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NZ743351B2 - Methanol process - Google Patents
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NZ743351B2 - Methanol process - Google Patents

Methanol process Download PDF

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Publication number
NZ743351B2
NZ743351B2 NZ743351A NZ74335116A NZ743351B2 NZ 743351 B2 NZ743351 B2 NZ 743351B2 NZ 743351 A NZ743351 A NZ 743351A NZ 74335116 A NZ74335116 A NZ 74335116A NZ 743351 B2 NZ743351 B2 NZ 743351B2
Authority
NZ
New Zealand
Prior art keywords
synthesis
methanol
gas
process according
gas mixture
Prior art date
Application number
NZ743351A
Other versions
NZ743351A (en
Inventor
Kar Chi Yiu
Original Assignee
Johnson Matthey Davy Technologies Limited
Filing date
Publication date
Priority claimed from GBGB1600794.0A external-priority patent/GB201600794D0/en
Application filed by Johnson Matthey Davy Technologies Limited filed Critical Johnson Matthey Davy Technologies Limited
Publication of NZ743351A publication Critical patent/NZ743351A/en
Publication of NZ743351B2 publication Critical patent/NZ743351B2/en

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    • 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
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2203/00—Processes utilising sub- or super atmospheric pressure
    • B01J2203/06—High pressure synthesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/10—Constitutive chemical elements of heterogeneous catalysts of Group I (IA or IB) of the Periodic Table
    • B01J2523/17—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/20—Constitutive chemical elements of heterogeneous catalysts of Group II (IIA or IIB) of the Periodic Table
    • B01J2523/27—Zinc
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/30—Constitutive chemical elements of heterogeneous catalysts of Group III (IIIA or IIIB) of the Periodic Table
    • B01J2523/31—Aluminium
    • 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
    • C01B2203/0211—Processes for making hydrogen or synthesis gas containing a reforming step containing a non-catalytic reforming step
    • C01B2203/0216—Processes for making hydrogen or synthesis gas containing a reforming step containing a non-catalytic reforming step containing a non-catalytic 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
    • C01B2203/0283—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
    • C01B2203/06—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
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification
    • C01B3/506—Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification at low temperatures
    • 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
    • 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
    • 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
    • C07C29/152—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 characterised by the reactor used
    • 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
    • C07C29/153—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 characterised by the catalyst used
    • C07C29/154—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 characterised by the catalyst used containing copper, silver, gold, or compounds thereof
    • 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
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
    • 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

Abstract

process is described for the synthesis of methanol comprising the steps of: (i) passing a first synthesis gas mixture comprising a make-up gas through a first synthesis reactor containing a cooled methanol synthesis catalyst to form a first product gas stream, (ii) recovering methanol from the first product gas stream thereby forming a first methanol- depleted gas mixture, (iii) combining the first methanol-depleted gas mixture with a loop recycle gas stream to form a second synthesis gas mixture, (iv) passing the second synthesis gas mixture through a second synthesis reactor containing a cooled methanol synthesis catalyst to form a second product gas stream, (v) recovering methanol from the second product gas stream thereby forming a second methanol-depleted gas mixture, and (vi) using at least part of the second methanol-depleted gas mixture as the loop recycle gas stream, wherein the first synthesis reactor has a higher heat transfer per cubic metre of catalyst than the second synthesis reactor, none of the loop recycle gas stream is fed to the first synthesis gas mixture and the recycle ratio of the loop recycle gas stream to form the second synthesis gas mixture is in the range 1.1 :1 to 6:1.

