressed to a feed pressure of about 775 psia and is passed to the first membrane unit 210 as feed stream 200. The permeate stream 300 from the first membrane unit 210 contains about 93% car-bon dioxide and is at about 105 psia 3l~ pressure. The carbon dioxide recovery at the feed stage membrane unit is fixed at a relatively low level ~ 50%) to increase the carbon dioxide purity; however, this stream still contains about 6% methane, which represents about 10% methane lost to the overall process if not recovered. The permeate stream 300 is, therefore, sent to an additional 3!;
~ 3 i~
membrane unit ~not shown) where further purification of carbon dioxide or further recovery of methane is accomplished. The resultant purified strearn from this additional membrane unit contains 98.5% carbon dioxide and only 0.7% methane. The reject stream produced from this additional 5, membrane unit contains 89~ carbon dioxide and 10% methane, and is recyc:Led at about 100 psia pressure to the feed gas entering the first membrane unit 210.
The reject stream 400 from the first membrane unit 210 has a methane concentration of 51% and is directly fed to the second membrane unit 220 to produce a methane-enriched reject stream 800 having a methane concentration of 80%, at a high pressure and a methane-lean permeate stream 700 at about 100 psia pressure. The methane-enriched reject stream 800 from the second membrane unit 220 is subsequently fed to PSA
unit .!30 to produce a purified methane product stream 500 at a concentration of about 98% or higher at high pressure.
l'he gas adsorbed in the PSA unit 230: i.e., carbon dioxide, can be recovered as a purified carbon dioxide co-product stream or alternatively, the total desorbed gas mixture 600 can be recycled and mixed with the feed stream 100.
l'he details of the feed stream and the other ~ey process streams for this example are given in Table 5 below. These calculations were based on a 10% methane recovery at the PSA unit.
, c~
~ a~ O
o o r- ~~ o o u ~ a~
u~ t' ~
O ~~ ~ cn o o~n ~1 0 r~ ~ o o O
co r' ~
CD ~ ~ I~ O
. . . .
O O C~ ~D ~ O O O
1' _I ~1 cn CD O
. . . .
O1-- o UO~1-- ~ ~
L? ~l' ?
O U ~ ~O ~ O O O
~4 0 0 ~1 ~1 ~
OU~ O U ~ O O O
O1' ~ t~
C:
~n ~ ~ u o ~ O
a ~ 0~~~~ ~ o ~ o o o g o ~D ~ O ~ O
O OU~ O
O~1 ~ U~ ~
., J~ ~
? a 0~,, ~ô .a 6 W
Z1~ .~,. w - -~ r _~ W ~
W
~ , o Z O ~
The data reported in Table S above shows that the process being carried out in Example 3 provides for the recovery of a methane product stream having a purity of about 98% and a recovery greater than 99%.
5, Example 4 A process was simulated for the recovery of argon from ammonia purged gas in accordance with the general scheme set out in Piqure 2.
The am~onia purge gas which forms the feed stream 100 has a composition of about. 62~ hydrogen, 20% nitrogen, 11~ methan2 and 7% argon ii under a 10 pressure of approximately 2,000 psia and at a tempe.atur~ Or about 95~F.
This stream is obtained from an ammonia plant after the removal of ammonia from the purged gas by any kno:m technique, such as by absorption.
The feed stream 100 is combined with recycled stream 9'0 to give a combined feed 200 containing 70% ~2 and 8.7~ Ar and is fed to a first membrane unit 210. The permeate stream 300 from the fir~t mem~rane unit 210 cor.tains 9~.5% hydr~gen and ser.t back to the a~enia plant. The recovery of hydrogen from this pro-ess is hi~h; i.e., about 98eo. The non-permeate stream 400 from the me~rane unit.210 forms the feed to a se~ond men~ralle unit 220 and is separated to provide reject stredm B~0 containing 5% H2 and 24.9% argon. The concentration of hydrogen in this steeam determines the relative am~unt of ar~on and hydrogen in the product stream 500 from the adsorption unit 230. A smaller concentration of hydrc,gen will give stream 500 a hiqher argon concentration thus reducing further purification requirements but the me.l~rane area of unit 220 must be enlarged and the permeate stream from membrane unit 220 would increase for recycle. For any given application, a detailed economic analysis would dictate the optimum combination of hydrogen and argon in stream 800 which is passed to the adsorption unit 230. In the present analysis, it was arbitrarily chosen to be 5~ H2. The permeate stream 700 from membrane unit 220 containing 3.9% argon is recycled to the first membrane unit 210. The presence of this recycle back to the feed stream allows the present process to be run with a high recovery of argon.
3'5 The reject stream 800 from the second membrane unit 220 contains 24.9% argon and is sent to an adsorption unit capable of adsorbing nitrogen and methane relative to argon and hydrogen. The recovery of N2 ancl CH4 from the adsorption process was taken to be 90% and that 5 of argon to be 50~. Consequently, the adsorption process not only produces a product stream 500 containing 83.3% argon and 16.7~ H2 but also produces a co-product stream 520 containing 63.9% N2 and 35.1%
CH4. A purged stream 600 is also recovered from the adsorption unit to form a part of the recycled stream 950 to the first membrane unit 210.
This recycled stream keeps the total argon recovery for the over~ll process at a high level; i.e., about 86%.
The argon product, stream 500, contains some hydrogen which can be removed by any known process or combination of processes, for example argon could be cryogenically condensed or hydrogen could be removed by oxidation after which the water formed could be condensed and/or adsorbed, or an additional membrane unit could be used to remove the hydrogen.
Conventionally, argon is recovered from ammonia purged gas by cryogenic means. Such cryogenic systems are complicated and costly, 20 requiring an attendant refrigeration system for the operation of a low-temperature separation unit. Moreover, the cryogenic plants are not amenable to quick turn downs and encounter problems associated with feed gas variations and plant stability. This is due to the fact that the cryogenic units are subject to operational variances of the ammonia plant 2'; and not vice versa. See, Isalski, W. H., "25 Years of Purged Gas Recovery" Nitrogen, lOl, 152 (1984). The present process scheme which consists of a membrane unit followed by an adsorption unit is 00re amenable to feed turn downs and is easier to operate than previous methods.
T'he details of the key process streams obtained from the simulation of the above-described process are set out in Table 6 below.
35, .~eqo~r~-l ~r o U ~ o~
o U o o ~ U~ o ~ 4 ~ ~
a~ o o ~ o o ,~
L~ O d~ O
O U~
O ~1 ~ r~
8 ~ ~ .~
s~ o o 1' u In ~ ~p o O ~1 ~: . . . .
g o ~ r- o o ,.
~- ~O O ~ ~D r~
o O O g ~ o ~ r~ ~~
~ ~ ~ o Q
E~ Q ~ ~~
~ o o~ ) oU~
:r: u o1-- co ~1 ~r P, ~
o o o o o a~ . . . .
O O O ~ O ~1 1 ~0 0 0 0 ~ o,1 ~ .
