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WO1996006064A1 - Procede d'elaboration de methanol a partir d'effluents gazeux - Google Patents

Procede d'elaboration de methanol a partir d'effluents gazeux Download PDF

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Publication number
WO1996006064A1
WO1996006064A1 PCT/KR1995/000109 KR9500109W WO9606064A1 WO 1996006064 A1 WO1996006064 A1 WO 1996006064A1 KR 9500109 W KR9500109 W KR 9500109W WO 9606064 A1 WO9606064 A1 WO 9606064A1
Authority
WO
WIPO (PCT)
Prior art keywords
mixture
methanol
gas
carbon dioxide
conversion
Prior art date
Application number
PCT/KR1995/000109
Other languages
English (en)
Inventor
Sung Jin Uhm
Seong Hwan Han
Suk Mok Song
Oh Shim Joo
Original Assignee
Korea Institute Of Science And Technology
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 Korea Institute Of Science And Technology filed Critical Korea Institute Of Science And Technology
Priority to JP8507956A priority Critical patent/JPH09510734A/ja
Publication of WO1996006064A1 publication Critical patent/WO1996006064A1/fr

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/04—Methanol
    • 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
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a process for the production of methanol from carbon dioxide by way of employing a reverse water gas shift reaction.
  • the output from the fixed-bed reactor (20) is then fed to a synthesis loop incorporating a second reactor (30) wherein methanol is eventually produced.
  • the Goehna method still suffers from the disadvantage in that a large quantity of water present in the output from the first reactor undermines the whole process.
  • the molar ratio of C0 2 in the gaseous mixture to be fed into the second reactor is too high; and, consequently, the volume of the C0 2 gas recycled into the second reactor and the amount of the purge gas remain excessively high, rendering the process commercially impracticable.
  • a process for preparing methanol which comprises: (a) compressing a gaseous mixture of carbon dioxide and hydrogen;
  • Fig. 1 provides a schematic flow diagram showing a two- step prior art process for the production of methanol from C0 2 and H 2 ; and Fig. 2 presents a schematic flow diagram illustrating the inventive process for the production of methanol.
  • methanol can be economically produced from carbon dioxide, which may be recovered in vast amounts from various industrial processes as a by-product.
  • a part of carbon dioxide is first converted into carbon monoxide by a reverse water gas shift reaction at a high temperature; water produced during the conversion process is removed; and then the remaining gaseous mixture thereof is subjected to a methanol synthesis reaction to produce methanol.
  • a gaseous mixture of carbon dioxide and hydrogen is compressed and introduced into a conversion column wherein a part of the carbon dioxide contained in the mixture is converted to carbon monoxide.
  • the gaseous feed mixture may contain carbon dioxide and hydrogen in a molar ratio ranging from 1:0.1 to 1:100, preferably from 1:1 to 1:10, and, more preferably, from 1:2 to 1:4.
  • the conversion process may be carried out at a temperature ranging from 100 to 1,000 °C, preferably from 300 to 800 °C, and, more preferably, from 400 to 600 °C under a pressure ranging from 1 to 200 atm, preferably, from 10 to 100 atm, and, more preferably, from 10 to 50 atm, in the presence of a catalyst.
  • the catalyst which may be used in the present invention includes those used conventionally for the water gas shift reaction, e.g., metallic compounds of such metals as Cu, Mo, Fe, Cr, Ni, Zn, W, V, Ni, Pd, Co, Rh, Sn or Al, or a mixture thereof supported on various supporting materials such as ZnO, A1 2 0 3 , SiO, ZnO/Al 2 0 3 , lanthanide oxide, actinide oxide, MgO and the like.
  • the inlet temperature of the conversion column is preferably controlled to be higher than the outlet temperature of the conversion column.
  • the inlet temperature of the conversion column may range from 100 to 1,000 °C, preferably, from 300 to 800 °C, and, more preferably, from 400 to 600 °C; and the outlet temperature may range up to 900 °C, preferably, from 200 to 700 °C, and, more preferably, from 350 to 550 °C.
  • the rate of conversion from carbon dioxide to carbon monoxide may lie in a range from 10 to 90 %. That is, the partial molar ratio of carbon dioxide to the sum of carbon dioxide and carbon monoxide (hereinafter called "A" value) may be in the range of 0.1 to 0.9.
  • the conversion rate may range preferably from 20 to 80 %, and, more preferably, from 40 to 60 %.
  • the conversion rate may be controlled by adjusting the conversion condition such as the outlet temperature of the conversion column, flow rate of the gas recycled into the conversion column and content of water in the feed gas. Specifically, the conversion rate becomes lowered as the outlet temperature or the flow rate of the recycled gas becomes higher, or as the water content becomes higher.
  • the resulting product mixture which comprises a gas phase mixture containing carbon monoxide produced by the conversion process, non-converted carbon dioxide and hydrogen, and a liquid phase mixture containing water is introduced into a gas-liquid separator to remove the liquid phase mixture or water.
