CA2287743A1 - Process for the production of synthesis gas - Google Patents

Process for the production of synthesis gas Download PDF

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Publication number
CA2287743A1
CA2287743A1 CA002287743A CA2287743A CA2287743A1 CA 2287743 A1 CA2287743 A1 CA 2287743A1 CA 002287743 A CA002287743 A CA 002287743A CA 2287743 A CA2287743 A CA 2287743A CA 2287743 A1 CA2287743 A1 CA 2287743A1
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Prior art keywords
reforming section
feeding
possibly
hydrocarbons
flow
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CA002287743A
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French (fr)
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CA2287743C (en
Inventor
Marco Badano
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Casale SA
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Ammonia Casale SA
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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
    • 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
    • C01B3/38—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 using catalysts
    • C01B3/382—Multi-step processes
    • 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
    • C01B3/025—Preparation or purification of gas mixtures for ammonia synthesis
    • 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
    • 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
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam 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
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
    • 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
    • C01B2203/0288—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step containing two CO-shift steps
    • 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
    • C01B2203/06—Integration with other chemical processes
    • 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
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/061—Methanol production
    • 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
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/068—Ammonia synthesis
    • 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
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0838—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
    • C01B2203/0844—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1005—Arrangement or shape of catalyst
    • C01B2203/1011—Packed bed of catalytic structures, e.g. particles, packing elements
    • 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
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
    • 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
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1247—Higher hydrocarbons
    • 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
    • C01B2203/141—At least two reforming, decomposition or partial oxidation steps in parallel
    • 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
    • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
    • 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
    • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
    • C01B2203/143—Three or more reforming, decomposition or partial oxidation steps in series
    • 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
    • C01B2203/146—At least two purification steps in series
    • 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
    • C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C01B2203/82—Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus

Abstract

A process for the production of synthesis gas for obtaining compounds such as ammonia or methanol, in which hydrocarbons and steam are reacted first in a primary reforming section (11) and then - together with oxygen - in a secondary reforming section (12), thus obtaining CO, CO2, H2 and possibly N2 which are then fed to a carbon monoxide conversion section (13, 14), is distinguished by the fact of reacting hydrocarbons, steam and oxygen in an autothermal reforming section (20) provided in parallel with respect to other reforming sections (11, 12), and feeding the so produced CO, CO2, H2 and possibly N2 to the carbon monoxide conversion section (13, 14).

Claims (10)

1. Process for the production of synthesis gas for obtaining compounds such as ammonia or methanol, comprising the steps of:
- feeding a first flow comprising hydrocarbons and a first gas flow comprising steam to a primary reforming section;
- feeding a first gas flow comprising oxygen and possibly nitrogen to a secondary reforming section;
- reacting said hydrocarbons and said steam first in the primary reforming section and then - together with said oxygen - in the secondary reforming section, obtaining a first gas phase comprising CO, CO2, H2 and possibly N2;
- feeding said first gas phase comprising CO, CO2, H2 and possibly N2 to a carbon monoxide conversion section;
characterised in that it further comprises the steps of:
- feeding a second flow comprising hydrocarbons, a second gas flow comprising steam and a second gas flow comprising oxygen and possibly nitrogen to an autothermal reforming section arranged in parallel with respect to said primary and secondary reforming sections;
- reacting said hydrocarbons, said steam and said oxygen in said autothermal reforming section, obtaining a second gas phase comprising CO, CO2, H2 and possibly N2;
- feeding said second gas phase comprising CO, CO2, H2 and possibly N2 to said carbon monoxide conversion section.
2. Process according to claim 1, characterised in that said second gas flow comprising oxygen comprises oxygen enriched air.
3. Process according to claim 1, characterised in that it further comprises the step of subjecting at least a part of said second gas flow comprising hydrocarbons and said second gas flow comprising steam to a pre-reforming treatment before being fed to said autothermal reforming section.
4. Process according to claim 1, characterised in that it further comprises the step of feeding a portion of said first flow comprising hydrocarbons to said autothermal reforming section.
5. Plant for producing synthesis gas for obtaining compounds such as ammonia or methanol, comprising:
- a primary reforming section (11) and secondary reforming section (12) arranged in series for obtaining a first gas phase comprising CO, CO2, H2 and possibly N2;
- respective means (1, 2) for feeding a first flow comprising hydrocarbons and a first gas flow comprising steam to said primary reforming section (11);
- means (3) for feeding a first gas flow comprising oxygen and possibly nitrogen to said secondary reforming section (12);
- means (1) for feeding said first gas phase comprising CO, CO2, H2 and possibly N2 to a carbon monoxide conversion section (13, 14);
characterised in that it comprises:
- an autothermal reforming section (20) for obtaining a second gas phase comprising CO, CO2, H2 and possibly N2;
- respective means (5-7) for feeding a second flow comprising hydrocarbons, a second gas flow comprising steam and a second gas flow comprising oxygen and possibly nitrogen to said autothermal reforming section (20);

