WO2015181214A1 - Increasing co/co2 ratio in syngas by reverse water gas shift - Google Patents

Increasing co/co2 ratio in syngas by reverse water gas shift Download PDF

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Publication number
WO2015181214A1
WO2015181214A1 PCT/EP2015/061668 EP2015061668W WO2015181214A1 WO 2015181214 A1 WO2015181214 A1 WO 2015181214A1 EP 2015061668 W EP2015061668 W EP 2015061668W WO 2015181214 A1 WO2015181214 A1 WO 2015181214A1
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Prior art keywords
gas
stream
proceeding
production plant
rwgs
Prior art date
Application number
PCT/EP2015/061668
Other languages
French (fr)
Inventor
Niels Ulrik Andersen
Original Assignee
Haldor Topsøe A/S
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Publication date
Application filed by Haldor Topsøe A/S filed Critical Haldor Topsøe A/S
Priority to EA201692381A priority Critical patent/EA201692381A1/en
Priority to US15/313,053 priority patent/US20170197829A1/en
Priority to MX2016015414A priority patent/MX2016015414A/en
Priority to CN201580027440.9A priority patent/CN106414313A/en
Publication of WO2015181214A1 publication Critical patent/WO2015181214A1/en

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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
    • 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
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C10K3/026—Increasing the carbon monoxide content, e.g. reverse water-gas shift [RWGS]
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/06—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by mixing with gases
    • 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
    • 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
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation 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
    • C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0405—Purification by membrane separation
    • 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
    • C01B2203/042—Purification by adsorption on solids
    • C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
    • 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
    • C01B2203/046—Purification by cryogenic separation
    • 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
    • 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

