US20100000154A1 - Method for separating sulphur out of a gas that contains sulphur - Google Patents

Method for separating sulphur out of a gas that contains sulphur Download PDF

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Publication number
US20100000154A1
US20100000154A1 US12/480,217 US48021709A US2010000154A1 US 20100000154 A1 US20100000154 A1 US 20100000154A1 US 48021709 A US48021709 A US 48021709A US 2010000154 A1 US2010000154 A1 US 2010000154A1
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United States
Prior art keywords
sulphur
gas
separation process
absorptive separation
recited
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.)
Abandoned
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US12/480,217
Inventor
Robert Adler
Markus Mayer
Ekkehardt KLEIN
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Linde GmbH
Original Assignee
Linde GmbH
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Filing date
Publication date
Application filed by Linde GmbH filed Critical Linde GmbH
Assigned to LINDE AKTIENGESELLSCHAFT reassignment LINDE AKTIENGESELLSCHAFT ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ADLER, ROBERT, MAYER, MARKUS, Klein, Ekkehardt
Publication of US20100000154A1 publication Critical patent/US20100000154A1/en
Abandoned legal-status Critical Current

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    • 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
    • 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
    • B01D53/14—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 absorption
    • B01D53/1487—Removing organic compounds
    • 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
    • B01D53/14—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 absorption
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • 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
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/16—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/24—Hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/306—Organic sulfur compounds, e.g. mercaptans

Definitions

  • the invention relates to a method for separating sulphur out of a gas that contains sulphur, particularly hydrogen or natural gas, wherein the gas is compressed and the sulphur is removed via an absorptive separation process.
  • Species-related methods for separating sulphur from a gas containing sulphur are used for example at natural gas filling stations.
  • the natural gas for use as fuel is drawn from the existing natural gas supply network, dried, and compressed to a storage pressure that may reach 300 bar.
  • the sulphur content in the natural gas that is drawn from the supply network is usually too high to be processed effectively with today's engine and exhaust gas cleaning technology.
  • the catalytic converters needed for subsequent cleaning of the exhaust gas are damaged by the sulphur that is currently included in the natural gas, with the result that they cease to function properly before the end of their specified service lives.
  • TAT tetrahydrothiophene
  • mercaptan sulphur tetrahydrothiophene
  • the sulphur content in natural gas must not fall below a prescribed fraction.
  • the absorber materials that are suitable for removing sulphur must usually be at an operating temperature from 40 to 80° C. These temperatures are generally assured by explosion-proof electric heaters allocated to the absorbers.
  • the object of the present invention is to suggest a species-related method for separating sulphur out of a gas that contains sulphur, particularly hydrogen or natural gas, which avoids the problems described above and particularly enables use of an additional heating device for the absorptive separating process to be dispensed with.
  • a species-related method for separating sulphur out of a gas that contains sulphur is suggested that is characterized in that the sulphur-containing gas is compressed, or at least precompressed, before it is introduced into the absorptive separation process.
  • the sulphur-containing gas is preferably compressed before its introduction into the absorptive separation process to at least such a degree that the compression heat generated thereby enables the absorber material or materials used in the absorptive separation process to be heated to the requisite temperature. As a consequence, it is no longer necessary to use additional heating devices for the absorptive separation process.
  • the FIGURE illustrates an absorption process A for the selective removal of sulphur.
  • a gas that contains sulphur is introduced into this process via line segments 1 , 2 and 3 .
  • this gas is natural gas drawn from the public natural gas supply network.
  • the sulphur-containing gas is compressed by a single- or two-stage compressor or a single- or multistage compressor unit V 1 such that the heat of compression generated by the process is sufficient to heat the absorber material or materials used in absorptive separation process A to the temperature required for the process. Additional heating devices for heating the absorber material or materials to the requisite temperature are not required.
  • the natural gas containing the sulphur is compressed in the compressor or compressor unit V 1 to a pressure between 10 and 30 bar, preferably between 15 and 25 bar.
  • Heat exchanger E which may be provided optionally, is used to cool the natural gas that has been compressed, and thus also heated in the compressor or compressor unit V 1 , to an optimal temperature for the purposes of selectivity of the absorber material or materials used in downstream absorptive separation process A.
  • absorptive separation process A includes an absorption column preferably having a capacity of 50 l.
  • a drying material is preferably provided in absorption column A as well. In general, this drying material may be located upstream and/or downstream from the absorption material that is used to separate the sulphur.
  • Bypass line 5 is preferably equipped with a control valve 6 and may be used for diverting a partial flow of the sulphur-containing (natural) gas around absorptive separation process A. In this way, it is possible to vary the quantity of gas that passes through absorptive separation process A. The degree of sulphur reduction in the gas that contains the sulphur may thus be regulated or varied according to requirements
  • absorptive separation process A may be modified in such manner that other, preferably undesirable components besides sulphur are removed from the sulphur-containing gas as well.
  • the cleaned gas then passes through line segments 4 and 7 to a second single- or multistage compressor or a second single- or multistage compressor unit V 2 , in either of which it may optionally be compressed to desired final pressure.
  • the compressed gas is then forwarded through line 8 for subsequent use, for example intermediate storage.
  • the method according to the invention for separating sulphur out of a gas that contains sulphur is able to be used for an extremely wide range of gases and gas mixtures in which at least some of the sulphur contained is to be removed by absorption.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Gas Separation By Absorption (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Separation Of Gases By Adsorption (AREA)
  • Industrial Gases (AREA)

