WO2024035255A1 - Procédé de conversion de dioxyde de carbone en monoxyde de carbone - Google Patents

Procédé de conversion de dioxyde de carbone en monoxyde de carbone Download PDF

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Publication number
WO2024035255A1
WO2024035255A1 PCT/MY2023/050060 MY2023050060W WO2024035255A1 WO 2024035255 A1 WO2024035255 A1 WO 2024035255A1 MY 2023050060 W MY2023050060 W MY 2023050060W WO 2024035255 A1 WO2024035255 A1 WO 2024035255A1
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WO
WIPO (PCT)
Prior art keywords
reactor
carbon
feed gas
source
carbon dioxide
Prior art date
Application number
PCT/MY2023/050060
Other languages
English (en)
Inventor
Hazratul Mumtaz Binti LAHURI
Syarifah Nurfaizah Binti SYED ADBUL RAHMAN
Yi Herng CHAN
Alia Binti KHALID
Original Assignee
Petroliam Nasional Berhad (Petronas)
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 Petroliam Nasional Berhad (Petronas) filed Critical Petroliam Nasional Berhad (Petronas)
Publication of WO2024035255A1 publication Critical patent/WO2024035255A1/fr

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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
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
    • B01J19/122—Incoherent waves
    • B01J19/126—Microwaves
    • 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
    • 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/049—Composition of the impurity the impurity being carbon
    • 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
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0855—Methods of heating the process for making hydrogen or synthesis gas by electromagnetic heating

Definitions

  • the invention relates to process for converting carbon dioxide to carbon monoxide using the reverse Boudouard reaction.
  • Carbon dioxide emissions due to the burning of fossil fuels is one of the leading sources of global warming. Therefore reducing the amount of carbon dioxide released into the atmosphere through carbon sequestration can help with this problem.
  • the Reverse Boudouard reaction is the process of converting carbon dioxide into carbon monoxide by gasifying carbon-based materials with carbon dioxide as shown in Equation 1:
  • the carbon monoxide product can be used to produce syngas (typically a mixture of 30 to 60% carbon monoxide, 25 to 30% hydrogen, 5 to 15% carbon dioxide, and 0 to 5% methane, depending on the raw materials and processes), a fuel gas mixture which is of use in industry.
  • syngas typically a mixture of 30 to 60% carbon monoxide, 25 to 30% hydrogen, 5 to 15% carbon dioxide, and 0 to 5% methane, depending on the raw materials and processes
  • Carbon dioxide can be employed as a single feed gas or can be combined with methane impurity to form a binary feed gas for the gasification of carbon-based materials.
  • the presence of methane impurity in the carbon dioxide feed gas produces a trace amount of hydrogen as shown in Equation 2, which reduces the amount of hydrogen required to produce syngas:
  • An aim of the invention therefore is to provide an improved method for converting carbon dioxide to carbon monoxide to overcome the above issues.
  • a process for converting carbon dioxide to carbon monoxide comprising the steps of: introducing a feed gas, a carbon source such as high sulphur petroleum coke, and an alkali metal salt catalyst into a reactor, said feed gas comprising carbon dioxide, optionally with methane; operating said reactor at a temperature of up to 900°C and at a pressure of up to 5 bar to convert the feed gas and carbon source into a product comprising carbon monoxide, optionally with hydrogen; characterised in that the reactor utilises a microwave source for heating the reactor and the reactor contains silica carbide to improve mass and heat transfer between the feed gas and carbon source.
  • silica carbide as the reactor bed material enables better absorption of micro wave radiation, conversion of micro wave radiation into heat and heat retention. Additionally, silica carbide ball can be utilised to reduce the pressure drop across the reactor.
  • microwave gasification is able to achieve a 90% CO2 conversion compared to prior art processes that employ thermal heating. Additionally, the microwave gasification process is instantaneous due to volumetric heating in comparison to conventional thermal heating where a longer duration is required during operation due to the nature of thermal heating (convection and conduction of heat).
  • the microwave source typically powered at 1 to 5 kW irradiates the petroleum coke (petcoke) with a radiation frequency of approximately 2450MHz.
  • a high pressure is not required, as the reactor can be operated at 5 bar or less.
  • the low power, temperature and pressure requirement leads to significant energy savings and a lower carbon footprint.
  • the microwave source is solid state and/or a magnetron
  • the carbon source has a sulphur content of 4% w/w or more. Typically the carbon source has a sulphur content of 5-6% w/w.
  • the feed gas comprises methane.
  • the resulting product comprises hydrogen which reduces the amount of hydrogen required to produce syngas.
  • the feed gas comprises up to 12% methane.
  • a further advantage is that the process utilises carbon dioxide obtained from natural gas and petrochemical plants and petroleum coke which is a waste material from refineries.
  • the catalyst is potassium carbonate, sodium carbonate, calcium carbonate, magnesium oxide, calcium oxide, calcium hydroxide, or combinations thereof.
  • the catalyst is potassium carbonate.
  • FIG. 1 is a schematic diagram of a reactor for gasifying petroleum coke in accordance with an embodiment of the invention.
  • Figure 1 illustrates a reactor (2) comprising a carbon source inlet (6) for receiving high sulphur petroleum coke (petcoke) mixed with a catalyst such as an alkali metal salt from a feeder (4), and a feed gas inlet (8) for receiving carbon dioxide, with or without methane impurity.
  • the catalyst is introduced to improve the reactivity of the petcoke.
  • the reactor is a fixed bed reactor equipped with a microwave source (10) so that it can be heated to a temperature of up to 900°C and beyond if required.
  • a microwave source 10
  • the product is subjected to further processing by a particulate separator (14), a cooler (16) and an amine scrubber (18) to yield syngas (22) which can be collected at the outlet (20). Any unreacted ashes can be removed via the ash outlet (24), although they can also be recycled as a carbon source.
  • the reactor is equipped with silica carbide as bed material which enables better absorption of microwave radiation, conversion of microwave radiation into heat and heat retention.
  • silica carbide ball can be utilised to reduce the pressure drop across the reactor.
  • the microwave source typically powered at 1 to 5 kW irradiates the petcoke with a radiation frequency of approximately 2450MHz.
  • the microwave source is solid state and/or a magnetron.
  • a high pressure is not required, as the reactor can be operated at 5 bar or less.
  • the low power, temperature and pressure requirement leads to significant energy savings and a lower carbon footprint.
  • the microwave gasification process allows for volumetric heating where microwave radiation is absorbed by the materials in the reactor and is converted into heat, the microwave gasification process is instantaneous when compared to a conventional gasifier where a longer duration is required during operation, especially during start up and shut down, due to the nature of thermal heating (convection and conduction of heat).
  • Microwave volumetric heating results in consistent and even temperature distribution across the materials in the reactor as compared to thermal heating which is based on conduction and convection causing uneven temperature distribution across the materials in the reactor.
  • microwave gasification process is able to achieve a 90% CO2 conversion compared to a 46% CO2 conversion achieved by a conventional gasifier. This is due to the utilisation of silica carbide in the microwave reactor which improves heat and mass transfer between feed gas and petcoke. Also, carbon being a good microwave absorbing material is able to convert microwave radiation into heat at a higher rate when compared to thermal heating employed in a conventional gasifier.
  • the invention allows waste from existing processes to be converted into useful materials, while also improving on the conventional methods of doing so.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Toxicology (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