Definitions

  • the existing reactors, re ⁇ formers etc. may put restraints on the possibilities for the updated process and/or plant.
  • the catalyst volume in an existing plant may provide a limit for a pro ⁇ cess which means that the revamp cannot in an advantageous setup result in a need for an increased catalyst volume.
  • con ⁇ straints are made on reformers, reactors etc. there is a need for alternative processes and plants which increase efficiency without increasing the capacity needs above the available .
  • a first object of the present process and plant is pro ⁇ vided means for improving the amount and composition of a synthesis gas without increasing the need for reform ⁇ er/reactor/catalyst volume.
  • a synthesis gas generation step arranged to receive a hydrocarbon or carboneous feed stock and in a synthesis gas generation process provide a syngas
  • a production step arranged to receive the syngas and produce a product stream
  • a reverse water gas shift step arranged to receive a 3 ⁇ 4 rich gas stream and a CO 2 feed and in a RWGS process ob- tain a reverse shifted gas stream, and
  • means for adding said reverse shifted gas stream to the synthesis gas stream whereby a plant which enable the production of a mixed synthesis gas stream having an improved CO/CO 2 ratio without resulting in an increase in the needed duty of the synthesis gas generation step for exam ⁇ ple comprising a reformer and/or an increased catalyst vol- ume/heat transfer area in the production step.
  • the production step can be a methanol synthesis loop ar ⁇ ranged to receive the syngas/reverse shifted gas mixture and produce a Methanol-rich product stream
  • the production step may also e.g. be a purification unit producing a product gas rich in Carbonmonoxide .
  • the synthesis gas generation step can in some advantageous embodiments be a reforming step, a gasification step, or a partial oxidation step depending on what feed is provided and/or on the production step. I.e. the synthesis genera ⁇ tion step can be selected to provide an optimized inlet gas to the production step.
  • the synthesis gas genera ⁇ tion step does not need to be dimensioned to receive the reverse shifted gas stream. This may be highly desirable in setups wherein volume/capacity of the synthesis gas genera ⁇ tion step is an issue, which for example can be the case in revamps of existing plants.
  • the RWGS step comprises a hydrogen recovery unit up- stream the RWGS process the stream which enters the RWGS process has an increased 3 ⁇ 4 ratio and a decreased content of other substances compared to the stream which enters the RWGS step.
  • the hydrogen recovery unit can be of different types such as a membrane unit, PSA unit or cryogenic unit.
  • a residual gas stream may be provid ⁇ ed e.g. to burners etc.
  • the 3 ⁇ 4 rich gas stream can be a purge gas from the Methanol production loop.
  • the purge gas can contain various substances which advantageously may be removed in which cases the purge gas can be passed through a hydrogen recovery unit as described above before it is fed to the
  • the 3 ⁇ 4 rich stream may be sent directly to the RWGS step.
  • the CO2 feed can be provided by various means.
  • the CO2 can be provided from underground natural CO2 rich gas reservoir.
  • the CO2 can also be provided from a purification unit
  • the RWGS step can be arranged in different ways with a range of suited catalysts.
  • the RWGS step may comprise a High Temperature Shift Catalyst (e.g. Tops0e SK- 201 or SK-501) or an UltraHigh Temperature Shift Catalyst for the RWGS process.
  • the production unit is a purification unit producing a CO stream or CO-rich stream the production unit may for example be a membrane unit or a cryogenic unit.
  • a RWGS production step is used to provide a stream with an increased CO content, which stream with an increased CO content is added to the synthesis gas to ob ⁇ tain a mixed synthesis gas with a higher CO content thereby optimizing the production in the production loop.
