GB2168719A - Producing synthesis gas - Google Patents

Producing synthesis gas Download PDF

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Publication number
GB2168719A
GB2168719A GB08427289A GB8427289A GB2168719A GB 2168719 A GB2168719 A GB 2168719A GB 08427289 A GB08427289 A GB 08427289A GB 8427289 A GB8427289 A GB 8427289A GB 2168719 A GB2168719 A GB 2168719A
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United Kingdom
Prior art keywords
gas
effluent
carbon dioxide
hydrogen
unit
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.)
Granted
Application number
GB08427289A
Other versions
GB2168719B (en
GB8427289D0 (en
Inventor
Anthony Horton
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Humphreys and Glasgow Ltd
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Humphreys and Glasgow Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Humphreys and Glasgow Ltd filed Critical Humphreys and Glasgow Ltd
Priority to GB08427289A priority Critical patent/GB2168719B/en
Publication of GB8427289D0 publication Critical patent/GB8427289D0/en
Publication of GB2168719A publication Critical patent/GB2168719A/en
Application granted granted Critical
Publication of GB2168719B publication Critical patent/GB2168719B/en
Expired legal-status Critical Current

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Classifications

    • 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
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/48—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
    • 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
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • 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
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/148—Details of the flowsheet involving a recycle stream to the feed of the process for making hydrogen or synthesis gas

Abstract

A feed hydrocarbon, e.g. gas leaving a Fischer Tropsch synthesis reactor containing carbon monoxide, is mixed with recycled CO2, passed to a CO2 removal unit where a calculated amount of CO2 is removed and the effluent is then passed to a reformer to produce synthesis gas, tail gas from the reformer is passed through a CO shift catalyst and the effluent therefrom is combined with the feed hydrocarbon. Proper operation of the shift converter allows control over the carbon oxides/hydrogen ratio in to the systhesis reactor.

Description

SPECIFICATION A process to produce a desired synthesis gas composition There are in the world many cheap sources of hydrocarbons such as flared natural gas and also othercheap sources of carbon-containing fuels. This process utilises these to produce a synthesis gas, that is a gas containing an oxide or oxides of carbon and hydrogen which gas is often used for, e.g. the production of synthetic crude utilising Fischer Tropsch technology, methanol, OXO alcohols. The invention is described by way of the Fischer-Tropsch synthesis gas but the invention may be applied to othertechnology wherein a tail gas which mav be recycled is produced.
Taking; as typical hydrocarbon, natural gas, art a suitable pressure, this is combined with a recycle stream containing carbon dioxide and passed to a carbon dioxide removal unit which removes a carefully calculated portion of the carbon dioxide, and sulphur compounds such as H2S. The gases from which some of the carbon dioxide has been removed may be compressed and pre-heated and may pass through a guard desulphurisation unit and is then passed to either a tubular steam reformer or, preferably, a partial oxidation unit, in which the said gas is reacted with an oxygen-containing gas at high temperature. The effluent from the reforming device may be cooled and is then fed to the synthesis gas utilisation device such as Fischer-Tropsch synthesis (FTS) reactor.As part of the FTS unit operation a tail gas containing carbon monoxide arises and this tail gas, possibly after pre-heating, may be combined with some steam and passed through a carbon monoxide water gas shift reactor (shift reactor) of carefully designed performance, which reactor may also be equipped with a by-pass so as better two control the amount of carbon monoxide shifted. The effluent from the shift reactor is recycled upstream ofthe carbon dioxide removal unit.
By carefully controiling the amount of carbon monoxide shift and the amount of carbon dioxide removed, the carbon/hydrogen balance in the effluent from the reformer is controlled.
Shouldthefeed gas contain inertgassuch as nitrogen, it may be necessarytotakea purge stream offthetail gas in orderto prevent a build up of inert gas in the system.
If there is a requirement for hydrogen ora high hydrogen containing gas, then the amount of carbon monoxide shifted and carbon dioxide removed, may be altered so as to give extra hydrogen in the reforming device effluent which may be removed by means such as a permeable membrane unit or a pressure swing adsorption or cryogenic unit.
In the case of tail gas arising from an FTS unit such tail gas may well contain olefins which, in the case of the reforming device being a partial oxidation unit, do not have to be separately hydrogenated as would be the case if the reforming device is a tubular steam reformer.
Thus by means of th is invention synthesis gas of a desired composition may easily be obtained without necessarily further processing the effluent from the reforming device unless such further processing takes the form of removing hydrogen for which there is a specific application as opposed to having to remove hydrogen in orderto alterthe hydrogen: carbon ratio tothedesired level.
In this application there is provided an invention characterised by: A. the addition of a carbon dioxide containing stream to a feed hydrocarbon B. passing the mixture to a carbon dioxide removal unit C. passing the effluent from B. into a reforming device D. passing the effluent from the reforming device into synthesis gas utilisation unit E. passingthetail gas arising from D.through a carbon monoxide shift catalyst in a controlled way F. combining the effluent from E with the feed as in A.
1. A process for the production of a synthesis gas containing carbon monoxide and hydrogen of a desired ratio which is characterised by: A. the addition of a carbon dioxide containing stream to a feed hydrocarbon B. passing the mixture to a carbon dioxide removal unit C. passing the effluent from B. into a reforming device D. passing the effluent from the reforming device into a synthesis gas utilisation unit E. passing the tail gas arising from D. through a carbon monoxide shift catalyst in a controlled way F. combining the effluent from Ewith the feed as in A.
2. A process as claimed in claim 1 whereinthe amount of carbon monoxide shift and carbon dioxide recovery are adjusted so as to produce an excess of hydrogen which excess is removed from the effluent from the reforming device so asto leave synthesis gas ofthe desired composition and give the desired quantity of hydrogen.
**WARNING** end of DESC field may overlap start of CLMS **.