Abstract

A method is described for separating sulphur out of a sulphur-containing gas, particularly hydrogen or natural gas, wherein the gas is compressed and the sulphur is removed in an absorptive separation process. According to the invention, the sulphur-containing gas is compressed, or at least precompressed before being passed into the absorptive separation process.

Description

    CROSS REFERENCE TO RELATED APPLICATION
  • This application claims priority from German Patent Application Serial No. DE 102008 031 509.5, filed Jul. 3, 2008.
    • BACKGROUND OF THE INVENTION
  • The invention relates to a method for separating sulphur out of a gas that contains sulphur, particularly hydrogen or natural gas, wherein the gas is compressed and the sulphur is removed via an absorptive separation process.
  • Species-related methods for separating sulphur from a gas containing sulphur are used for example at natural gas filling stations. At natural gas filling stations, the natural gas for use as fuel is drawn from the existing natural gas supply network, dried, and compressed to a storage pressure that may reach 300 bar. The sulphur content in the natural gas that is drawn from the supply network is usually too high to be processed effectively with today's engine and exhaust gas cleaning technology. In particular, the catalytic converters needed for subsequent cleaning of the exhaust gas are damaged by the sulphur that is currently included in the natural gas, with the result that they cease to function properly before the end of their specified service lives.
  • Because of legal provisions regarding odorising natural gas when it is used as fuel—tetrahydrothiophene (THT) and/or mercaptan sulphur are added to the natural gas for this purpose—the sulphur content in natural gas must not fall below a prescribed fraction.
  • For natural gas processing on a large, industrial scale, selective sulphur absorption processes have been in use for some time. The absorber materials that are suitable for removing sulphur must usually be at an operating temperature from 40 to 80° C. These temperatures are generally assured by explosion-proof electric heaters allocated to the absorbers.
    • BRIEF SUMMARY OF THE INVENTION
  • The object of the present invention is to suggest a species-related method for separating sulphur out of a gas that contains sulphur, particularly hydrogen or natural gas, which avoids the problems described above and particularly enables use of an additional heating device for the absorptive separating process to be dispensed with.
  • To solve this object, a species-related method for separating sulphur out of a gas that contains sulphur is suggested that is characterized in that the sulphur-containing gas is compressed, or at least precompressed, before it is introduced into the absorptive separation process.
  • In this context, the sulphur-containing gas is preferably compressed before its introduction into the absorptive separation process to at least such a degree that the compression heat generated thereby enables the absorber material or materials used in the absorptive separation process to be heated to the requisite temperature. As a consequence, it is no longer necessary to use additional heating devices for the absorptive separation process.
  • Further advantageous configurations of the method according to the invention for separating sulphur out of a gas that contains sulphur, which represent the objects of the subordinate claims, are characterized in that
      • the sulphur-containing gas that is introduced into the absorptive separation process is at a temperature between 20 and 200° C., preferably between 40 and 100° C.,
      • the gas that is extracted from the separation process undergoes postcompression,
      • at least a partial stream of the sulphur-containing gas is diverted around the absorptive separation process, the quantity of this partial stream preferably being variable,
      • the sulphur-containing gas that is introduced into the absorptive separation process is cooled after it has been (pre)compressed,
      • the absorptive separation process is designed such that besides sulphur at least one additional component is at least partially separated from the sulphur-containing gas, and
      • the gas from which sulphur has been removed is delivered to a vehicle for use as a power source and/or fuel.
    BRIEF DESCRIPTION OF THE DRAWINGS
  • In the following, the method according to the invention for separating sulphur out of a gas that contains sulphur as well as other configurations thereof will be explained in greater detail with reference to the embodiment shown in the FIGURE. The embodiment shown in the figure may be used in particular at natural gas filling stations that are provided for the purpose of filling vehicles of any kind with compressed natural gas.
    •  DETAILED DESCRIPTION OF THE INVENTION
  • The FIGURE illustrates an absorption process A for the selective removal of sulphur. A gas that contains sulphur is introduced into this process via line segments 1, 2 and 3. In the case of a natural gas filling station, this gas is natural gas drawn from the public natural gas supply network. The sulphur-containing gas is compressed by a single- or two-stage compressor or a single- or multistage compressor unit V1 such that the heat of compression generated by the process is sufficient to heat the absorber material or materials used in absorptive separation process A to the temperature required for the process. Additional heating devices for heating the absorber material or materials to the requisite temperature are not required.
  • In the case of a natural gas filling station, the natural gas containing the sulphur is compressed in the compressor or compressor unit V1 to a pressure between 10 and 30 bar, preferably between 15 and 25 bar.
  • Heat exchanger E, which may be provided optionally, is used to cool the natural gas that has been compressed, and thus also heated in the compressor or compressor unit V1, to an optimal temperature for the purposes of selectivity of the absorber material or materials used in downstream absorptive separation process A.
  • In practical terms, absorptive separation process A includes an absorption column preferably having a capacity of 50 l. Besides the absorption material that is used to selectively remove sulphur from the sulphur-containing gas, a drying material is preferably provided in absorption column A as well. In general, this drying material may be located upstream and/or downstream from the absorption material that is used to separate the sulphur.
  • Bypass line 5, represented by a dashed line, is preferably equipped with a control valve 6 and may be used for diverting a partial flow of the sulphur-containing (natural) gas around absorptive separation process A. In this way, it is possible to vary the quantity of gas that passes through absorptive separation process A. The degree of sulphur reduction in the gas that contains the sulphur may thus be regulated or varied according to requirements
  • If it is necessary and/or desired, absorptive separation process A may be modified in such manner that other, preferably undesirable components besides sulphur are removed from the sulphur-containing gas as well.
  • With its sulphur content reduced to the desired lower limit, the cleaned gas then passes through line segments 4 and 7 to a second single- or multistage compressor or a second single- or multistage compressor unit V2, in either of which it may optionally be compressed to desired final pressure. The compressed gas is then forwarded through line 8 for subsequent use, for example intermediate storage.
  • It should be noted in particular that the method according to the invention for separating sulphur out of a gas that contains sulphur is able to be used for an extremely wide range of gases and gas mixtures in which at least some of the sulphur contained is to be removed by absorption.