Claims (17)

Claims.
1. A process for the synthesis of methanol comprising the steps of: (i) passing a first synthesis gas mixture comprising a make-up gas through a first synthesis reactor containing a cooled methanol synthesis catalyst to form a first product gas stream, (ii) recovering methanol from the first product gas stream thereby forming a first methanol-depleted gas mixture, (iii) combining the first methanol-depleted gas mixture with a loop recycle gas stream to form a second synthesis gas mixture, (iv) passing the second synthesis gas mixture through a second synthesis reactor containing a cooled methanol synthesis catalyst to form a second product gas stream, (v) recovering methanol from the second product gas stream thereby forming a second methanol-depleted gas mixture, and (vi) using at least part of the second methanol-depleted gas mixture as the loop recycle gas stream, wherein the first synthesis reactor has a higher heat transfer per cubic metre of catalyst than the second synthesis reactor, none of the loop recycle gas stream is fed to the first synthesis gas mixture and the recycle ratio of the loop recycle gas stream to form the second synthesis gas mixture is in the range 1.1:1 to 6:1.
2. A process according to claim 1 wherein the make-up gas contains carbon monoxide in the range 10-20%vol and is passed directly to the first methanol synthesis reactor without dilution with other gases.
3. A process according to claim 1 wherein the make-up gas contains carbon monoxide in the range 20-35% vol and is diluted with a hydrogen-containing gas stream selected from a purge gas stream from other methanol processes or a hydrogen gas stream.
4. A process according to any one of claims 1 to 3 wherein a single circulator is used for feeding the combined loop recycle gas and the first methanol depleted gas mixture to the second synthesis reactor.
5. A process according to any one of claims 1 to 4 wherein the recycle ratio of the loop recycle gas stream to form the second synthesis gas mixture is in the range 1.5:1 to 6:1. 15
6. A process according to any one of claims 1 to 5 wherein the recycle ratio of the loop recycle gas stream to form the second synthesis gas mixture is in the range 2:1 to 6:1.
7. A process according to any one of claims 1 to 6 wherein the first synthesis reactor comprises a methanol synthesis catalyst disposed in tubes that are cooled by water under pressure, the second synthesis reactor comprises a fixed bed of a methanol synthesis catalyst that is cooled in heat exchange with either water under pressure or a synthesis gas mixture selected from the first synthesis gas mixture and the second synthesis gas mixture.
8. A process according to any one of claims 1 to 7 wherein the first synthesis reactor is axial flow steam-raising converter.
9. A process according to any one of claims 1 to 8 wherein the second synthesis reactor is selected from a radial flow steam-raising converter, a tube-cooled converter, a gascooled converter or a quench reactor.
10. A process according to any one of claims 1 to 9 wherein the methanol synthesis catalysts are copper-containing methanol synthesis catalysts.
11. A process according to any one of claims 1 to 10 wherein the methanol synthesis catalysts are compositions comprising copper, zinc oxide and alumina.
12. A process according to any one of claims 1 to 11 wherein methanol synthesis in the first and second reactors is performed at pressures in the range 20 to 120 bar abs and temperatures in the range 130oC to 350oC.
13. A process according to any one of claims 1 to 12 wherein the gas mixtures fed to the first and second synthesis reactors are heated in gas-gas heat exchangers using the product gases from the reactors.
14. A process according to any one of claims 1 to 13 wherein the product gas streams from the first and second synthesis reactors are cooled in one or more stages of heat exchange to condense methanol therefrom.
15. A process according to any one of claims 1 to 14 wherein a purge gas stream is recovered from the second methanol depleted gas mixture and is used for hydrogen recovery, or is subjected to one or more further processing stages including autothermal reforming, water-gas shift and methanol synthesis. 16
16. A process according to claim 15 wherein the condensed methanol is recovered using gas-liquid separators, combined and passed for further processing, in one or more stages of distillation to produce a purified methanol product.
17. A process according to any one of claims 1 to 16, substantially as herein described with reference to any example thereof and with or without reference to the accompanying drawing.
NZ743351A 2016-12-16 Methanol process NZ743351B2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB1600794.0A GB201600794D0 (en) 2016-01-15 2016-01-15 Methanol process
PCT/GB2016/053960 WO2017121981A1 (en) 2016-01-15 2016-12-16 Methanol process

Publications (2)

Publication Number Publication Date
NZ743351A NZ743351A (en) 2024-02-23
NZ743351B2 true NZ743351B2 (en) 2024-05-24

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