- means (5) for feeding said second gas phase comprising CO, CO2, H2 and possibly N2 to said carbon monoxide conversion section (13, 14).
6. Plant according to the claim 5, characterised in that it further comprises:
- a pre-reforming section (19);
- means (5) for feeding at least a part of said second gas flow comprising hydrocarbons and said second gas flow comprising steam to said pre-reforming section (19);
- means (5) for connecting said pre-reforming section (19) with said autothermal reforming section (20).
7. Plant according to claim 5, characterised in that it further comprises means (8) for feeding a portion of said first flow comprising hydrocarbons to said autothermal reforming section (20).
8. Method of retrofitting a plant for the production of synthesis gas for obtaining compounds such as ammonia or methanol, of the type comprising a primary reforming section (11) and a secondary reforming section (12) provided in series for obtaining a first gas phase comprising CO, CO2, H2 and possibly N2, respective means (1, 2) for feeding a first flow comprising hydrocarbons and a first gas flow comprising steam to said primary reforming section (11), means (3) for feeding a first gas flow comprising oxygen and possibly nitrogen to said secondary reforming section (12), means (1) for feeding said first gas phase comprising CO, CO2, H2 and possibly N2 to a carbon monoxide conversion section (13, 14), said method comprising the steps of:
- providing an autothermal reforming section (20) for obtaining a second gas phase comprising CO, CO2, H2 and possibly N2;

- providing respective means (5-7) for feeding a second flow comprising hydrocarbons, a second gas flow comprising steam and a second gas flow comprising oxygen and possibly nitrogen to said autothermal reforming section (20);
- providing means (5) for feeding said second gas phase comprising CO, CO2, H2 and possibly N2 to said carbon monoxide conversion section (13, 14).
9. Method according to claim 8, characterised in that it further comprises the steps of:
- providing a pre-reforming section (19);
- providing means (5) for feeding at least a part of said second flow comprising hydrocarbons and said second gas flow comprising steam to said pre-reforming section (19);
- providing means (5) for connecting said pre-reforming section (19) with said autothermal reforming section (20).
10. Method according to claim 8, characterised in that it further comprises the steps of:
- providing means (8) for feeding a portion of said first flow comprising hydrocarbons, and possibly a portion of said first gas flow comprising steam, to said autothermal reforming section (20).
CA2287743A 1998-11-03 1999-10-29 Process for the production of synthesis gas Expired - Lifetime CA2287743C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP98203695.6 1998-11-03
EP98203695A EP0999178B1 (en) 1998-11-03 1998-11-03 Process for the production of synthesis gas

Publications (2)

Publication Number Publication Date
CA2287743A1 true CA2287743A1 (en) 2000-05-03
CA2287743C CA2287743C (en) 2010-05-25

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Family Applications (1)

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CA2287743A Expired - Lifetime CA2287743C (en) 1998-11-03 1999-10-29 Process for the production of synthesis gas

Country Status (9)

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US (2) US6207078B1 (en)
EP (1) EP0999178B1 (en)
CN (1) CN1166555C (en)
AU (1) AU5713099A (en)
BR (1) BR9917439A (en)
CA (1) CA2287743C (en)
DE (1) DE69835357T2 (en)
ID (1) ID25973A (en)
SA (1) SA00200870B1 (en)

Families Citing this family (29)