Claims (9)

1. A method for separating sulphur out of a gas that contains sulphur, particularly hydrogen or natural gas, wherein the gas is compressed and the sulphur is removed via an absorptive separation process, characterized in that the sulphur-containing gas is compressed, or at least precompressed before it is introduced into the absorptive separation process.
2. The method as recited in claim 1, characterized in that the sulphur-containing gas is compressed before its introduction into the absorptive separation process to at least such a degree that the compression heat generated thereby enables the absorber material or materials used in the absorptive separation process to be heated to the requisite temperature.
3. The method as recited in claim 1t characterized in that the sulphur-containing gas that is introduced into the absorptive separation process is at a temperature between 20 and 200° C.
4. The method as recited in claim 1, characterized in that the sulphur-containing gas that is introduced into the absorptive separation process is at a temperature preferably between 40 and 100° C.
5. The method as recited in claim 1, characterized in that the gas that is extracted from the absorptive separation process undergoes postcompression.
6. The method as recited in claim 1, characterized in that at least a partial stream of the sulphur-containing gas is diverted around the absorptive separation process, the quantity of this partial stream preferably being variable.
7. The method as recited in claim 1, characterized in that the sulphur-containing gas that is introduced into the absorptive separation process is cooled after it has been (pre)compressed.
8. The method as recited in claim 1, characterized in that the absorptive separation process is designed such that besides sulphur at least one additional component is at least partially separated from the sulphur-containing gas.
9. The method as recited in claim 1, characterized in that the gas from which sulphur has been removed is delivered to a vehicle for use as a power source and/or fuel.
US12/480,217 2008-07-03 2009-06-08 Method for separating sulphur out of a gas that contains sulphur Abandoned US20100000154A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008031509.5 2008-07-03
DE102008031509A DE102008031509A1 (en) 2008-07-03 2008-07-03 Process for separating sulfur from a sulfur-containing gas