  • the production loop can for example be a methanol produc ⁇ tion unit producing a methanol rich product stream or e.g. be a CO production/purification unit producing a CO rich stream.
  • the 3 ⁇ 4 rich gas stream is a purge gas from a Methanol loop a highly effective process is achieved wherein the off gas from the methanol production is used to optimize the composition of the syngas used in the methanol production.
  • the RWGS shifted gas stream can advanta ⁇ geously be produced over a High Temperature Shift Catalyst (e.g. Tops0e SK-201 or SK-501) or a UltraHigh Temperature Shift Catalyst.
  • a High Temperature Shift Catalyst e.g. Tops0e SK-201 or SK-501
  • a UltraHigh Temperature Shift Catalyst e.g. Tops0e SK-201 or SK-501
  • the RWGS inlet temperature can be in the range of 250 - 750 °C. Often higher temperatures may be preferred as the RWGS conversion is favoured by higher temperatures. E.g. the inlet temperature can be 350°C or above, such as 500°C or above. As the reverse water gas shift reaction is an endothermic reaction the outlet temperature in an adiabatic reactor will be lower than the inlet temperature, typically the temperature drop will be in the range 50-250°C, such as 60 - 125.
  • the reverse shift reac ⁇ tion converts 5-75% of the CO 2 into CO, resulting in a re ⁇ verse shifted gas which has a CO/CO 2 ratio of 0.05 - 3, such as above 0.1 and/or below 2.
  • the syngas may mainly comprise Hydrogen, Car- bonmonoxide, Carbondioxide, Methane, and Water (small amounts of f.inst. Nitrogen, Argon, and Helium may also be present)
  • the syngas may comprise
  • the syngas generally comprises Hydrogen, Carbonmonoxide, Methane, Wa ⁇ ter, and Carbondioxide (small amounts of for example Nitro ⁇ gen, Argon, and Helium may also be present) before the CO 2 removal step where the reverse shifted gas advantageous can be added
  • the 3 ⁇ 4 rich gas stream may e.g. comprise Hydrogen, Carbonmonoxide, Carbondioxide, Water, and Methane.
  • the 3 ⁇ 4 rich stream comprises
  • the present process and plant may advantageously be part of a revamp of an existing plant such as a methanol production plant .
  • An example of parameters for the RWGS step is given below:
  • Fig. 1 shows a diagram of the plan/process according to the present invention wherein a synthesis gas generation step 1 is arranged to receive a hydrocarbon or carboneous feed stock 2 and in a synthesis gas generation process provide a syngas 3.
  • a production step 4 is arranged to receive the syngas and produce a product stream (5) .
  • a reverse water gas shift step 6 is arranged to receive a 3 ⁇ 4 rich gas stream 7 and a CO 2 feed 8 and in a RWGS process obtain a reverse shifted gas stream 9.
  • the plant/process furthermore has means 10 for adding said reverse shifted gas stream to the synthesis gas stream.
  • a 3 ⁇ 4 recovery unit 11 can be arranged to pro ⁇ vide a gas stream 7 which has an increased 3 ⁇ 4 concentration compare to what is received from the production step 4.
  • a 3 ⁇ 4 recovery unit may for example be used where a purge 12 from the production step 4 is used to provide the 3 ⁇ 4 rich stream.
  • a residual gas stream 13 may be provided e.g. to burners etc.
  • a pro ⁇ cess and a plant by which a mixture of CO 2 and 3 ⁇ 4 stream is send to a reactor with a catalyst active towards the Water Gas Shift Reaction, a RWG shift (C0 2 + H 2 -» CO + H 2 0) can be obtained, improving the CO/CO 2 ratio, and thus the reac- tivity of the synthesis gas, reducing the required catalyst volume and/or heat transfer area in the production step, such as a methanol synthesis reactor.
  • the present process and plant may be a particular advantage for revamp pro ⁇ jects, where the size of reformer and/or Methanol reactor is given by existing structures.