J~
o ~U
., ~ o~
J _~
nl ~ O
X ~ ,1Z~
o 8 As can be seen from the results reported in Table 6 above, a product strearn rich in argon can be obtained from the present process. While the product stream consists of two different components, in general this is not a problem because the two resultant components may be easily separated or used together, with the real problem of removing nitrogen and methane, being solved by the process.
Examp]e 5 The process scheme as depicted in Figure 2 was simulated for the separation and recovery of 99.5% inert gas (nitrogen and argon) from air. This scheme is almost identical to the case presented in Example 2 above, with the difference being that the feed gas mixture is air, and the major component besides oxygen is nitrogen instead of argon. The present scheme was developed for air separation usinq me.~brane characteristics representing currently available membranes, and a kinetic-based PSA system.
One particular benefit of this process scheme is that the PSA unit is used to adsorb ~2-10~ oxygen versus -21~ oxygen in a stand-alone unit, thereby increasing the inert gas recovery and productivity of the PSA unit. Another benefit of this process scheme is that most of the contaminants; e.g., CO2, H20, etc., contained in the air will be removed by the membrane units. This improves the operation of the adsorption unit since typical adsorbents prefer C02 and H2O over ~2' 2!; Since the primary value associated with the feed gas for this application is the power used to compress it, additional flexibility is added to the cycle so that, if the oxygen purity of the second permeate stream 700 from membrane unit 220 is greater than that of air, it may be mixed with the first permeate stream 300 and recovered as an 3(~ oxygen-enriched stream instead of being combined with the desorbed stream 600 and recycled to the feed gas. This can be done for this particular application because product recovery is less of a concern with the inert gas product ~stream 500) purity being the most important parameter.
3'i t~
The details of the key process streams for this example are given in Table 7 below. These results clearly indicate that the process scheme depicl:ed in Figure 2 is suitable for recovering an inert gas ti.e., nitrogen and argon) at high purity, i.e. 99.5 mole % from an air feed.
5, The first permeate stream 300 from the first membrane unit 210 can also be recovered as an oxygen-enriched stream; i.e., 39 mole % oxyqen.
]:t was calculated that this process scheme can recover as much as twice the amount of product at less power consumption than either the kinetic-based adsorption unit or membrane unit when used as a stand-alone proce~;s.
2!j 35, u~ ~ r' o o o o ~~
o o ~ o~ ll a O ~ ~D
~o o o ~l o o~ o . ~, O ~ ~~ ~ ~ I
~0 Oa? ~ ~~D
,~ ? O O ~1 0a~ o J ~ o r~ c S~ O U ~ ~CO~1 0 ~ o ~1 ~ ~~n U~
O u~ o oI O
~~ O 1~ _I _I ~ I
w Oa) .C u~ a~D
. . .
O U- ~ u ~ O
O a~
~ ~O O_I~ O
O ~a~ ~ oa~
~ J O U~ ~ OU~ O
Z ~ o .~
~J
o S~
0~o S ~ A
a) u~-- .--~ ~ O C
z a~ C
;'' r~ r J O ~ ~
O ~ r_ n ,~
J ~ ~
rn gas separation processes, when the product gas has a high value, a very high purity and recovery are often desired. The present invention provides process schemes that can efficiently recover a purified product (99+~) at high recovery (80+%) from a gas mixture containing at least one ~; other component. The method of the present invention takes advantage of the favorable characteristics and minimizes the deficiencies of the membrane and adsorption units.
Stand-alone membrane units are generally considered very efficient for bulk separations on a relatively smaller scale, however, these ~o systems are not generally efficient, if not impractical, in producing a high purity product ~>99%~ at very high recovery ~>90%). When membrane units are used in a cascade to get high recoveries and/or purities, intermediate compression is often reguired and a relatively large amount of energy and membrane area are necessary.
lS ';tand-alone adsorption units, on the other hand, are very effective in producing a purified gas stream, but they require the purity of feed streams to be relatively high; e.g., 70%. The performance of these units generally suffers from a relatively low recovery which can be further reduced if the pressure of the feed is very high.
~he present invention not only gives a purified product stream at high recovery but also consumes much less power and/or results in substa~ntial process simplifications, reduced investments, and improved economics. Mbny embodiments of the invention provide for the recovery of a second product stream enriched in a component other than that of the purified product.
Hiaving thus described the present invention, what is now deemed appropriate for Letters Patent is set out in the following appended claims.
31~
OF A GAS STREAM
TECHNICAL FIELD OF THE INVENTION
The present invention relates to the separation and recovery of a component from a multi-component gas stream.
BACKGROUND OF THE INVENTION
In the past, processes designed to produce a high purity product stream at high recovery from feed streams containing up to 90 mole ~ of the desired component required multiple staged membrane systems or multi-bed Pressure Swing Adsorption ("PSA") units. The use of stand-alone membrane units to produce a very high purity stream; i.e.
greater than 99%, was found to be inefficient since large me~brane areas and power de -nds were required in order to achieve this high purity at a high recovery. PSA units, on the other hand, proved to be very efficient in producing a high purity stream from feed streams containing the desired gas at concentrations greater than 70 mole %, but become less l!i efficient for treating relatively low pur~ty; i.e. less than 70% streams to yield a high purity product at high recovery.
U.S. Patent 4,229,188 teaches a process for recovering hydrogen from a gas mixture containing hydrogen and normally liquid hydrocarbons. The feed stream is passed to a selective adsorption unit to initially 2~ separate the feed, and the purge stream from the adsorption unit is subsequently treated in a membrane separator to recover an additional amount of the desired component. The process design disclosed in this patent, however, is only an efficient scheme for feed streams that are highly concentrated in the desired components; i.e. have a concentration 2!j of greater than 70 mole % of the desired component.
~.S. Patent 4,238,204 discloses a process for recovering a light gas in both high purity and high yield from a gas mixture containing said light gas and other c ,~o~ents. The gas mixture is initially directed to a selective adsorption unit which produces a high purity light gas and a 3() .
- 2 - ~ t~ (3 :~.
purged gas containing at least a portion of the liqht gas. The purged gas from the adsorption unit is subsequently passed to a membrane permeator selectively permeable to the light gas in order to recover the permeated gas comprising light gas of improved purity from said permeator cj and recycling said permeated gas to the selective adsorption unit. As with U.S. Patent 4,229,188, this process scheme is also only suitable for feed streams which are relatively highly concentrated in the desired feed component; i.e. greater than 70 mole %.
U.S. Patent 4,398,926 discloses a process for recovering hydrogen from a high pressure stream having a hydrogen content of up to about 90 mole ~. The feed stream is passed to a separator containing a permeable membrane capable of selectively permeating hydrogen. The separator is used to achieve a bulk separation of the desired hydrogen component from impurities contained in the gas stream. The separated hydrogen is recovered at reduced pressure and passed to a pressure swing adsorption system adapted for operation at reduced pressure.
Additionally, the off gas from the separator is recovered essentially at the higher pressure of the feed gas stream, and at least a portion of this stream is throttled to a lower pressure and passed to the pressure swing adsorption system as a co-feed gas in order to increase the recovery of the desired component.
BRIEF SUMMARY OF THE INVENTION
The present invention is a process for separating and recovering a desired c~ onent at high purity and high recovery from a multi-component gas stream comprising components which have different permeabilities through a semi-permeable membrane.