Claims (2)

**WARNING** start of CLMS field may overlap end of DESC **. SPECIFICATION A process to produce a desired synthesis gas composition There are in the world many cheap sources of hydrocarbons such as flared natural gas and also othercheap sources of carbon-containing fuels. This process utilises these to produce a synthesis gas, that is a gas containing an oxide or oxides of carbon and hydrogen which gas is often used for, e.g. the production of synthetic crude utilising Fischer Tropsch technology, methanol, OXO alcohols. The invention is described by way of the Fischer-Tropsch synthesis gas but the invention may be applied to othertechnology wherein a tail gas which mav be recycled is produced. Taking; as typical hydrocarbon, natural gas, art a suitable pressure, this is combined with a recycle stream containing carbon dioxide and passed to a carbon dioxide removal unit which removes a carefully calculated portion of the carbon dioxide, and sulphur compounds such as H2S. The gases from which some of the carbon dioxide has been removed may be compressed and pre-heated and may pass through a guard desulphurisation unit and is then passed to either a tubular steam reformer or, preferably, a partial oxidation unit, in which the said gas is reacted with an oxygen-containing gas at high temperature. The effluent from the reforming device may be cooled and is then fed to the synthesis gas utilisation device such as Fischer-Tropsch synthesis (FTS) reactor.As part of the FTS unit operation a tail gas containing carbon monoxide arises and this tail gas, possibly after pre-heating, may be combined with some steam and passed through a carbon monoxide water gas shift reactor (shift reactor) of carefully designed performance, which reactor may also be equipped with a by-pass so as better two control the amount of carbon monoxide shifted. The effluent from the shift reactor is recycled upstream ofthe carbon dioxide removal unit. By carefully controiling the amount of carbon monoxide shift and the amount of carbon dioxide removed, the carbon/hydrogen balance in the effluent from the reformer is controlled. Shouldthefeed gas contain inertgassuch as nitrogen, it may be necessarytotakea purge stream offthetail gas in orderto prevent a build up of inert gas in the system. If there is a requirement for hydrogen ora high hydrogen containing gas, then the amount of carbon monoxide shifted and carbon dioxide removed, may be altered so as to give extra hydrogen in the reforming device effluent which may be removed by means such as a permeable membrane unit or a pressure swing adsorption or cryogenic unit. In the case of tail gas arising from an FTS unit such tail gas may well contain olefins which, in the case of the reforming device being a partial oxidation unit, do not have to be separately hydrogenated as would be the case if the reforming device is a tubular steam reformer. Thus by means of th is invention synthesis gas of a desired composition may easily be obtained without necessarily further processing the effluent from the reforming device unless such further processing takes the form of removing hydrogen for which there is a specific application as opposed to having to remove hydrogen in orderto alterthe hydrogen: carbon ratio tothedesired level. In this application there is provided an invention characterised by: A. the addition of a carbon dioxide containing stream to a feed hydrocarbon B. passing the mixture to a carbon dioxide removal unit C. passing the effluent from B. into a reforming device D. passing the effluent from the reforming device into synthesis gas utilisation unit E. passingthetail gas arising from D.through a carbon monoxide shift catalyst in a controlled way F. combining the effluent from E with the feed as in A. CLAIMS
1. A process for the production of a synthesis gas containing carbon monoxide and hydrogen of a desired ratio which is characterised by: A. the addition of a carbon dioxide containing stream to a feed hydrocarbon B. passing the mixture to a carbon dioxide removal unit C. passing the effluent from B. into a reforming device D. passing the effluent from the reforming device into a synthesis gas utilisation unit E. passing the tail gas arising from D. through a carbon monoxide shift catalyst in a controlled way F. combining the effluent from Ewith the feed as in A.
2. A process as claimed in claim 1 whereinthe amount of carbon monoxide shift and carbon dioxide recovery are adjusted so as to produce an excess of hydrogen which excess is removed from the effluent from the reforming device so asto leave synthesis gas ofthe desired composition and give the desired quantity of hydrogen.
GB08427289A 1984-10-29 1984-10-29 A process to produce and utilize a synthesis gas of a controlled carbon monoxide hydrogen ratio Expired GB2168719B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
GB08427289A GB2168719B (en) 1984-10-29 1984-10-29 A process to produce and utilize a synthesis gas of a controlled carbon monoxide hydrogen ratio