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

Abstract

The present application relates to a production plant comprising - a synthesis gas generation step (1) arranged to receive a hydrocarbon or carboneous feedstock (2) and in a synthesis gas generation process provide a syngas, - a production step (4) arranged to receive the syngas and produce a product stream (5), - a reverse water gas shift step (4) arranged to receive a H2 rich gas stream (7) and a C02 feed (8) and in a RWGS step obtain a reverse shifted gas stream (9), and - means (10) for adding said reverse shifted gas stream (9) to the synthesis gas stream (3).

Description

INCREASING CO/C02 RATIO IN SYNGAS BY REVERSE WATER GAS SHIFT
In revamps of existing plants the existing reactors, re¬ formers etc. may put restraints on the possibilities for the updated process and/or plant. For example the catalyst volume in an existing plant may provide a limit for a pro¬ cess which means that the revamp cannot in an advantageous setup result in a need for an increased catalyst volume. Thus in existing plants or other situations where con¬ straints are made on reformers, reactors etc. there is a need for alternative processes and plants which increase efficiency without increasing the capacity needs above the available .
In a first object of the present process and plant is pro¬ vided means for improving the amount and composition of a synthesis gas without increasing the need for reform¬ er/reactor/catalyst volume.
These and other advantages are achieved by a production plant comprising
a synthesis gas generation step arranged to receive a hydrocarbon or carboneous feed stock and in a synthesis gas generation process provide a syngas
a production step arranged to receive the syngas and produce a product stream
a reverse water gas shift step arranged to receive a ¾ rich gas stream and a CO2 feed and in a RWGS process ob- tain a reverse shifted gas stream, and
means for adding said reverse shifted gas stream to the synthesis gas stream whereby a plant which enable the production of a mixed synthesis gas stream having an improved CO/CO2 ratio without resulting in an increase in the needed duty of the synthesis gas generation step for exam¬ ple comprising a reformer and/or an increased catalyst vol- ume/heat transfer area in the production step.
The production step can be a methanol synthesis loop ar¬ ranged to receive the syngas/reverse shifted gas mixture and produce a Methanol-rich product stream
The production step may also e.g. be a purification unit producing a product gas rich in Carbonmonoxide .
The synthesis gas generation step can in some advantageous embodiments be a reforming step, a gasification step, or a partial oxidation step depending on what feed is provided and/or on the production step. I.e. the synthesis genera¬ tion step can be selected to provide an optimized inlet gas to the production step.
If the reverse shifted gas stream is provided downstream the synthesis gas generation step the synthesis gas genera¬ tion step does not need to be dimensioned to receive the reverse shifted gas stream. This may be highly desirable in setups wherein volume/capacity of the synthesis gas genera¬ tion step is an issue, which for example can be the case in revamps of existing plants.
If the RWGS step comprises a hydrogen recovery unit up- stream the RWGS process the stream which enters the RWGS process has an increased ¾ ratio and a decreased content of other substances compared to the stream which enters the RWGS step.
Depending on the setup used the hydrogen recovery unit can be of different types such as a membrane unit, PSA unit or cryogenic unit.
From the recovery unit a residual gas stream may be provid¬ ed e.g. to burners etc.
For example the ¾ rich gas stream can be a purge gas from the Methanol production loop. The purge gas can contain various substances which advantageously may be removed in which cases the purge gas can be passed through a hydrogen recovery unit as described above before it is fed to the
RWGS process. Alternatively the ¾ rich stream may be sent directly to the RWGS step.
The CO2 feed can be provided by various means. For example the CO2 can be provided from underground natural CO2 rich gas reservoir.
The CO2 can also be provided from a purification unit
(amine wash, PSA, etc.) removing CO2 from a synthesis gas, flue gas, or natural gas depending on which sources of CO2 are available or otherwise desirable in a given setup.
The RWGS step can be arranged in different ways with a range of suited catalysts. For example, the RWGS step may comprise a High Temperature Shift Catalyst (e.g. Tops0e SK- 201 or SK-501) or an UltraHigh Temperature Shift Catalyst for the RWGS process. In setups where the production unit is a purification unit producing a CO stream or CO-rich stream the production unit may for example be a membrane unit or a cryogenic unit.