The process comprises passing the multi-component feed gas stream to a plurality of membrane separation units to produce a gas stream concentrated in one or more desired components. The concentrated stream is passed to an adsorption unit which contains an adsorbent which selectively adsorbs the non-desired gaseous components to produce a product stream which can have a concentration of up to 9S mole ~ or greater of the desired c-~L~or?nt. The gaseous c~ ,- ents which were adsorbed in the adsorption unit are subsequently desorbed and recycled and combined with the feed gas stream entering the membrane separation unit. In some instances, a portion of the desorbed gas may be suffic:iently concentrated in a particular component to be withdrawn as a purge or a co-product stream.
5, The present process provides an efficient means to recover one component from a gas mixture containing at least one otner c-n"onent.
The interactions between the membrane and adsorption units compliment each other's operation to provide an efficient process for producing a high purity product stream at recoveries greater than can be achieved by either unit operated individually.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a schematic flow diaqram of one embodiment of the present invention wherein the desired product is a more permeable component of the feed gas mixture.
Figure 2 is a schematic flow diagram of one embodiment of the present invention wherein the desired product is a less permeable component of the feed gas mixture.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is a process for recovering one or more components from a gas mixture. The process involves hybridizing a semi-permeable membrane-based unit or units with an adsorption unit. A
multi-component feed gas mixture containing at least two major components wherein the permeation rate through a membrane unit of one major component is different from the other major components is passed to a plurality of membrane separation units to produce a gas stream concentrated in the desired component. A major component in a feed gas mixture is one whose concentration exceeds 1 volume %, and typically 310 exceeds 4 volume %.
The membrane unit used in this invention can be any membrane device with some selectivity for separating one major gaseous component from the other major - ,onents in the feed gas mixture when a pressure differential is maintained across the membrane. Each membrane unit may consist of a single membrane device or, alternatively, several membrane 13~3~0 l devices plumbed and operated so as to achieve the separation in the most efficient manner; e.g., a cascade of membranes with internal recycle streams between various stages of the membrane unit. Typically, the membrane devices are manufactured in modules, each having certain !j semi-permeable membrane areas for permeation. Semi-permeable membrane materials currently available which can be employed in this process include: polysulfone, cellulose acetate, polyimide, polyamide, silicone rubber, polyphenylene oxide, etc.
The resultant stream from the membrane separation unit concentrated in one or more desired components: i.e., the concentrated stream, is passed to an adsorption unit which contains an adsorbent capable of selectively adsorbing non-desired components, thereby producing a product stream having a high concentration of the desired component. A product stream having a total concentration of the desired components up to at 1.5 least 95 mole % and preferably greater than 99 mole % can be achieved.
In typical embodiments, the product stream will represent at least an 80 mole % and preferably at least a 90 mole % recovery based upon the feed.
The adsorption unit can be kinetic or equilibrium-based and operated as pressure swing, temperature swing, vacuum swing or any other suitable method or combination thereof. Examples of adsorbents typically used in these units include molecular sieves, such as carbon molecular sieves and zeolit:ic materials such as cation exchanged zeolites from the faujasite and mordenite families.
While the term adsorption is used herein, it should be realized that, depending upon the totality of operating conditions and gaseous components, absorption or other similar type purification units may suitably be substituted without deviating from the spirit of the invention.
The non-desired components which were adsorbed in the adsorption unit are subsequently desorbed and recycled along with a portion of the desired r n~onents to the feed gas mixture entering the membrane separation units. A portion of the desired components can be employed as a rinse stream for the adsorption unit following the desorption step.
The rinse stream may then be recycled along with the desorbed ~n~
components. At some point during the desorption cycle, the concentration of one or more of the non-desired c~ nPnts may be sufficiently high to purge a portion of this stream from the process or make it available as a co-product.
5, Units or systems to remove very low levels of conta~i~ts such as ~2~ N2~ H2~ CO2, H2O, etc. can be added to further treat any of the process streams. Such systems are commercially available and can be added as needed to any of the hybrid schemes of the present invention.
Figure l represents one embodiment of the present invention wherein a more permeable component of the feed gas mixture is separated and recovered as a purified product. The gaseous feed mixture 10 containing, up to 90 mole % of the desired component, and preferably between 20-85 mole G5~ is mixed with the compressed recycle stream 95, to give a combir-ed feed stream 20. The combined feed stream 20 is passed to a first membrane unit 21 to form a first permeate stream 30 and a first reject: stream 40. The permeate stream 30, from the first membrane unit Zl is concentrated in the desired component and is fed to an adsorption unit 23 for a final purification to produce a purified product streann 50. Depending upon the pressure level of the permeate stream 30, 2'0 the st:ream can optionally be compressed before it is fed to the adsorption unit 23. The first reject stream 40 from the first membrane unit, 21, is fed to a second membrane unit 22 to produce a second permeate stream 70 and a second reject stream 80. The recovery level of the desired component in the second permeate stream 70 from the second membrane unit 22 is fixed depending upon the desired recovery level or optimum recovery level determined by economic analyses. If necessary, one can fix the recovery level at this stage to be very high such that the overall product recovery level is greater than 99%; a level which is generally very difficult to achieve with the prior art schemes. The 3,0 pressllre of the second permeate stream 70 is generally fixed to be equivalent to that of the purge stream 60 from the adsorption unit 23 so that t:hey can be mixed to form stream 90, compressed in compressor 93, and recycled as compressed stream 95 to the feed gas mixture 10.
Alternatively, the streams could be at different pressures and fed to indivïdual stages of compressor 93. The second reject stream 80 from the ~ x~
second membrane unit 22 may be recovered as a high pressure stream and either expanded separately to recover energy, or utilized for other operations or simply discarded. Depending upon concentration and compos'ition, a portion of the desorbed c~ Ants may optionally be recovered from the adsorption unit 23 as a co-product stream 52 and a separate portion 62 may optionally be passed through an intermediate membrane unit, such as unit 22, prior to being recycled. The key to this proceCs scheme is to fix the recovery of the desired compsnent at a moderate level ~30-90%, particularly 50-80~) at the first membrane unit 2;1, and at a high level; i.e., >50~ and preferably >80~, at the second membrane unit 22.
E'articular gas mixtures which are well suited for separation via this process scheme include: hydrogen-carbon monoxide; hydrogen-hydrocarbon; helium-hydrocarbon; helium-hydrocarbon-nitrogen; and metharle-nitrogen.
Figure 2 represents a process scheme that enriches one or more less permea,ble components as a reject stream in a series of membrane units and purifies the stream in an adsorption unit to recover the desired components as purified product. The major difference between this scheme from the one shown in Figure 1 is that the adsorption unit 230, is used to purify the reject stream 800 from a second membrane unit 220.
