WO2020148378A1 - Procédé de préparation de gaz de synthèse de méthanol - Google Patents

Procédé de préparation de gaz de synthèse de méthanol Download PDF

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Publication number
WO2020148378A1
WO2020148378A1 PCT/EP2020/051014 EP2020051014W WO2020148378A1 WO 2020148378 A1 WO2020148378 A1 WO 2020148378A1 EP 2020051014 W EP2020051014 W EP 2020051014W WO 2020148378 A1 WO2020148378 A1 WO 2020148378A1
Authority
WO
WIPO (PCT)
Prior art keywords
stream
synthesis gas
steam
added
reforming
Prior art date
Application number
PCT/EP2020/051014
Other languages
English (en)
Inventor
Per Juul Dahl
Thomas Rostrup-Nielsen
Original Assignee
Haldor Topsøe A/S
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 Haldor Topsøe A/S filed Critical Haldor Topsøe A/S
Priority to AU2020208917A priority Critical patent/AU2020208917A1/en
Priority to CN202080009622.4A priority patent/CN113677653A/zh
Publication of WO2020148378A1 publication Critical patent/WO2020148378A1/fr

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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
    • C01B3/38—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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/1516—Multisteps
    • C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for 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
    • C01B2203/02—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
    • C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide 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
    • C01B2203/06—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
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1258—Pre-treatment of the feed
    • 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
    • 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
    • Y02P20/141—Feedstock

Definitions

  • the present application is directed to the preparation of methanol synthesis gas. More particular, the invention uti lizes carbon dioxide introduced together with a hydrocarbon feed stream into a two-step reforming stage.
  • Production of synthesis gas e.g. for the methanol synthesis with natural gas feed is typically carried out by steam re forming or a combination of steam reforming and oxygen re forming .
  • the product gas from 2-step reforming comprises hydrogen, carbon monoxide, and carbon dioxide as well as other compo nents usually including methane and steam.
  • this invention provides in one aspect a method for the preparation of methanol synthesis gas comprising the steps of
  • methanol synthesis gas used hereinbefore and in the following description and claims shall be understood as any gas that can be used for methanol synthesis, e.g. make up gas or unconverted methanol synthesis recycled to a methanol reactor in a methanol loop.
  • the first and a part or all of second feed stream are mixed upstream the steam reforming step in step (d) .
  • the third stream comprising hydrogen is provided by one or more of:
  • a further stream comprising carbon diox ide is added in (a) to the stream comprising hydrocarbon upstream the steam reforming.
  • a further stream comprising carbon dioxide is added to the third stream comprising hydrogen.
  • the second feed stream comprising carbon dioxide is added to the first feed stream prior to the steam reforming step or to the feed stream leaving the re forming step in step (d) .
  • a further stream comprising carbon diox ide is added to the third stream comprising hydrogen.
  • the first synthesis gas has a module M of ⁇ 2.3, preferably 1.4 ⁇ M ⁇ 2.15, where M is (H2-CO2) / (CO+CO2) .
  • the module M in the third stream comprising hydrogen is larger than the module M in the first synthesis gas. In an embodiment of the invention, the module M of the third stream comprising hydrogen is > 1.9, preferably >
  • a mixture of the first synthesis gas stream and the third stream with optional CO2 added has a module M of between 1.8 and 2.3.
  • the carbon dioxide in the second feed stream or the further stream comprising carbon dioxide added to the third feed stream is obtained from flue or off-gas.
  • the steam reforming pro cess is performed in a tubular reformer, a bayonet tube re former or a convective reformer.
  • the first synthesis gas stream and the third stream with optional added CO2 is in a further step converted to a methanol product.
  • a suitable reforming catalyst composition for use in the steam reforming depends on the amount of carbon dioxide added to the feed and the type of reformer used in the steam reforming. In most cases, a nickel catalyst is suffi cient, but for high carbon dioxide contents in the feed, noble metal catalysts may be required for some types of steam reformers.
  • the carbon dioxide for use in the method according to the invention can advantageously be obtained from flue or off- gasses, such as e.g. flue gas stemming from the burners in the steam reformers.
  • the feed composition it might be preferred to desulfurize and prereform the first feed upstream the two- step reforming and/or the second feed upstream the steam reforming .
  • An advantage of the method according to the invention is i.a. a reduced energy consumption and a reduced CO2 foot print .
  • An additional advantage is that the method of the invention allows to generate a more reactive synthesis gas for metha nol production than the typical gas generated by two step reforming having a module close to 2.
  • the higher reactivity makes the methanol synthesis reaction proceed faster and thus less reactor volume and catalyst is needed.
  • the invention is addi tional useful in increasing production capacity of existing methanol plants based on two step reforming in the produc tion of methanol synthesis gas. Taking advantage of the possibility of generating a more reactive gas with the in ventions opens for the possibility of being able to in crease methanol production without having to add additional methanol synthesis reactor volume and catalyst or at least only a smaller volume than without the invention.
  • a further aspect of the invention is a method for revamping an existing methanol synthesis gas plant, comprising adding a steam reformer section and/or an electrolysis unit and/or a pipeline connected to an external hydrogen source in parallel to an existing two-step reforming section;
  • the two outlet lines can be combined before the connection or can be connected separately.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de préparation de gaz de synthèse de méthanol comprenant les étapes consistant à : (a) fournir un premier flux d'alimentation comprenant un hydrocarbure et de la vapeur ; (b) fournir un second flux d'alimentation comprenant du dioxyde de carbone en quantité pour arriver à un rapport dioxyde de carbone/hydrocarbure compris entre 0,1 et 0,8, de préférence entre 0,15 et 0,7 si le second flux d'alimentation est mélangé au premier flux ; (d) introduire le premier et le second flux dans un étage de reformage à la vapeur en deux étapes comprenant une étape de reformage à la vapeur et une étape de reformage auto-thermique ; (e) retirer un premier flux de gaz de synthèse ; (f) fournir un troisième flux d'alimentation comprenant de l'hydrogène ; et (g) utiliser le premier flux de gaz de synthèse et le troisième flux d'alimentation en tant que gaz de synthèse de méthanol.L'invention concerne en outre un procédé de perfectionnement d'une installation de gaz de synthèse de méthanol existante appropriée pour mettre en œuvre le procédé de préparation de gaz de synthèse de méthanol selon un premier aspect de l'invention.
PCT/EP2020/051014 2019-01-18 2020-01-16 Procédé de préparation de gaz de synthèse de méthanol WO2020148378A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU2020208917A AU2020208917A1 (en) 2019-01-18 2020-01-16 Method for the preparation of methanol synthesis gas
CN202080009622.4A CN113677653A (zh) 2019-01-18 2020-01-16 制备甲醇合成气的方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DKPA201900073 2019-01-18
DKPA201900073 2019-01-18