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EP1188713A3 (en) 2000-09-18 2003-06-25 Haldor Topsoe A/S Production of hydrogen and carbon monoxide containing synthesis gas by partial oxidation
DE10055818A1 (en) 2000-11-10 2002-05-23 Ammonia Casale Sa Catalytic production of ammonia, especially for direct conversion into urea, using nitrogen-hydrogen starting gas mixture obtained from natural gas by autothermal reforming and catalytic conversion
EP1219566A1 (en) 2000-12-27 2002-07-03 L'air Liquide, S.A. à Directoire et Conseil de Surveillance pour l'Etude et l'Exploitation des Procédés Georges Claude Integrated process and installation for the production of synthesis gas
DE10226210A1 (en) * 2002-06-13 2004-01-08 Lurgi Ag Plant part for the disassembly and cleaning of synthesis gas
DE10226209B4 (en) * 2002-06-13 2008-04-03 Lurgi Ag Plant and process for the production and decomposition of synthesis gases from natural gas
US8293186B2 (en) * 2004-07-29 2012-10-23 Gas Technologies Llc Method and apparatus for producing methanol
US9180426B2 (en) * 2004-07-29 2015-11-10 Gas Technologies, Llc Scrubber for methanol production system
US7910787B2 (en) 2004-07-29 2011-03-22 Gas Technologies Llc Method and system for methanol production
US7642293B2 (en) * 2004-07-29 2010-01-05 Gas Technologies Llc Method and apparatus for producing methanol with hydrocarbon recycling
US8202916B2 (en) 2004-07-29 2012-06-19 Gas Technologies Llc Method of and apparatus for producing methanol
US7578981B2 (en) * 2004-07-29 2009-08-25 Gas Technologies Llc System for direct-oxygenation of alkane gases
WO2006117499A1 (en) * 2005-05-03 2006-11-09 Quartey-Papafio Alexander H Synthesis gas production process
US7687669B2 (en) 2005-12-27 2010-03-30 Gas Technologies Llc Method for direct-oxygenation of alkane gases
US7879296B2 (en) 2005-12-27 2011-02-01 Gas Technologies Llc Tandem reactor system having an injectively-mixed backmixing reaction chamber, tubular-reactor, and axially movable interface
US20080040975A1 (en) * 2006-08-21 2008-02-21 Albert Calderon Method for maximizing the value of carbonaceous material
EP1985580A1 (en) * 2007-04-27 2008-10-29 Methanol Casale S.A. Process for producing methanol synthesis gas
BRPI0804120A2 (en) * 2008-09-09 2010-07-06 Petroleo Brasileiro Sa method for the production of ethylene and synthesis gas in circulating fluidized bed
EP2199253A1 (en) * 2008-12-18 2010-06-23 Ammonia Casale S.A. Process and equipment for the production of ammonia make-up syngas with an air separation unit as nitrogen source
US20110085967A1 (en) * 2009-10-14 2011-04-14 Troy Michael Raybold Hydrogen product method and apparatus
WO2013013895A1 (en) * 2011-07-25 2013-01-31 Haldor Topsøe A/S Process for production of synthesis gas
EA027871B1 (en) * 2011-12-19 2017-09-29 Стамикарбон Б.В. Эктин Андер Те Нейм Оф Мт Инновейшн Сентр Process for producing ammonia and urea
CN103303866A (en) * 2012-03-15 2013-09-18 上海汉兴能源科技有限公司 Method for producing hydrogen or/and hydrogen-carbon monoxide synthesis gas by converting light dydrocarbon raw material
PL2805914T3 (en) * 2013-05-23 2018-02-28 Haldor Topsøe A/S A process for co-production of ammonia, urea and methanol
DE102014209635A1 (en) 2014-05-21 2015-11-26 Thyssenkrupp Ag Synthesis of synthesis gas with two autothermal reformers
DE102017204208A1 (en) * 2017-03-14 2018-09-20 Thyssenkrupp Ag Process and plant for the production and preparation of a synthesis gas mixture
IL271938B2 (en) 2017-07-25 2024-04-01 Haldor Topsoe As Method for the preparation of synthesis gas
PL3658491T3 (en) 2017-07-25 2024-02-05 Topsoe A/S Method for the preparation of ammonia synthesis gas
US11820657B2 (en) 2021-10-06 2023-11-21 Saudi Arabian Oil Company Combined hydrogen and electricity production from aqueous ammonia feed
US11617981B1 (en) 2022-01-03 2023-04-04 Saudi Arabian Oil Company Method for capturing CO2 with assisted vapor compression

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Also Published As

Publication number Publication date
SA00200870B1 (en) 2006-09-09
BR9917439A (en) 2003-04-01
DE69835357D1 (en) 2006-09-07
EP0999178B1 (en) 2006-07-26
ID25973A (en) 2000-11-16
CA2287743C (en) 2010-05-25
EP0999178A1 (en) 2000-05-10
US20010006615A1 (en) 2001-07-05
US6207078B1 (en) 2001-03-27
CN1166555C (en) 2004-09-15
AU5713099A (en) 2000-05-04
CN1253114A (en) 2000-05-17
DE69835357T2 (en) 2007-08-23

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