The gaseous feed mixture lO0, containing up to a total of 90 mole and preferably between 20-85 mole % of the desired components is mixed with the compressed recycle stream 950 to produce a combined feed stream 200. The combined feed stream 200 is passed to a first membrane unit %lO to produce a first permeate stream 300 and a first reject stream 400. Depending upsn the recovery level desired in the product stream 500, the first membrane unit 210 can be configured into a multi-stage membrane unit. The first permeate stream 300 is collected for subsequent use or simply discarded. The first reject stream 400 is passed to a second membrane unit 220 to produce a second permeate stream 700 and a second reject stream ~00. The second reject stream 800, enriched in the de5ired c~ _onentS~ is passed to an adsorption unit 230 1 3 ~
containing an adsorption medium selective for adsorbing non-desired components, thereby producing a purified product stream 500, having a high concentration of the desired c~ pC entS.
The non-desired components are subsequently desorbed from the adsor~tion unit 230 as stream 600 and mixed with the second permeate stream 700 from membrane unit 220, which are generally at similar pressures, to form stream 900. Stream 900 is compressed to about feed pressure in compressor 930 to form compressed stream 950 which is subse~uently combined with the feed gas mixture 100. Alternatively, streams 600 and 700 may be at different pressures and can be fed to individual sta~es of the compressor 930. Depending upon concentration and composition, a portion of the desorbed components may optionally be recovered from the adsorption unit 230 as a co-product stream 520 and a separate portion 620 may optionally be passed through an intermediate ~5 membrane unit, such as unit 220, prior to being recycled. Gas mixtures which are well suited for separation using this process scheme include:
argon-oxygen; inert gas (nitrogen and argon)-oxygen, hydrocarbon-carbon dioxide; ar~on-NH3 purge gas; and nitrogen-methane.
rn all of the process schemes of the present invention, optional ;20 compressors or expanders may be utilized to vary the pressure of any of the gas streams, depending upon the gas mixture, treatment and product pressure, and pressure difference between any two streams which are subsequently combined. Compressors 93 and 930 in Figures 1 and 2 respectively are only representative of particular embodiments and may be ;!5 repos:itioned or eliminated as other process conditions are altered~
The examples presented below are presented only to illustrate the invenl:ion and are not meant to limit the scope of the invention.
Example 1 The objective of this example is to produce a purified helium (99.9~ mole %) stream at 210 psia from a 665 psia gas mixture containing 58.2 mole % helium. The properties of the feed gas stream are set out in Table 1 below.
- 8 - 1 3~ 0 Table 1 Feed Rate = 240 lb. moles/hr.
Pressure = 665 psia Temperature = 110~F
,j ElEED GAS COMPOSITION:
Component Mole Percent Helium 58.2 Nitrogen 40.5 Methane 1.3 1.0 E'rocess calculations were done for a membrane/PSA process in accorclance with the present invention a~ depicted in Figure 1 ~case 1) and also for several prior art membrane/PSA processes (cases 2 and 3).
1.5 Case 1 I'he feed stream 10, is first mixed with the recycle stream 95 to form a mixed stream 20 having a helium concentration of 66.6 mole ~.
Mixed stream 20 is then fed to the first membrane unit 21 to form a first 2 permeate stream 30 and a first reject stream 40. The permeate stream 30, containing 95% helium, is recovered at 220 psia and is fed to a PSA unit 23 to recover a purified helium product stream 50 at greater than 99 mole % purity at 99.4 mole % recovery. The purified helium product stream 50 is then either sold as a gaseous product or sent to a liquefying process. The reject stream 40 from the first membrane unit 21 is at almost the same pressure as the fresh feed 10 and is fed to the second membrane unit 22 to recover an additional amount of helium. The helium recovery level at the second membrane unit 22 is fixed depending upon the overall desired helium recovery. The pressure of the permeate stream 70 from this membrane stage is the same as the purge stream 60 containing non-desired components, i.e. nitrogen and methane, desorbed from the PSA
unit. Streams 60 and 70 are combined and compressed in compressor 93 to the pressure of the feed 10 and recycled to form a combined feed streaml 20. The reject stream 80 from the second membrane unit 22 which consists mainly of nitrogen and methane c~ ,~on~nts can be directly expanded to recover its energy or can be sent to a helium liguefaction area to provide makeup nitrogen and~or to recover its energy.
I'he details of the key process streams for this process are given in Table 2 below.
A summary of the total helium recovered, relative power consumed, and relative membrane area required for this case is presented in Table 3 below. Although the helium recovery is very high, modifications of the operating conditions of the me~rane and PSA units can further increase recovery.
Table 2 Key Process Streams for the Membrane~PSA Hybrid Process of Figure 1, Example 1, Case 1 Stream Number 10 100 20 30 40 80 70 50 Pressure (psia) 665 665 665 220 660 655 25 210 Total Flow (lb.moles/hr) 240 127.4 367.4 208.6 158.8 101.3 57.5 138.8 Compositior. ~mole ~~' Helium 58.2 82.3 66.6 95.0 29.2 0.9 79.0 100.0 Nitrogen 40.5 17.1 32.4 4.8 68.6 96.0 20.4 --Methane 1.3 0.6 1.0 0.2 2.2 3.1 0.6 --Case 2 In this case a membrane unit is primarily used as a preprocessor to upgrade the feed stream to a desired level of helium purity before the stream is fed to the adsorption unit. The feed gas mixture set out in Table 1 was first treated in a membrane unit to give a permeate stream containing 95% helium at 220 psia as was done in Case 1. This helium-enriched stream is then sent to the PSA unit to produce a purified helium stream at a 210 psia pressure. Although this scheme uses less membrane area and power, it suffers from a significantly lower helium recovery as depicted as case 2 in Table 3 below.
Case 3 The feed gas mixture of Table 1 was treated in a scheme wherein a first membrane unit is used to recover the desired level of helium from the feed stream and a second membrane unit is used to produce a helium strea~m sufficiently enriched so that it can be fed to a PSA unit.
The feed stream is first mixed with the helium enriched stream from the second membrane unit. This mixed stream is then fed to the first membrane unit. The helium recovery level at this stage is fixed such ;~0 that the overall helium recovery level is consistent with Case 1. The permeate stream from the first membrane unit is then mixed with the purge stream from the PSA unit, compressed and subsequently fed to the second membr.~ne unit. The permeate stream from ~he second membrane unit is recovered at a 220 psia pressure and fed to the PSA unit to produce a ;!5 helium product stream.
~ n general, this scheme differs from the new concept in that the first membrane unit, which processes a large stream, is required to operalte at a very high recovery level. As shown in Table 3, this scheme ~case 3) uses more power and me~brane area than the new suggested 3~ concept.
3,5 - 12 - ~ c'~
Table 3 Comparison of the Cases Presented in Example 1 Case Heli~n Recovery (%) 99.4 43.5 99.4 Relative Power 1.0 0.0 1.76 Relative Area 1.0 0.26 1.10 .0 In summary, Example 1 clearly illustrates that the process scheme of the present invention (case 1) gives a purified product stream at very high recovery and is also very efficient compared to other schemes previously used to separate gas mixtures.
Example 2 ~'he following example illustrates the embodiment shown in Figure 2.
This concept is an attractive process scheme when the desired product is a less permeable component through the membrane units, which can be purified and recovered as a raffinate stream from the adsorption unit.
This e!mbodiment has an added advantage in that the desired product can be recove!red as a high pressure stream without additional compression.