Also provided is a process for adjusting the CO/CO2 ratio in a synthesis gas, said process comprising
in a production loop producing a product stream from a synthesis gas,
- in an RWGS reactor producing a reverse shifted gas stream at least from a CO2 feed and a ¾ rich gas stream, and
adding the produced reversed shifted gas stream to the synthesis gas upstream the production loop. I.e. in the present process a RWGS production step is used to provide a stream with an increased CO content, which stream with an increased CO content is added to the synthesis gas to ob¬ tain a mixed synthesis gas with a higher CO content thereby optimizing the production in the production loop.
The production loop can for example be a methanol produc¬ tion unit producing a methanol rich product stream or e.g. be a CO production/purification unit producing a CO rich stream.
If the ¾ rich gas stream is a purge gas from a Methanol loop a highly effective process is achieved wherein the off gas from the methanol production is used to optimize the composition of the syngas used in the methanol production.
In the process the RWGS shifted gas stream can advanta¬ geously be produced over a High Temperature Shift Catalyst (e.g. Tops0e SK-201 or SK-501) or a UltraHigh Temperature Shift Catalyst.
The RWGS inlet temperature can be in the range of 250 - 750 °C. Often higher temperatures may be preferred as the RWGS conversion is favoured by higher temperatures. E.g. the inlet temperature can be 350°C or above, such as 500°C or above. As the reverse water gas shift reaction is an endothermic reaction the outlet temperature in an adiabatic reactor will be lower than the inlet temperature, typically the temperature drop will be in the range 50-250°C, such as 60 - 125.
In several advantageous embodiments the reverse shift reac¬ tion converts 5-75% of the CO2 into CO, resulting in a re¬ verse shifted gas which has a CO/CO2 ratio of 0.05 - 3, such as above 0.1 and/or below 2.
Generally the syngas may mainly comprise Hydrogen, Car- bonmonoxide, Carbondioxide, Methane, and Water (small amounts of f.inst. Nitrogen, Argon, and Helium may also be present) In the case of methanol production the syngas may comprise
H2 65-75 vol
CO 12-25 vol
C02 5-10 vol-
CH4 0-10 vol-
H20 Saturated If the production step is a CO purification step the syngas generally comprises Hydrogen, Carbonmonoxide, Methane, Wa¬ ter, and Carbondioxide (small amounts of for example Nitro¬ gen, Argon, and Helium may also be present) before the CO2 removal step where the reverse shifted gas advantageous can be added
H2 50-70 vol
CO 20-35 vol
C02 5-10 vol-
CH4 0-5 vol-%
H20 Saturated
The ¾ rich gas stream may e.g. comprise Hydrogen, Carbonmonoxide, Carbondioxide, Water, and Methane. In case of a methanol loop purge gas the ¾ rich stream comprises
H2 70-85 vol
CO 0-8 vol-%
C02 2-10 vol-
CH4 5-20 vol-
Methanol 0.3-1 vol
The present process and plant may advantageously be part of a revamp of an existing plant such as a methanol production plant . An example of parameters for the RWGS step is given below:
Figure imgf000009_0001
Fig. 1 shows a diagram of the plan/process according to the present invention wherein a synthesis gas generation step 1 is arranged to receive a hydrocarbon or carboneous feed stock 2 and in a synthesis gas generation process provide a syngas 3. A production step 4 is arranged to receive the syngas and produce a product stream (5) . A reverse water gas shift step 6 is arranged to receive a ¾ rich gas stream 7 and a CO2 feed 8 and in a RWGS process obtain a reverse shifted gas stream 9. The plant/process furthermore has means 10 for adding said reverse shifted gas stream to the synthesis gas stream. Upstream the reverse water gas shift process a ¾ recovery unit 11 can be arranged to pro¬ vide a gas stream 7 which has an increased ¾ concentration compare to what is received from the production step 4. Such a ¾ recovery unit may for example be used where a purge 12 from the production step 4 is used to provide the ¾ rich stream. From the recovery unit a residual gas stream 13 may be provided e.g. to burners etc. Thus according to the present invention is provided a pro¬ cess and a plant by which a mixture of CO2 and ¾ stream is send to a reactor with a catalyst active towards the Water Gas Shift Reaction, a RWG shift (C02 + H2 -» CO + H20) can be obtained, improving the CO/CO2 ratio, and thus the reac- tivity of the synthesis gas, reducing the required catalyst volume and/or heat transfer area in the production step, such as a methanol synthesis reactor. The present process and plant may be a particular advantage for revamp pro¬ jects, where the size of reformer and/or Methanol reactor is given by existing structures.