  • the gas phase mixture so separated is then introduced into a reactor via a compressor to produce a mixture containing methanol.
  • the reaction of the compressed gas phase mixture in the synthesis reactor may be conducted at conventional reaction conditions well known in the art, i.e., at a temperature ranging from 100 to 800 °C, preferably, from 150 to 400 °C, and, more preferably, from
  • the inlet and outlet temperatures of the reactor may range from 150 to 250 °C and from 200 to 300 °C, respectively.
  • the catalyst which may be used in the reaction includes those used conventionally in the art, e.g., a copper compound supported on a supporting material. If desired, a part of the gas phase mixture separated at the separator may be recycled into the conversion column via a compressor so as to increase the conversion rate.
  • methanol may be easily recovered as a liquid phase product by, e.g., passing it through a gas-liquid separator.
  • the remaining gaseous mixture may be recycled into the reactor via a compressor or vented off as a purge gas.
  • a gaseous mixture of carbon dioxide and hydrogen is compressed by a compressor (10) and then the compressed gaseous mixture is introduced into a conversion column (20) with or without the gas phase mixture recycled from a gas- liquid separator (30), to convert a part of the carbon dioxide contained in the mixture to carbon monoxide, thereby producing a gas phase mixture and a liquid phase mixture containing water.
  • the production mixture is then introduced into the gas-liquid separator (30) to remove the liquid phase contained therein at the bottom of the separator and recover the gas phase mixture from the top of the separator.
  • a part or all of the gas phase mixture recovered is introduced as a feed gas into a reactor (60) via a compressor (50) to produce a mixture containing methanol; and, if desired, a part of the gas phase mixture is recycled into the conversion column (20) via a compressor (40).
  • the mixture containing methanol is introduced into a separator (70) to recover methanol as a liquid phase product at the bottom part of the separator while the remaining gaseous mixture is recycled into the synthesis reactor (60) via a compressor (80) or vented off as a purge gas.
  • a gaseous mixture of 25:75 (v/v) of carbon dioxide and hydrogen was treated in accordance with the conversion process of the present invention (see Fig. 2) under various conversion conditions shown in Table 1.
  • the catalyst employed was Zn-Cr/alumina prepared by supporting zinc and chromium compounds on alumina by a coprecipitation method. The resulting products were analyzed by a gas chromatography and the A values thereof were calculated and are shown in Table 1.
  • a gaseous mixture of 25:75 (v/v) of carbon dioxide and hydrogen was introduced to a conversion column filled with 30 m 3 of 5% Mo0 3 /alumina as a catalyst at a flow rate of 150,000 m 3 /hr.
  • the conversion process was conducted at 600 °C under 20 atm while maintaining GHSV (Gas Hourly Space Velocity) of the mixture at 5,000 hr "1 .
  • the conversion rate of carbon dioxide to carbon monoxide was 61 %, and water was condensed in an amount of 18.5 wt% of the resulting product mixture.
  • Example 2 The same procedures described in Example 2 were repeated, except that the gaseous mixture was introduced directly at a flow rate of 150,000 m /hr into the reactor, and the inlet and outlet temperatures of the reactor were
  • methanol can be efficiently produced from carbon dioxide in a higher yield and productivity than the prior art process. Consequently, emission of waste carbon dioxide into environment can be minimized, thus reducing air pollution.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Procédé permettant de produire de manière économique et avec un rendement élevé du méthanol à partir du dioxide de carbone. Ce procédé consiste à comprimer un mélange gazeux de dioxide de carbone et d'hydrogène; à introduire ce mélange gazeux comprimé dans une colonne de conversion; à convertir une partie du dioxide de carbone contenu dans le mélange en monoxide de carbone en présence d'un catalyseur, dans la colonne de conversion, pour obtenir un mélange en phase gazeuse et un mélange en phase liquide; à extraire le mélange en phase liquide dans un séparateur gaz/liquide; à introduire le mélange en phase gazeuse du séparateur gaz/liquide dans un réacteur tout en recyclant, éventuellement, une partie de ce mélange dans la colonne de conversion; à faire réagir le mélange en phase gazeuse comprimé introduit dans le réacteur en présence d'un catalyseur pour produire un mélange contenant du méthanol; et à récupérer le méthanol sous forme de produit en phase liquide du mélange.
PCT/KR1995/000109 1994-08-19 1995-08-19 Procede d'elaboration de methanol a partir d'effluents gazeux WO1996006064A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP8507956A JPH09510734A (ja) 1994-08-19 1995-08-19 廃ガスからのメタノールの製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1019940020457A KR0138587B1 (ko) 1994-08-19 1994-08-19 새로운 메탄올 합성방법
KR1994/20457 1994-08-19