Calculations were done to produce a high purity argon stream from a gas mixture containing 50% oxygen and 50~ argon. The membrane characteristics used to simulate this example are for advanced membranes currently being developed; for example, U.S. patent 4,584,359 teaches a cobalt complex vinyl polymer membrane that possesses a very high permeability of oxygen with respect to other components such as nitrogen, argon, etc. The PSA unit used to simulate this case is a kinetic-based system which preferably adsorbs oxygen over argon; however, this particular PSA unit can be replaced with an equilibrium-based unit depending upon the specific separation desired in a process situation.
In this process, the feed stream, 100, is first mixed with the recycle stream, 950, before it is fed to the first membrane unit, 210 as - 13 ~ t~
stream 200 having a 52.1 mole% argon concentration. The permeate stream 300 from the first membrane unit 210 contains about 97% oxygen and is recovered at a 20 psia pressure. Again, the oxygen recovery at the feed stage membrane unit is fi~ed at a relatively low level ~~50%) in order to increase the oxygen purity and to minimize the argon losses in the permea,te stream 300. The reject stream 400 has a concentration of 68.2 mole ~; argon and is directly fed to the second membrane unit 220 to produce an argon-enriched reject stream 800, having an argon concer.~tration of 97.5 mole %, at a high pressure and to recover an argon-lean permeate strea~ 700 which is recycled after recompression.
The o~ygen recovery level at the second membrane unit can vary depending upon the argon purity and recovery desired for the second reject stream 800. The argon-enriched second reject stream 800 is then fed to the PSA unit to produce a purified argon product stream 500 at a concentration near 100% at high pressure. The eurge stream 600 from the PSA unit is at 20 psia pressure and is mixed with permeate stream 700 from the second membrane unit and recycled to the feed.
The details of the feed stream and the other key process streams for this process scheme are given in Table ~ below. These calculations were done based on the assumptions that all permeate streams from the membrane units and the purge stream from the PSA unit were maintained at 20 psia pressure, and the argon recovery at the PSA unit was fixed at 50%.
2l5 - 1 4 - ~- 3 ~
~ o o o CO , o o ~ ~ , o U ~ ,, o o ~ ,, o ~ U~
I' ~ In u~
.
o o a~
o o o~
~ er O t~
1~ o u r~ ~ C~
O O L~
.~ , .
,. . .
.q o o ~
o ~ u- a ~r .~ ~ O o a~
o ~ o a' o o a~
~ U- , o er U~
o a) ~ ~1 E
~ o o o o o U~ o _I o U~ U
~q a) S~
:C ~, o~~
~I a) I~J S E
~o --J~ 0~ r o .
F
O
~ U
v EO~ ~- ~
The data reported in Table 4 above show that the process scheme carried out in Example 2 above provides for the recovery of an argon product stream having a purity of about 100%. Total argon recovery is also very high since the only argon lost from the system is that 5, contained in the permeate from the first membrane unit which is regulated to keep the argon loss at a minimum.
Examp:Le 3 A second particular process scheme was carried in accordance with the general scheme illustrated in Figure 2. In this scheme, the permeate stream 300 from the first membrane unit 210 is further processed in a separate membrane unit ~not shown) to increase the purity of the more permeable component thus increasing the recovery of the desired less permeable component.
lS C'alculations were done to produce a high purity methane stream 500 from a gas mixture containing 55% methane, 41% carbon dioxide, and a remaining mixture containing nitrogen, oxygen and water vapor. This gas composition is typical of landfill gas. Characteristics of currently available membranes were used to simulate this process and the adsorption unit used was a PSA unit such as a kinetic-based or equilibrium-based system which preferably adsorbs carbon dioxide over methane.
ln this process, the feed stream 100 is first mixed with the purged stream from the PSA unit and the mixed stream is compressed to an intermediate pressure of about 100 psia. After compression, this mixed streaml is then mixed with the permeate stream from the second membrane separation unit 220. The resultant stream is then compressed to a feed pressure of about 775 psia and is passed to the first membrane unit 210 as feed stream 200. The permeate stream 300 from the first membrane unit 210 contains about 93% car-bon dioxide and is at about 105 psia 3l~ pressure. The carbon dioxide recovery at the feed stage membrane unit is fixed at a relatively low level ~ 50%) to increase the carbon dioxide purity; however, this stream still contains about 6% methane, which represents about 10% methane lost to the overall process if not recovered. The permeate stream 300 is, therefore, sent to an additional 3!;
~ 3 i~
membrane unit ~not shown) where further purification of carbon dioxide or further recovery of methane is accomplished. The resultant purified strearn from this additional membrane unit contains 98.5% carbon dioxide and only 0.7% methane. The reject stream produced from this additional 5, membrane unit contains 89~ carbon dioxide and 10% methane, and is recyc:Led at about 100 psia pressure to the feed gas entering the first membrane unit 210.
The reject stream 400 from the first membrane unit 210 has a methane concentration of 51% and is directly fed to the second membrane unit 220 to produce a methane-enriched reject stream 800 having a methane concentration of 80%, at a high pressure and a methane-lean permeate stream 700 at about 100 psia pressure. The methane-enriched reject stream 800 from the second membrane unit 220 is subsequently fed to PSA
unit .!30 to produce a purified methane product stream 500 at a concentration of about 98% or higher at high pressure.
l'he gas adsorbed in the PSA unit 230: i.e., carbon dioxide, can be recovered as a purified carbon dioxide co-product stream or alternatively, the total desorbed gas mixture 600 can be recycled and mixed with the feed stream 100.
l'he details of the feed stream and the other ~ey process streams for this example are given in Table 5 below. These calculations were based on a 10% methane recovery at the PSA unit.
, c~
~ a~ O
o o r- ~~ o o u ~ a~
u~ t' ~
O ~~ ~ cn o o~n ~1 0 r~ ~ o o O
co r' ~
CD ~ ~ I~ O
. . . .
O O C~ ~D ~ O O O
1' _I ~1 cn CD O
. . . .
O1-- o UO~1-- ~ ~
L? ~l' ?
O U ~ ~O ~ O O O
~4 0 0 ~1 ~1 ~
OU~ O U ~ O O O
O1' ~ t~
C:
~n ~ ~ u o ~ O
a ~ 0~~~~ ~ o ~ o o o g o ~D ~ O ~ O
O OU~ O
O~1 ~ U~ ~
., J~ ~
? a 0~,, ~ô .a 6 W
Z1~ .~,. w - -~ r _~ W ~
W
~ , o Z O ~
The data reported in Table S above shows that the process being carried out in Example 3 provides for the recovery of a methane product stream having a purity of about 98% and a recovery greater than 99%.
5, Example 4 A process was simulated for the recovery of argon from ammonia purged gas in accordance with the general scheme set out in Piqure 2.
The am~onia purge gas which forms the feed stream 100 has a composition of about. 62~ hydrogen, 20% nitrogen, 11~ methan2 and 7% argon ii under a 10 pressure of approximately 2,000 psia and at a tempe.atur~ Or about 95~F.
This stream is obtained from an ammonia plant after the removal of ammonia from the purged gas by any kno:m technique, such as by absorption.
