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NZ743349B2 - Methanol process - Google Patents
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NZ743349B2 - Methanol process - Google Patents

Methanol process Download PDF

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Publication number
NZ743349B2
NZ743349B2 NZ743349A NZ74334916A NZ743349B2 NZ 743349 B2 NZ743349 B2 NZ 743349B2 NZ 743349 A NZ743349 A NZ 743349A NZ 74334916 A NZ74334916 A NZ 74334916A NZ 743349 B2 NZ743349 B2 NZ 743349B2
Authority
NZ
New Zealand
Prior art keywords
methanol
synthesis
gas
process according
gas mixture
Prior art date
Application number
NZ743349A
Other versions
NZ743349A (en
Inventor
Kar Chi Yiu
Original Assignee
Johnson Matthey Davy Technologies Limited
Filing date
Publication date
Priority claimed from GBGB1600793.2A external-priority patent/GB201600793D0/en
Application filed by Johnson Matthey Davy Technologies Limited filed Critical Johnson Matthey Davy Technologies Limited
Publication of NZ743349A publication Critical patent/NZ743349A/en
Publication of NZ743349B2 publication Critical patent/NZ743349B2/en

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Classifications

    • 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
    • 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
    • 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
    • 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 and a first loop recycle gas stream 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 second 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) forming the first and second loop recycle gas streams from the second methanol-depleted gas mixture, wherein the first synthesis reactor has a higher heat transfer per cubic metre of catalyst than the second synthesis reactor and the recycle ratio of the first loop recycle gas stream to form the first synthesis gas mixture is in the range 0.1 to 1 :1, and the recycle ratio of the second loop recycle gas stream to form the second synthesis gas mixture is in the range 1.1 :1 to 6:1.

Claims (24)

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 and a first loop recycle gas stream 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 methanoldepleted gas mixture, (iii) combining the first methanol-depleted gas mixture with a second 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)forming the first and second loop recycle gas streams from the second methanol-depleted gas mixture, wherein the first synthesis reactor has a higher heat transfer per cubic metre of catalyst than the second synthesis reactor and the recycle ratio of the first loop recycle gas stream to form the first synthesis gas mixture is in the range 0.1 to 1:1, and the recycle ratio of the second 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 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.
3. A process according to claim 1 or 2, 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.
4. A process according to any one of claims 1 to 3, wherein the make-up gas contains carbon monoxide in the range 20-35% vol.
5. A process according to any one of claims 1 to 4 wherein the loop recycle gas streams are circulated by means of a two-stage circulator comprising a first stage and a second stage, or alternatively by two separate circulators.
6. A process according to any one of claims 1 to 5 wherein the loop recycle gas streams are circulated by means of two circulators arranged either in a single casing having one inlet and two outlets at different pressures, a single casing having two inlets at different pressures and one outlet, or in two separate casings. 18
7. A process according to claim 5 or 6 wherein a circulator comprises a first stage and a second stage, the first stage is fed with the first methanol-depleted gas mixture and the second stage is fed with the second recycle loop gas stream, and the first methanol-depleted gas mixture and the second recycle loop gas stream are combined in the circulator to provide the second synthesis gas.
8. A process according to claim 7 wherein the methanol-depleted gases fed to the circulator are enriched by a portion of the make-up gas.
9. A process according to claim 5 or 6 wherein a circulator comprises a first stage and a second stage, the first stage is fed with the second methanol-depleted gas stream minus any purge gas and produces two separate loop recycle gas streams; one from the circulator first stage, which is combined with the first methanol-depleted gas mixture and fed to the second synthesis reactor, and one from the circulator second stage, which is fed to the first synthesis reactor.
10. A process according to claim 9 wherein the first methanol-depleted gas mixture contains a portion of the make-up gas.
11. A process according to claim 5 or 6 wherein two separate circulators are used, a first circulator is fed with the first methanol-depleted gas mixture and a second circulator is fed with the second methanol-depleted gas stream, minus any purge stream, the second circulator product is divided into the first and second recycle loop gas streams, and the second recycle loop gas stream is mixed with the first methanol-depleted gas stream product of the first circulator.
12. A process according to claim 11 where the first methanol-depleted gas stream product of the first circulator is diluted with a portion of the make-up gas.
13. A process according to any one of claims 1 to 12 wherein the first synthesis reactor comprises a methanol synthesis catalyst disposed in tubes that are cooled by water under pressure, and 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.
14. A process according to any one of claims 1 to 13 wherein the first synthesis reactor is an axial flow steam-raising converter.
15. A process according to any one of claims 1 to 14 wherein the second synthesis reactor is selected from a radial flow steam-raising converter, a tube-cooled converter, a gas-cooled converter or a quench reactor. 19
16. A process according to any one of claims 1 to 15 wherein the methanol synthesis catalysts are copper-containing methanol synthesis catalysts.
17. A process according to any one of claims 1 to 16 wherein the methanol synthesis catalysts are compositions comprising copper, zinc oxide and alumina.
18. A process according to any one of claims 1 to 17 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.
19. A process according to claim 18 wherein the pressure in the second synthesis reactor is higher than the pressure in the first synthesis reactor.
20. A process according to any one of claims 1 to 19 wherein the gas mixtures fed to the first and/or second synthesis reactors are heated in gas-gas heat exchangers using the product gases from the reactors.
21. A process according to any one of claims 1 to 20 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.
22. A process according to any one of claims 1 to 21 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.
23. A process according to claim 21 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.
24. A process according to any one of claims 1 to 23, substantially as herein described with reference to any example thereof, and with or without reference to the accompanying drawings.
NZ743349A 2016-12-16 Methanol process NZ743349B2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB1600793.2A GB201600793D0 (en) 2016-01-15 2016-01-15 Methanol process
PCT/GB2016/053959 WO2017121980A1 (en) 2016-01-15 2016-12-16 Methanol process

Publications (2)

Publication Number Publication Date
NZ743349A NZ743349A (en) 2024-02-23
NZ743349B2 true NZ743349B2 (en) 2024-05-24

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