Publications (1)

Publication Number Publication Date
WO1996006064A1 true WO1996006064A1 (fr) 1996-02-29

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PCT/KR1995/000109 WO1996006064A1 (fr) 1994-08-19 1995-08-19 Procede d'elaboration de methanol a partir d'effluents gazeux

Country Status (3)

Country Link
JP (1) JPH09510734A (fr)
KR (1) KR0138587B1 (fr)
WO (1) WO1996006064A1 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5911964A (en) * 1993-06-25 1999-06-15 Cosmo Research Institute Method for reducing carbon dioxide using a catalyst for reduction of carbon dioxide
US8288446B2 (en) 2007-06-25 2012-10-16 Saudi Basic Industries Corporation Catalytic hydrogenation of carbon dioxide into syngas mixture
WO2013085861A1 (fr) 2011-12-08 2013-06-13 Saudi Basic Industries Corporation Catalyseur à base d'un oxyde mixte pour la conversion du dioxyde de carbone en gaz de synthèse, son procédé de préparation et utilisation
US8551434B1 (en) 2012-06-29 2013-10-08 Saudi Basic Industries Corporation Method of forming a syngas mixture
US8658554B2 (en) 2009-11-04 2014-02-25 The United States Of America, As Represented By The Secretary Of The Navy Catalytic support for use in carbon dioxide hydrogenation reactions
US8961829B2 (en) 2007-04-27 2015-02-24 Saudi Basic Industries Corporation Catalytic hyrogenation of carbon dioxide into syngas mixture
WO2015066117A1 (fr) 2013-10-29 2015-05-07 Saudi Basic Industries Corporation Procédé d'hydrogénation de dioxyde de carbone d'un gaz synthétique et intégration du procédé dans des procédés de conversion de gaz synthétique
WO2015103592A1 (fr) 2014-01-06 2015-07-09 Saudi Basic Industries Corporation Procédé d'hydrogénation du dioxyde de carbone d'un gaz de synthèse
CN105622344A (zh) * 2014-11-03 2016-06-01 中国石油化工股份有限公司 一种二氧化碳加氢合成甲醇的工艺方法
CN110845304A (zh) * 2019-12-02 2020-02-28 北京烨晶科技有限公司 三聚氰胺尾气联产甲醇的方法、装置及其应用
CN110950737A (zh) * 2019-12-02 2020-04-03 北京烨晶科技有限公司 硝酸副产二氧化碳生产甲醇的方法、装置及其应用
CN119391951A (zh) * 2025-01-02 2025-02-07 浙江华远汽车科技股份有限公司 一种渗碳废气中的二氧化碳循环利用系统及方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2601445C (fr) * 2005-03-16 2012-10-02 Fuelcor Llc Systemes, procedes et compositions permettant de produire des composes hydrocarbones synthetiques
US8791166B2 (en) * 2008-07-24 2014-07-29 University Of Southern California Producing methanol and its products exclusively from geothermal sources and their energy
CN103209946B (zh) * 2010-11-19 2016-06-15 三井化学株式会社 甲醇的制造方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0494350A2 (fr) * 1991-01-11 1992-07-15 Uhde GmbH Procédé et installation pour la synthèse de méthanol