The feed stream 100 is combined with recycled stream 9'0 to give a combined feed 200 containing 70% ~2 and 8.7~ Ar and is fed to a first membrane unit 210. The permeate stream 300 from the fir~t mem~rane unit 210 cor.tains 9~.5% hydr~gen and ser.t back to the a~enia plant. The recovery of hydrogen from this pro-ess is hi~h; i.e., about 98eo. The non-permeate stream 400 from the me~rane unit.210 forms the feed to a se~ond men~ralle unit 220 and is separated to provide reject stredm B~0 containing 5% H2 and 24.9% argon. The concentration of hydrogen in this steeam determines the relative am~unt of ar~on and hydrogen in the product stream 500 from the adsorption unit 230. A smaller concentration of hydrc,gen will give stream 500 a hiqher argon concentration thus reducing further purification requirements but the me.l~rane area of unit 220 must be enlarged and the permeate stream from membrane unit 220 would increase for recycle. For any given application, a detailed economic analysis would dictate the optimum combination of hydrogen and argon in stream 800 which is passed to the adsorption unit 230. In the present analysis, it was arbitrarily chosen to be 5~ H2. The permeate stream 700 from membrane unit 220 containing 3.9% argon is recycled to the first membrane unit 210. The presence of this recycle back to the feed stream allows the present process to be run with a high recovery of argon.
3'5 The reject stream 800 from the second membrane unit 220 contains 24.9% argon and is sent to an adsorption unit capable of adsorbing nitrogen and methane relative to argon and hydrogen. The recovery of N2 ancl CH4 from the adsorption process was taken to be 90% and that 5 of argon to be 50~. Consequently, the adsorption process not only produces a product stream 500 containing 83.3% argon and 16.7~ H2 but also produces a co-product stream 520 containing 63.9% N2 and 35.1%
CH4. A purged stream 600 is also recovered from the adsorption unit to form a part of the recycled stream 950 to the first membrane unit 210.
This recycled stream keeps the total argon recovery for the over~ll process at a high level; i.e., about 86%.
The argon product, stream 500, contains some hydrogen which can be removed by any known process or combination of processes, for example argon could be cryogenically condensed or hydrogen could be removed by oxidation after which the water formed could be condensed and/or adsorbed, or an additional membrane unit could be used to remove the hydrogen.
Conventionally, argon is recovered from ammonia purged gas by cryogenic means. Such cryogenic systems are complicated and costly, 20 requiring an attendant refrigeration system for the operation of a low-temperature separation unit. Moreover, the cryogenic plants are not amenable to quick turn downs and encounter problems associated with feed gas variations and plant stability. This is due to the fact that the cryogenic units are subject to operational variances of the ammonia plant 2'; and not vice versa. See, Isalski, W. H., "25 Years of Purged Gas Recovery" Nitrogen, lOl, 152 (1984). The present process scheme which consists of a membrane unit followed by an adsorption unit is 00re amenable to feed turn downs and is easier to operate than previous methods.
T'he details of the key process streams obtained from the simulation of the above-described process are set out in Table 6 below.
35, .~eqo~r~-l ~r o U ~ o~
o U o o ~ U~ o ~ 4 ~ ~
a~ o o ~ o o ,~
L~ O d~ O
O U~
O ~1 ~ r~
8 ~ ~ .~
s~ o o 1' u In ~ ~p o O ~1 ~: . . . .
g o ~ r- o o ,.
~- ~O O ~ ~D r~
o O O g ~ o ~ r~ ~~
~ ~ ~ o Q
E~ Q ~ ~~
~ o o~ ) oU~
:r: u o1-- co ~1 ~r P, ~
o o o o o a~ . . . .
O O O ~ O ~1 1 ~0 0 0 0 ~ o,1 ~ .
J~
o ~U
., ~ o~
J _~
nl ~ O
X ~ ,1Z~
o 8 As can be seen from the results reported in Table 6 above, a product strearn rich in argon can be obtained from the present process. While the product stream consists of two different components, in general this is not a problem because the two resultant components may be easily separated or used together, with the real problem of removing nitrogen and methane, being solved by the process.
Examp]e 5 The process scheme as depicted in Figure 2 was simulated for the separation and recovery of 99.5% inert gas (nitrogen and argon) from air. This scheme is almost identical to the case presented in Example 2 above, with the difference being that the feed gas mixture is air, and the major component besides oxygen is nitrogen instead of argon. The present scheme was developed for air separation usinq me.~brane characteristics representing currently available membranes, and a kinetic-based PSA system.
One particular benefit of this process scheme is that the PSA unit is used to adsorb ~2-10~ oxygen versus -21~ oxygen in a stand-alone unit, thereby increasing the inert gas recovery and productivity of the PSA unit. Another benefit of this process scheme is that most of the contaminants; e.g., CO2, H20, etc., contained in the air will be removed by the membrane units. This improves the operation of the adsorption unit since typical adsorbents prefer C02 and H2O over ~2' 2!; Since the primary value associated with the feed gas for this application is the power used to compress it, additional flexibility is added to the cycle so that, if the oxygen purity of the second permeate stream 700 from membrane unit 220 is greater than that of air, it may be mixed with the first permeate stream 300 and recovered as an 3(~ oxygen-enriched stream instead of being combined with the desorbed stream 600 and recycled to the feed gas. This can be done for this particular application because product recovery is less of a concern with the inert gas product ~stream 500) purity being the most important parameter.
3'i t~
The details of the key process streams for this example are given in Table 7 below. These results clearly indicate that the process scheme depicl:ed in Figure 2 is suitable for recovering an inert gas ti.e., nitrogen and argon) at high purity, i.e. 99.5 mole % from an air feed.
5, The first permeate stream 300 from the first membrane unit 210 can also be recovered as an oxygen-enriched stream; i.e., 39 mole % oxyqen.
]:t was calculated that this process scheme can recover as much as twice the amount of product at less power consumption than either the kinetic-based adsorption unit or membrane unit when used as a stand-alone proce~;s.
2!j 35, u~ ~ r' o o o o ~~
o o ~ o~ ll a O ~ ~D
~o o o ~l o o~ o . ~, O ~ ~~ ~ ~ I
~0 Oa? ~ ~~D
,~ ? O O ~1 0a~ o J ~ o r~ c S~ O U ~ ~CO~1 0 ~ o ~1 ~ ~~n U~
O u~ o oI O
~~ O 1~ _I _I ~ I
w Oa) .C u~ a~D
. . .
O U- ~ u ~ O
O a~
~ ~O O_I~ O
O ~a~ ~ oa~
~ J O U~ ~ OU~ O
Z ~ o .~
~J
o S~
0~o S ~ A
a) u~-- .--~ ~ O C
z a~ C
;'' r~ r J O ~ ~
O ~ r_ n ,~
J ~ ~
rn gas separation processes, when the product gas has a high value, a very high purity and recovery are often desired. The present invention provides process schemes that can efficiently recover a purified product (99+~) at high recovery (80+%) from a gas mixture containing at least one ~; other component. The method of the present invention takes advantage of the favorable characteristics and minimizes the deficiencies of the membrane and adsorption units.