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB08427289A GB2168719B (en) 1984-10-29 1984-10-29 A process to produce and utilize a synthesis gas of a controlled carbon monoxide hydrogen ratio

Publications (3)

Publication Number Publication Date
GB8427289D0 GB8427289D0 (en) 1984-12-05
GB2168719A true GB2168719A (en) 1986-06-25
GB2168719B GB2168719B (en) 1988-10-19

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Family Applications (1)

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GB08427289A Expired GB2168719B (en) 1984-10-29 1984-10-29 A process to produce and utilize a synthesis gas of a controlled carbon monoxide hydrogen ratio

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997011904A1 (en) * 1995-09-25 1997-04-03 Eastman Chemical Company Production of hydrogen and carbon monoxide
US6521143B1 (en) 2000-04-13 2003-02-18 Air Products And Chemicals, Inc. Co-production of carbon monoxide-rich syngas wth high purity hydrogen
WO2003016250A1 (en) * 2001-08-17 2003-02-27 Johnson Matthey Plc Production of hydrocarbons
WO2006056594A1 (en) * 2004-11-26 2006-06-01 Shell Internationale Research Maatschappij B.V. Method for treatment of a gas
WO2006134471A2 (en) * 2005-06-14 2006-12-21 Sasol Technology (Proprietary) Limited Process for the preparation and conversion of synthesis gas
WO2007069197A2 (en) * 2005-12-15 2007-06-21 Sasol Technology (Proprietary) Limited Production of hydrocarbons from natural gas
EP1860063A1 (en) * 2006-05-22 2007-11-28 Shell Internationale Researchmaatschappij B.V. Process for preparing a paraffin product
EP1935845A1 (en) * 2006-12-22 2008-06-25 Shell Internationale Researchmaatschappij B.V. Process for producing hydrocarbons from a hydrocarbonaceous feedstock
WO2014102288A1 (en) * 2012-12-28 2014-07-03 Shell Internationale Research Maatschappij B.V. Process for preparing a paraffin product

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB978256A (en) * 1962-07-19 1964-12-23 Koppers Gmbh Heinrich Process for the continuous cracking of gasoline hydrocarbons
GB1302135A (en) * 1968-03-29 1973-01-04
GB1391034A (en) * 1973-02-05 1975-04-16 Metallgesellschaft Ag Process for the manufacture of a gas interchangeable with natural gas
GB1522994A (en) * 1975-09-18 1978-08-31 British Gas Corp Shift conversion processes
GB1544245A (en) * 1976-05-21 1979-04-19 British Gas Corp Production of substitute natural gas