Claims

Production plant comprising
- a synthesis gas generation step arranged to receive a hydrocarbon or carboneous feed stock and in a synthesis gas generation process provide a syngas
- a production step arranged to receive the syngas and produce a product stream
- a reverse water gas shift step arranged to receive a ¾ rich gas stream and a CO2 feed and in a RWGS step obtain a reverse shifted gas stream, and
- means for adding said reverse shifted gas stream to the synthesis gas stream.
. Production plant according to claim 1 wherein the pro duction step is a methanol synthesis loop arranged to receive the syngas/reverse shifted gas mixture and produce a Methanol-rich product stream. 3. Production plant according to claim 1 wherein the production step is a purification unit producing a product gas rich in Carbonmonoxide .
Production plant according to any of the proceeding claims wherein the synthesis gas generation step is a reforming step, a gasification step, or a partial oxi dation step.
5. Production plant according to any of the proceeding claims wherein the reverse shifted gas stream is pro¬ vided downstream the synthesis gas generation step.
6. Production plant according to any of the proceeding claims wherein the RWGS step comprises a hydrogen re¬ covery unit upstream the RWGS step.
7. Production plant according to any of the proceeding claims wherein the ¾ rich gas stream is a purge gas 12 from the production step.
8. Production plant according to any of the proceeding claims wherein the CO2 feed is provided from under¬ ground natural CO2 rich gas reservoir.
9. Production plant according to any of the proceeding claims wherein the CO2 feed is provided from a purifi¬ cation unit such as amine wash, PSA, etc. removing CO2 from a synthesis gas, flue gas, or natural gas.
10. Production plant according to any of the proceed¬ ing claims wherein the RWGS step comprises a High Tem¬ perature Shift Catalyst (e.g. Tops0e SK-201 or SK-501) or a UltraHigh Temperature Shift Catalyst.
11. Production plant according to any of the proceeding claims wherein the hydrogen recovery unit is a membrane unit, PSA unit or cryogenic unit.
12. Production plant according to a claim 3 wherein the purification unit producing a CO stream or CO-rich stream is a membrane unit or a cryogenic unit.
13. A process for adjusting the CO/CO2 ratio in a synthesis gas, said process comprising
- in a Methanol loop producing a Methanol stream from a synthesis gas
- in a RWGS loop producing in a RWGS step a shifted gas stream at least from a CO2 feed and a ¾ rich gas stream, and
- adding the produced shifted gas stream to the syn¬ gas upstream the Methanol loop.
14. A process according to claim 13 wherein the ¾
rich gas stream is a purge gas from the Methanol loop.
15. A process according to any of the proceeding
claims 13-14 wherein the shifted gas stream is pro¬ duced over a High Temperature Shift Catalyst (e.g.
Tops0e SK-201 or SK-501) or a UltraHigh Temperature Shift Catalyst. 16. A process according to any of the proceeding
claims 13-15 wherein the RWGS inlet temp is 250 - 750 °C.
A process according to any of the proceeding claims 13-16 wherein the RWGS outlet temp is 200- °C.
18. A process according to any of the proceeding
claims 13- 17 wherein the produced reverse shifted gas has a CO/CO2 ratio of 0.05 - 3.
PCT/EP2015/061668 2014-05-27 2015-05-27 Increasing co/co2 ratio in syngas by reverse water gas shift WO2015181214A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EA201692381A EA201692381A1 (en) 2014-05-27 2015-05-27 INCREASE CO / CO PROPORTION IN SYNTHETIC GAS THROUGH WATER GAS SHIFT REVERSE
US15/313,053 US20170197829A1 (en) 2014-05-27 2015-05-27 Increasing co/co2 ratio in syngas by reverse water gas shift
MX2016015414A MX2016015414A (en) 2014-05-27 2015-05-27 Increasing co/co2 ratio in syngas by reverse water gas shift.
CN201580027440.9A CN106414313A (en) 2014-05-27 2015-05-27 Increasing co/co2 ratio in syngas by reverse water gas shift

Applications Claiming Priority (2)

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DKPA201400286 2014-05-27
DK201400286 2014-05-27

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CN110603347A (en) * 2017-05-11 2019-12-20 托普索公司 Process for generating synthesis gas for use in hydroformylation plants

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US20090012188A1 (en) * 2006-08-08 2009-01-08 Alexandre Rojey Process for the production of synthesis gas with conversion of CO2 into hydrogen
WO2010069549A1 (en) * 2008-12-17 2010-06-24 Saudi Basic Industries Corporation Process for increasing the carbon monoxide content of a syngas mixture
US20120241676A1 (en) * 2009-08-04 2012-09-27 Sk Innovations Co., Ltd. Method for gasification of carbon-containing materials by thermal decomposition of methane and conversion of carbon dioxide
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GB2168718A (en) * 1984-10-29 1986-06-25 Humphreys & Glasgow Ltd Producing synthesis gas
WO2005026093A1 (en) * 2003-09-17 2005-03-24 Korea Institute Of Science And Technology Method for the production of dimethyl ether
US20090012188A1 (en) * 2006-08-08 2009-01-08 Alexandre Rojey Process for the production of synthesis gas with conversion of CO2 into hydrogen
WO2010069549A1 (en) * 2008-12-17 2010-06-24 Saudi Basic Industries Corporation Process for increasing the carbon monoxide content of a syngas mixture
US20120241676A1 (en) * 2009-08-04 2012-09-27 Sk Innovations Co., Ltd. Method for gasification of carbon-containing materials by thermal decomposition of methane and conversion of carbon dioxide
WO2013190500A2 (en) * 2012-06-21 2013-12-27 Saudi Basic Industries Corporation Process for producing a synthesis gas mixture

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