Stand-alone membrane units are generally considered very efficient for bulk separations on a relatively smaller scale, however, these ~o systems are not generally efficient, if not impractical, in producing a high purity product ~>99%~ at very high recovery ~>90%). When membrane units are used in a cascade to get high recoveries and/or purities, intermediate compression is often reguired and a relatively large amount of energy and membrane area are necessary.
lS ';tand-alone adsorption units, on the other hand, are very effective in producing a purified gas stream, but they require the purity of feed streams to be relatively high; e.g., 70%. The performance of these units generally suffers from a relatively low recovery which can be further reduced if the pressure of the feed is very high.
~he present invention not only gives a purified product stream at high recovery but also consumes much less power and/or results in substa~ntial process simplifications, reduced investments, and improved economics. Mbny embodiments of the invention provide for the recovery of a second product stream enriched in a component other than that of the purified product.
Hiaving thus described the present invention, what is now deemed appropriate for Letters Patent is set out in the following appended claims.
31~
Claims (32)
1. A process for recovering a desired component from a multi-component feed gas stream, said process comprising:
a) passing said feed gas stream to a plurality of membrane separation units to produce a stream concentrated in the desired component;
b) passing said concentrated stream to an adsorption unit containing an adsorbent that selectively adsorbs non-desired gaseous components present in said stream to produce a product stream further concentrated in the desired component;
c) desorbing the gaseous components from said adsorbent; and d) recycling said desorbed gaseous components to the feed gas stream entering the membrane separation units.
a) passing said feed gas stream to a plurality of membrane separation units to produce a stream concentrated in the desired component;
b) passing said concentrated stream to an adsorption unit containing an adsorbent that selectively adsorbs non-desired gaseous components present in said stream to produce a product stream further concentrated in the desired component;
c) desorbing the gaseous components from said adsorbent; and d) recycling said desorbed gaseous components to the feed gas stream entering the membrane separation units.
2. A process in accordance with Claim 1 wherein at least a portion of the desorbed gaseous components is recovered as a co-product.
3. A process in accordance with Claim l wherein a stream depleted in the desired component is also produced by the plurality of membrane separation units.
4. A process in accordance with Claim 1 wherein at least a portion of said desorbed gaseous components are passed through an intermediate membrane unit prior to being recycled to the feed gas.
5. A process in accordance with Claim 1 wherein said adsorption unit is operated as pressure swing, vacuum swing, temperature swing or a combination thereof.
6. A process in accordance with Claim 1 wherein said adsorption unit is rinsed with a portion of the desired component after the adsorbed components are desorbed.
7. A process in accordance with Claim 6 wherein said portion of the desired components used to rinse the adsorption unit are recycled along with the desorbed components to the feed stream
8. A process for separating a more permeable component of a multi-component feed gas mixture from a less permeable component and subsequently recovering said more permeable component as a purified product, said process comprising:
a) passing said multi-component feed gas mixture to a first membrane separation unit to produce a first permeate stream and a first reject stream:
b) passing said first permeate stream to an adsorption unit containing an adsorbent which selectively adsorbs less permeable components present in said permeate stream thereby producing a purified product stream;
c) desorbing the less permeable components from said adsorbent;
d) recycling said desorbed components to the feed gas stream entering the first membrane separation unit;
e) passing said first reject stream to a second membrane-separation unit to produce a second permeate stream and a second reject stream; and f) combining said second permeate with said desorbed components prior to being recycled to the feed gas stream.
a) passing said multi-component feed gas mixture to a first membrane separation unit to produce a first permeate stream and a first reject stream:
b) passing said first permeate stream to an adsorption unit containing an adsorbent which selectively adsorbs less permeable components present in said permeate stream thereby producing a purified product stream;
c) desorbing the less permeable components from said adsorbent;
d) recycling said desorbed components to the feed gas stream entering the first membrane separation unit;
e) passing said first reject stream to a second membrane-separation unit to produce a second permeate stream and a second reject stream; and f) combining said second permeate with said desorbed components prior to being recycled to the feed gas stream.
9. A process in accordance with Claim 8 wherein at least a portion of said desorbed components is recovered as a co-product.
10. A process in accordance with Claim 8 wherein at least a portion of said desorbed gaseous components are passed through an intermediate membrane unit prior to being recycled to the feed gas.
11. A process in accordance with Claim 8 wherein said multi-component feed gas mixture contains helium as a more permeable component and nitrogen or hydrocarbons as a less permeable component.
12. A process in accordance with Claim 8 wherein said multi-component feed gas mixture contains hydrogen as a more permeable component and carbon monoxide or hydrocarbons as a less permeable component.
13. A process in accordance with Claim 8 wherein said adsorption unit is operated as pressure swing, vacuum swing, temperature swing or a combination thereof.
14. A process in accordance with Claim 8 wherein the second reject stream is collected as a second product.
15. A process in accordance with Claim 8 wherein said feed gas mixture has a concentration of between 20-85 mole % of the more permeable component.
16. A process in accordance with Claim 8 wherein the combined desorbed components and the second permeate stream are compressed to feed gas pressure prior to being combined with the feed gas stream.
17. A process in accordance with Claim 8 wherein the purified product stream has a concentration of greater than 99 mole % of the more permeable component.
18. A process for separating a less permeable component of a multi-component feed gas mixture from a more permeable component and subsequently recovering said less permeable component as a purified product, said process comprising:
a) passing said multi-component feed gas mixture to a first membrane separation unit to produce a first permeate stream and a first reject stream;
b) passing said first reject stream to a second membrane separation unit to produce a second permeate stream and a second reject stream:
c) passing said second reject stream to an adsorption unit containing an adsorbent which selectively adsorbs more permeable components present in said reject stream thereby producing a purified product stream;
d) desorbing the more permeable components from said adsorbent; and e) recycling said desorbed components to the feed gas stream entering the first membrane separation unit.
a) passing said multi-component feed gas mixture to a first membrane separation unit to produce a first permeate stream and a first reject stream;
b) passing said first reject stream to a second membrane separation unit to produce a second permeate stream and a second reject stream:
c) passing said second reject stream to an adsorption unit containing an adsorbent which selectively adsorbs more permeable components present in said reject stream thereby producing a purified product stream;
d) desorbing the more permeable components from said adsorbent; and e) recycling said desorbed components to the feed gas stream entering the first membrane separation unit.
19. A process in accordance with Claim 18 wherein at least a portion of the desorbed components is recovered as a co-product.
20. A process in accordance with Claim 18 wherein at least a portion of said desorbed gaseous components are passed through an intermediate membrane unit prior to being recycled to the feed gas.
21. A process in accordance with Claim 18 wherein said purified product stream has a concentration greater than 99 mole % of the less permeable component.
22. A process in accordance with Claim 18 wherein said second permeate stream is combined with the desorbed components from the adsorption unit prior to being recycled to the feed gas stream.
23. A process in accordance with Claim 18 wherein said first permeate stream is collected as a second product stream enriched in a component other than that of the purified product stream.
24. A process in accordance with Claim 23 wherein said second permeate stream is combined with the first permeate stream and collected as a combined permeate stream.