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB978256A (en) * 1962-07-19 1964-12-23 Koppers Gmbh Heinrich Process for the continuous cracking of gasoline hydrocarbons
GB1302135A (en) * 1968-03-29 1973-01-04
GB1391034A (en) * 1973-02-05 1975-04-16 Metallgesellschaft Ag Process for the manufacture of a gas interchangeable with natural gas
GB1522994A (en) * 1975-09-18 1978-08-31 British Gas Corp Shift conversion processes
GB1544245A (en) * 1976-05-21 1979-04-19 British Gas Corp Production of substitute natural gas

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997011904A1 (en) * 1995-09-25 1997-04-03 Eastman Chemical Company Production of hydrogen and carbon monoxide
US6521143B1 (en) 2000-04-13 2003-02-18 Air Products And Chemicals, Inc. Co-production of carbon monoxide-rich syngas wth high purity hydrogen
WO2003016250A1 (en) * 2001-08-17 2003-02-27 Johnson Matthey Plc Production of hydrocarbons
AU2005308772B2 (en) * 2004-11-26 2009-03-26 Shell Internationale Research Maatschappij B.V. Method for treatment of a gas
WO2006056594A1 (en) * 2004-11-26 2006-06-01 Shell Internationale Research Maatschappij B.V. Method for treatment of a gas
US7812060B2 (en) 2004-11-26 2010-10-12 Shell Oil Company Method for treatment of a gas
WO2006134471A2 (en) * 2005-06-14 2006-12-21 Sasol Technology (Proprietary) Limited Process for the preparation and conversion of synthesis gas
WO2006134471A3 (en) * 2005-06-14 2007-08-23 Sasol Tech Pty Ltd Process for the preparation and conversion of synthesis gas
CN101273112B (en) * 2005-06-14 2013-02-13 沙索技术有限公司 Process for the preparation and conversion of synthesis gas
US8106102B2 (en) 2005-06-14 2012-01-31 Sasol Technology (Proprietary) Limited Process for the preparation and conversion of synthesis gas
GB2442646A (en) * 2005-06-14 2008-04-09 Sasol Tech Pty Ltd Process for the preparation and conversion of synthesis gas
WO2007069197A2 (en) * 2005-12-15 2007-06-21 Sasol Technology (Proprietary) Limited Production of hydrocarbons from natural gas
GB2446755A (en) * 2005-12-15 2008-08-20 Sasol Technology Production of hydrocarbons from natural gas
US7879919B2 (en) 2005-12-15 2011-02-01 Sasol Technology (Proprietary) Limited Production of hydrocarbons from natural gas
WO2007069197A3 (en) * 2005-12-15 2007-11-15 Sasol Tech Pty Ltd Production of hydrocarbons from natural gas
EP1860063A1 (en) * 2006-05-22 2007-11-28 Shell Internationale Researchmaatschappij B.V. Process for preparing a paraffin product
EP1935845A1 (en) * 2006-12-22 2008-06-25 Shell Internationale Researchmaatschappij B.V. Process for producing hydrocarbons from a hydrocarbonaceous feedstock
WO2014102288A1 (en) * 2012-12-28 2014-07-03 Shell Internationale Research Maatschappij B.V. Process for preparing a paraffin product
US9528049B2 (en) 2012-12-28 2016-12-27 Shell Oil Company Process for preparing a paraffin product
EA030387B1 (en) * 2012-12-28 2018-07-31 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Process for preparing a paraffin product

Also Published As

Publication number Publication date
GB2168719B (en) 1988-10-19
GB8427289D0 (en) 1984-12-05

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Legal Events

Date Code Title Description
732E Amendments to the register in respect of changes of name or changes affecting rights (sect. 32/1977)
732E Amendments to the register in respect of changes of name or changes affecting rights (sect. 32/1977)
PCNP Patent ceased through non-payment of renewal fee

Effective date: 19931029