Publications (1)

Publication Number Publication Date
WO2020148378A1 true WO2020148378A1 (fr) 2020-07-23

Family

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Family Applications (2)

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PCT/EP2020/051014 WO2020148378A1 (fr) 2019-01-18 2020-01-16 Procédé de préparation de gaz de synthèse de méthanol
PCT/EP2020/051011 WO2020148376A1 (fr) 2019-01-18 2020-01-16 Procédé de préparation de gaz de synthèse de méthanol

Family Applications After (1)

Application Number Title Priority Date Filing Date
PCT/EP2020/051011 WO2020148376A1 (fr) 2019-01-18 2020-01-16 Procédé de préparation de gaz de synthèse de méthanol

Country Status (4)

Country Link
CN (2) CN113329969A (fr)
AR (2) AR117827A1 (fr)
AU (2) AU2020208917A1 (fr)
WO (2) WO2020148378A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022155425A1 (fr) * 2021-01-14 2022-07-21 Bd Energy Systems, Llc Procédé de production de méthanol à faible émission de co2 et dispositif de production

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000009441A2 (fr) * 1998-08-13 2000-02-24 Imperial Chemical Industries Plc Reformage a la vapeur
US20090012332A1 (en) * 2001-10-01 2009-01-08 Technology Convergence Inc. Methanol production process
WO2013013895A1 (fr) * 2011-07-25 2013-01-31 Haldor Topsøe A/S Procédé de production de gaz de synthèse
WO2016083434A1 (fr) * 2014-11-25 2016-06-02 Haldor Topsøe A/S Procédé de génération de gaz de synthèse par recyclage de gaz de combustion
WO2019020519A1 (fr) * 2017-07-25 2019-01-31 Haldor Topsøe A/S Procédé de préparation d'un gaz de synthèse
WO2019020515A1 (fr) * 2017-07-25 2019-01-31 Haldor Topsøe A/S Procédé de préparation d'un gaz de synthèse

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1033267C (zh) * 1991-07-09 1996-11-13 帝国化学工业公司 合成气的生产方法
EP2228358A1 (fr) * 2009-03-13 2010-09-15 Methanol Casale S.A. Récupération de CO2 dans un processus de synthèse de méthanol
WO2013062415A1 (fr) * 2011-10-26 2013-05-02 Stamicarbon B.V. Acting Under The Name Of Mt Innovation Center Procédé de production de syngaz pour la production de méthanol
DE102012112705A1 (de) * 2012-12-20 2014-06-26 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Verfahren zur Herstellung von Methanol aus Kohlendioxid
US9115045B2 (en) * 2013-04-26 2015-08-25 Praxair Technology, Inc. Method and system for producing methanol using an oxygen transport membrane based reforming system
US9637432B2 (en) * 2014-12-17 2017-05-02 Praxair Technology, Inc. Method and system for producing methanol using partial oxidation
CA2984609A1 (fr) * 2015-05-01 2016-11-10 Velocys Technologies, Ltd. Procede d'exploitation d'une installation integree de conversion de gaz en liquides

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000009441A2 (fr) * 1998-08-13 2000-02-24 Imperial Chemical Industries Plc Reformage a la vapeur
US20090012332A1 (en) * 2001-10-01 2009-01-08 Technology Convergence Inc. Methanol production process
WO2013013895A1 (fr) * 2011-07-25 2013-01-31 Haldor Topsøe A/S Procédé de production de gaz de synthèse
WO2016083434A1 (fr) * 2014-11-25 2016-06-02 Haldor Topsøe A/S Procédé de génération de gaz de synthèse par recyclage de gaz de combustion
WO2019020519A1 (fr) * 2017-07-25 2019-01-31 Haldor Topsøe A/S Procédé de préparation d'un gaz de synthèse
WO2019020515A1 (fr) * 2017-07-25 2019-01-31 Haldor Topsøe A/S Procédé de préparation d'un gaz de synthèse

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022155425A1 (fr) * 2021-01-14 2022-07-21 Bd Energy Systems, Llc Procédé de production de méthanol à faible émission de co2 et dispositif de production

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Publication number Publication date
WO2020148376A1 (fr) 2020-07-23
AR117827A1 (es) 2021-08-25
CN113677653A (zh) 2021-11-19
CN113329969A (zh) 2021-08-31
AU2020208917A1 (en) 2021-06-17
AR117826A1 (es) 2021-08-25
AU2020208782A1 (en) 2021-06-10

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