25. A process in accordance with Claim 18 wherein the feed gas mixture comprises argon as a less permeable component and oxygen as a more permeable component.
26. A process in accordance with Claim 18 wherein the purified product stream comprises one or more hydrocarbons.
27. A process in accordance with Claim 18 wherein said adsorption unit is operated as pressure swing, vacuum swing, temperature swing or a combination thereof.
28. A process for separating nitrogen from air and subsequently recovering nitrogen as a purified product, said process comprising:
a) passing an air stream to a membrane separation unit to produce an oxygen-enriched permeate stream and a reject stream;
b) passing said reject stream to an adsorption unit containing an adsorbent which is selective for oxygen, thereby producing a purified nitrogen product stream; and c) desorbing the oxygen from the adsorbent and recycling it back to the air stream entering the separator.
a) passing an air stream to a membrane separation unit to produce an oxygen-enriched permeate stream and a reject stream;
b) passing said reject stream to an adsorption unit containing an adsorbent which is selective for oxygen, thereby producing a purified nitrogen product stream; and c) desorbing the oxygen from the adsorbent and recycling it back to the air stream entering the separator.
29. A process in accordance with Claim 28 wherein said reject stream is further separated by a second membrane prior to being passed to the adsorption unit, thereby producing a second oxygen-enriched stream and a reject stream which is then passed to the adsorption unit.
30. A process in accordance with Claim 29 wherein both oxygen-enriched permeate streams are combined and collected as a second product.
31. A process in accordance with Claim 28 wherein the adsorption unit is rinsed with a portion of the nitrogen product after the oxygen is desorbed.
32. A process in accordance with Claim 28 wherein said purified nitrogen is recovered along with argon as a purified inert product stream.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US926,695 | 1986-11-03 | ||
US06/926,695 US4701187A (en) | 1986-11-03 | 1986-11-03 | Process for separating components of a gas stream |
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CA1340001C true CA1340001C (en) | 1998-08-18 |
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Application Number | Title | Priority Date | Filing Date |
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CA000550376A Expired - Fee Related CA1340001C (en) | 1986-11-03 | 1987-10-27 | Process for separating components of a gas stream |
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US (1) | US4701187A (en) |
EP (1) | EP0266745A3 (en) |
JP (1) | JP2664169B2 (en) |
KR (1) | KR920007855B1 (en) |
AU (1) | AU575755B2 (en) |
BR (1) | BR8705906A (en) |
CA (1) | CA1340001C (en) |
MX (1) | MX163428B (en) |
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US11548784B1 (en) | 2021-10-26 | 2023-01-10 | Saudi Arabian Oil Company | Treating sulfur dioxide containing stream by acid aqueous absorption |
US11926799B2 (en) | 2021-12-14 | 2024-03-12 | Saudi Arabian Oil Company | 2-iso-alkyl-2-(4-hydroxyphenyl)propane derivatives used as emulsion breakers for crude oil |
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JPS588283B2 (en) * | 1976-03-23 | 1983-02-15 | 株式会社東芝 | Mixed gas separation equipment |
US4130403A (en) * | 1977-08-03 | 1978-12-19 | Cooley T E | Removal of H2 S and/or CO2 from a light hydrocarbon stream by use of gas permeable membrane |
US4180552A (en) * | 1978-03-20 | 1979-12-25 | Monsanto Company | Process for hydrogen recovery from ammonia purge gases |
US4255591A (en) * | 1978-11-20 | 1981-03-10 | Monsanto Company | Carbonylation process |
US4238204A (en) * | 1979-06-18 | 1980-12-09 | Monsanto Company | Selective adsorption process |
US4229188A (en) * | 1979-06-18 | 1980-10-21 | Monsanto Company | Selective adsorption process |
JPS5815130A (en) * | 1981-07-22 | 1983-01-28 | Toshiba Corp | Infrared detector |
JPS58151305A (en) * | 1982-03-03 | 1983-09-08 | Nippon Sanso Kk | Production of oxygen |
JPS58150788A (en) * | 1982-03-03 | 1983-09-07 | 日本酸素株式会社 | Method of separating and removing water and carbonic acid gas of air utilizer |
US4466946A (en) * | 1982-03-12 | 1984-08-21 | Standard Oil Company (Indiana) | CO2 Removal from high CO2 content hydrocarbon containing streams |
US4398926A (en) * | 1982-04-23 | 1983-08-16 | Union Carbide Corporation | Enhanced hydrogen recovery from low purity gas streams |
EP0100923B1 (en) * | 1982-07-29 | 1986-02-05 | Linde Aktiengesellschaft | Process and apparatus for separating a gas mixture |
DE3337572A1 (en) * | 1983-10-15 | 1985-04-25 | Linde Ag, 6200 Wiesbaden | METHOD AND DEVICE FOR SEPARATING A COMPONENT FROM A GAS MIXTURE |
US4639257A (en) * | 1983-12-16 | 1987-01-27 | Costain Petrocarbon Limited | Recovery of carbon dioxide from gas mixture |
US4518399A (en) * | 1984-08-24 | 1985-05-21 | Monsanto Company | Process for recovering gases from landfills |
JPS61127609A (en) * | 1984-11-27 | 1986-06-14 | Kobe Steel Ltd | Purification device for helium |
US4654063A (en) * | 1984-12-21 | 1987-03-31 | Air Products And Chemicals, Inc. | Process for recovering hydrogen from a multi-component gas stream |
US4645516A (en) * | 1985-05-24 | 1987-02-24 | Union Carbide Corporation | Enhanced gas separation process |
US4602477A (en) * | 1985-06-05 | 1986-07-29 | Air Products And Chemicals, Inc. | Membrane-aided distillation for carbon dioxide and hydrocarbon separation |
-
1986
- 1986-11-03 US US06/926,695 patent/US4701187A/en not_active Expired - Lifetime
-
1987
- 1987-10-27 CA CA000550376A patent/CA1340001C/en not_active Expired - Fee Related
- 1987-10-28 MX MX8997A patent/MX163428B/en unknown
- 1987-10-29 BR BR8705906A patent/BR8705906A/en unknown
- 1987-11-02 JP JP62275903A patent/JP2664169B2/en not_active Expired - Lifetime
- 1987-11-02 AU AU80574/87A patent/AU575755B2/en not_active Ceased
- 1987-11-03 KR KR1019870012332A patent/KR920007855B1/en not_active IP Right Cessation
- 1987-11-03 EP EP87116173A patent/EP0266745A3/en not_active Withdrawn
Also Published As
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---|---|
AU8057487A (en) | 1988-05-26 |
JPS63126522A (en) | 1988-05-30 |
JP2664169B2 (en) | 1997-10-15 |
KR920007855B1 (en) | 1992-09-18 |
BR8705906A (en) | 1988-06-14 |
EP0266745A3 (en) | 1989-04-19 |
AU575755B2 (en) | 1988-08-04 |
MX163428B (en) | 1992-05-12 |
US4701187A (en) | 1987-10-20 |
EP0266745A2 (en) | 1988-05-11 |
KR880005958A (en) | 1988-07-21 |
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