CA2671307A1 - Selective removal of nitrogen from natural gas by pressure swing adsorption - Google Patents

Selective removal of nitrogen from natural gas by pressure swing adsorption Download PDF

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Publication number
CA2671307A1
CA2671307A1 CA002671307A CA2671307A CA2671307A1 CA 2671307 A1 CA2671307 A1 CA 2671307A1 CA 002671307 A CA002671307 A CA 002671307A CA 2671307 A CA2671307 A CA 2671307A CA 2671307 A1 CA2671307 A1 CA 2671307A1
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Canada
Prior art keywords
nitrogen
stream
methane
selective
selective sorbent
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Granted
Application number
CA002671307A
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French (fr)
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CA2671307C (en
Inventor
William B. Dolan
Kenneth F. Butwell
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BASF Catalysts LLC
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Engelhard Corporation
William B. Dolan
Kenneth F. Butwell
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Publication of CA2671307A1 publication Critical patent/CA2671307A1/en
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Publication of CA2671307C publication Critical patent/CA2671307C/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
    • C07C7/13—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers by molecular-sieve technique
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • 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
    • 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
    • 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
    • B01D2253/1085—Zeolites characterized by a silicon-aluminium ratio
    • 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
    • B01D2253/25—Coated, impregnated or composite adsorbents
    • 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
    • B01D2253/30—Physical properties of adsorbents
    • B01D2253/302—Dimensions
    • B01D2253/308—Pore size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/102—Nitrogen
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40001—Methods relating to additional, e.g. intermediate, treatment of process gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40011—Methods relating to the process cycle in pressure or temperature swing adsorption
    • B01D2259/40043—Purging
    • B01D2259/4005—Nature of purge gas
    • B01D2259/40052—Recycled product or process gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40011—Methods relating to the process cycle in pressure or temperature swing adsorption
    • B01D2259/40043—Purging
    • B01D2259/4005—Nature of purge gas
    • B01D2259/40056—Gases other than recycled product or process gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40011—Methods relating to the process cycle in pressure or temperature swing adsorption
    • B01D2259/40077—Direction of flow
    • B01D2259/40081—Counter-current
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
    • B01D2259/40088—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating
    • B01D2259/4009—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating using hot gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/403—Further details for adsorption processes and devices using three beds
    • 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
    • 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
    • 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
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
    • Y02P20/156—Methane [CH4]
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S95/00—Gas separation: processes
    • Y10S95/90—Solid sorbent
    • Y10S95/901—Activated carbon
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S95/00—Gas separation: processes
    • Y10S95/90—Solid sorbent
    • Y10S95/902—Molecular sieve

Abstract

A process for the separation of nitrogen and hydrocarbons from a natural gas stream comprises passing the natural gas stream to a first pressure swing adsorption unit containing a hydrocarbon-selective sorbent so as to preferentially adsorb at least C4+ hydrocarbons to produce a first product stream, comprising methane, nitrogen and a reduced level of the hydrocarbons relative to the natural gas stream The first product stream is then passed to a second pressure swing absorption unit containing a nitrogen-selective sorbent so as to preferentially adsorb nitrogen and produce a second product stream enriched with methane, and a low pressure purge stream having a higher molar concentration of nitrogen than the first product stream.

Claims (13)

1. A pressure swing adsorption (PSA) process for the separation of nitrogen from a mixture of the same with methane which comprises:
a) passing a feed stream comprising said mixture in contact with a nitrogen-selective sorbent in a PSA unit so as to preferentially adsorb nitrogen and produce a methane-rich product stream containing at least 70 mol. %
methane and a low pressure purge stream having a higher molar concentration of nitrogen than said mixture; and (b) subsequent to step (a), periodically heating said nitrogen-selective sorbent with the methane-rich product stream to drive off accumulated methane from the sorbent.
2. The process of claim 1, wherein subsequent to step (b), said nitrogen-selective sorbent is cooled.
3. The process of claim 1, wherein said nitrogen-selective sorbent is a CTS-1 crystalline titanium silicate having a pore size of 3 to less than 4 A.
4. The process of claim 1, wherein said nitrogen-selective sorbent is a barium exchanged ETS-4 crystalline titanium silicate wherein barium comprises at least 30%
of the exchangeable cations of said titanium silicate.
5. The process of claim 2, wherein said nitrogen-selective sorbent is cooled by contact with a gas stream which contains at least 30 mole % nitrogen.
6. The process of claim 5, wherein said nitrogen-selective sorbent is cooled with a gas stream containing at least 90 mole % nitrogen.
7. The process of claim 6, wherein said stream to cool said nitrogen-selective sorbent comprises at least 90%
nitrogen with the balance methane.
8. The process of claim 1 comprising co-currently depressurizing said PSA unit to form a recycle stream rich in methane, said recycle stream having a pressure less than said methane-rich product stream, but greater than said purge stream, and recycling said recycle stream to said feed stream.
9. The process of claim 1, wherein said feed stream comprises natural gas.
10. The process of claim 2, wherein said cooling is provided by contacting said nitrogen-selective adsorbent with a gas stream fed countercurrent to the direction of said feed stream.
11. The process of claim 10, wherein said feed stream does not contain water or carbon dioxide.
12. The process of claim 2, wherein said cooling is provided by contacting said nitrogen-selective adsorbent with a gas stream fed cocurrent to the direction of said feed stream.
13. The process of claim 12, wherein said feed stream contains water and/or carbon dioxide.
CA002671307A 2000-10-30 2001-10-25 Selective removal of nitrogen from natural gas by pressure swing adsorption Expired - Lifetime CA2671307C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US09/699,664 2000-10-30
US09/699,664 US6444012B1 (en) 2000-10-30 2000-10-30 Selective removal of nitrogen from natural gas by pressure swing adsorption
CA2426024A CA2426024C (en) 2000-10-30 2001-10-25 Selective removal of nitrogen from natural gas by pressure swing adsorption

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CA2426024A Division CA2426024C (en) 2000-10-30 2001-10-25 Selective removal of nitrogen from natural gas by pressure swing adsorption

Publications (2)

Publication Number Publication Date
CA2671307A1 true CA2671307A1 (en) 2002-08-01
CA2671307C CA2671307C (en) 2010-01-19

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CA002671307A Expired - Lifetime CA2671307C (en) 2000-10-30 2001-10-25 Selective removal of nitrogen from natural gas by pressure swing adsorption
CA2426024A Expired - Lifetime CA2426024C (en) 2000-10-30 2001-10-25 Selective removal of nitrogen from natural gas by pressure swing adsorption

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Country Status (9)

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US (1) US6444012B1 (en)
EP (2) EP1666126B1 (en)
AT (2) ATE434473T1 (en)
AU (1) AU2002246890A1 (en)
CA (2) CA2671307C (en)
DE (2) DE60139081D1 (en)
ES (2) ES2326489T3 (en)
PT (2) PT1666126E (en)
WO (1) WO2002058818A2 (en)

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