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0494350A2 (fr) * 1991-01-11 1992-07-15 Uhde GmbH Procédé et installation pour la synthèse de méthanol

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KIRK-OTHMER, ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY, Third Edition, Vol. 15, JOHN WILEY & SONS, NEW YORK, CHICHESTER, BRISBANE, TORONTO, 1981, pages 400-408. *

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5911964A (en) * 1993-06-25 1999-06-15 Cosmo Research Institute Method for reducing carbon dioxide using a catalyst for reduction of carbon dioxide
US8961829B2 (en) 2007-04-27 2015-02-24 Saudi Basic Industries Corporation Catalytic hyrogenation of carbon dioxide into syngas mixture
US8288446B2 (en) 2007-06-25 2012-10-16 Saudi Basic Industries Corporation Catalytic hydrogenation of carbon dioxide into syngas mixture
US8658554B2 (en) 2009-11-04 2014-02-25 The United States Of America, As Represented By The Secretary Of The Navy Catalytic support for use in carbon dioxide hydrogenation reactions
CN103974767B (zh) * 2011-12-08 2016-09-28 沙特基础工业公司 用于将二氧化碳转化成合成气的基于混合氧化物的催化剂及制备和使用方法
CN103974767A (zh) * 2011-12-08 2014-08-06 沙特基础工业公司 用于将二氧化碳转化成合成气的基于混合氧化物的催化剂及制备和使用方法
US8962702B2 (en) 2011-12-08 2015-02-24 Saudi Basic Industries Corporation Mixed oxide based catalyst for the conversion of carbon dioxide to syngas and method of preparation and use
WO2013085861A1 (fr) 2011-12-08 2013-06-13 Saudi Basic Industries Corporation Catalyseur à base d'un oxyde mixte pour la conversion du dioxyde de carbone en gaz de synthèse, son procédé de préparation et utilisation
WO2014003817A1 (fr) 2012-06-29 2014-01-03 Saudi Basic Industries Corporation Procédé de formation d'un mélange de gaz de synthèse
US8551434B1 (en) 2012-06-29 2013-10-08 Saudi Basic Industries Corporation Method of forming a syngas mixture
WO2015066117A1 (fr) 2013-10-29 2015-05-07 Saudi Basic Industries Corporation Procédé d'hydrogénation de dioxyde de carbone d'un gaz synthétique et intégration du procédé dans des procédés de conversion de gaz synthétique
US9688593B2 (en) 2013-10-29 2017-06-27 Saudi Basic Industries Corporation Method for carbon dioxide hydrogenation of syngas and the integration of the process with syngas conversion processes
WO2015103592A1 (fr) 2014-01-06 2015-07-09 Saudi Basic Industries Corporation Procédé d'hydrogénation du dioxyde de carbone d'un gaz de synthèse
CN105622344A (zh) * 2014-11-03 2016-06-01 中国石油化工股份有限公司 一种二氧化碳加氢合成甲醇的工艺方法
CN110845304A (zh) * 2019-12-02 2020-02-28 北京烨晶科技有限公司 三聚氰胺尾气联产甲醇的方法、装置及其应用
CN110950737A (zh) * 2019-12-02 2020-04-03 北京烨晶科技有限公司 硝酸副产二氧化碳生产甲醇的方法、装置及其应用
CN119391951A (zh) * 2025-01-02 2025-02-07 浙江华远汽车科技股份有限公司 一种渗碳废气中的二氧化碳循环利用系统及方法

Also Published As

Publication number Publication date
KR0138587B1 (ko) 1998-05-01
JPH09510734A (ja) 1997-10-28
KR960007519A (ko) 1996-03-22

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