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US (1) US20100000154A1 (en)
EP (1) EP2140925A1 (en)
JP (1) JP2010012464A (en)
KR (1) KR20100004864A (en)
CN (1) CN101618290A (en)
AR (1) AR072676A1 (en)
BR (1) BRPI0901989A2 (en)
CA (1) CA2670356A1 (en)
DE (1) DE102008031509A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8518356B2 (en) 2010-07-27 2013-08-27 Air Products And Chemicals, Inc. Method and apparatus for adjustably treating a sour gas
CN114046188A (en) * 2021-12-01 2022-02-15 重庆科技学院 Closed natural gas pipeline power generation and filtration device

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102010050435A1 (en) * 2010-11-04 2012-05-10 Linde Aktiengesellschaft Process and device for decomposing gas mixtures
KR20190021497A (en) * 2012-07-24 2019-03-05 누베라 퓨엘 셀스, 엘엘씨 Distributed hydrogen extraction system

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2490283A (en) * 1947-02-03 1949-12-06 Shell Dev Addition of carbonmonoxide-hydrogen to unsaturated compounds
US4589896A (en) * 1985-01-28 1986-05-20 Air Products And Chemicals, Inc. Process for separating CO2 and H2 S from hydrocarbons
US5256172A (en) * 1992-04-17 1993-10-26 Keefer Bowie Thermally coupled pressure swing adsorption
US5842357A (en) * 1995-01-11 1998-12-01 Acrion Technologies, Inc. Landfill gas recovery
US20050287056A1 (en) * 2004-06-29 2005-12-29 Dakota Gasification Company Removal of methyl mercaptan from gas streams
US20060150812A1 (en) * 2002-12-17 2006-07-13 John Mak Configurations and methods for acid gas and contaminant removal with near zero emission
US7699914B1 (en) * 2005-12-09 2010-04-20 Morrow Luke N Triple-effect absorption system for recovering methane gas
US7879135B2 (en) * 2005-04-20 2011-02-01 Fluor Technologies Corporation Configurations and methods for claus plant operation with variable sulfur content

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10356276A1 (en) * 2003-11-28 2005-06-30 Tentscher, Wolfgang, Dr. Method for recovery of carbon dioxide from biogas comprises compressing biogas and treating product with regenerated absorption stream so that carbon dioxide and trace materials are removed to enrich absorption stream
DE102005013276A1 (en) * 2005-02-11 2006-08-24 Linde Ag Process and apparatus for purifying gas streams

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2490283A (en) * 1947-02-03 1949-12-06 Shell Dev Addition of carbonmonoxide-hydrogen to unsaturated compounds
US4589896A (en) * 1985-01-28 1986-05-20 Air Products And Chemicals, Inc. Process for separating CO2 and H2 S from hydrocarbons
US5256172A (en) * 1992-04-17 1993-10-26 Keefer Bowie Thermally coupled pressure swing adsorption
US5842357A (en) * 1995-01-11 1998-12-01 Acrion Technologies, Inc. Landfill gas recovery
US20060150812A1 (en) * 2002-12-17 2006-07-13 John Mak Configurations and methods for acid gas and contaminant removal with near zero emission
US20050287056A1 (en) * 2004-06-29 2005-12-29 Dakota Gasification Company Removal of methyl mercaptan from gas streams
US7879135B2 (en) * 2005-04-20 2011-02-01 Fluor Technologies Corporation Configurations and methods for claus plant operation with variable sulfur content
US7699914B1 (en) * 2005-12-09 2010-04-20 Morrow Luke N Triple-effect absorption system for recovering methane gas

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8518356B2 (en) 2010-07-27 2013-08-27 Air Products And Chemicals, Inc. Method and apparatus for adjustably treating a sour gas
US9090839B2 (en) 2010-07-27 2015-07-28 Air Products And Chemicals, Inc. Method and apparatus for adjustably treating a sour gas
CN114046188A (en) * 2021-12-01 2022-02-15 重庆科技学院 Closed natural gas pipeline power generation and filtration device

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CN101618290A (en) 2010-01-06
CA2670356A1 (en) 2010-01-03
AR072676A1 (en) 2010-09-15
JP2010012464A (en) 2010-01-21
KR20100004864A (en) 2010-01-13
BRPI0901989A2 (en) 2010-05-18
EP2140925A1 (en) 2010-01-06
DE102008031509A1 (en) 2010-01-07

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Owner name: LINDE AKTIENGESELLSCHAFT, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ADLER, ROBERT;MAYER, MARKUS;KLEIN, EKKEHARDT;REEL/FRAME:022983/0293;SIGNING DATES FROM 20090616 TO 20090703

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