L'invention concerne un procédé de conversion de dioxyde de carbone en monoxyde de carbone comprenant les étapes consistant à introduire un gaz d'alimentation comprenant du dioxyde de carbone, une source de carbone et un catalyseur dans un réacteur, faire fonctionner ledit réacteur à une température allant jusqu'à 900°C pour convertir le gaz d'alimentation et la source de carbone en un produit comprenant du monoxyde de carbone, le réacteur étant chauffé à l'aide d'une source de micro-ondes.
PCT/MY2023/050060 2022-08-08 2023-08-04 Procédé de conversion de dioxyde de carbone en monoxyde de carbone WO2024035255A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
MYUI2022004232 2022-08-08
MYUI2022004232 2022-08-08

Publications (1)

Publication Number Publication Date
WO2024035255A1 true WO2024035255A1 (fr) 2024-02-15

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PCT/MY2023/050060 WO2024035255A1 (fr) 2022-08-08 2023-08-04 Procédé de conversion de dioxyde de carbone en monoxyde de carbone

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5266175A (en) * 1990-07-31 1993-11-30 Exxon Research & Engineering Company Conversion of methane, carbon dioxide and water using microwave radiation
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
WO2016114599A2 (fr) * 2015-01-14 2016-07-21 전북대학교산학협력단 Dispositif et procédé de désulfuration de coke de pétrole faisant appel à la gazéification du dioxyde de carbone en lit fluidisé bouillonnant
US20160340195A1 (en) * 2011-12-20 2016-11-24 CCP Technology GmbH Process and system for conversion of carbon dioxide to carbon monixide
WO2020006512A1 (fr) * 2018-06-28 2020-01-02 Resynergi, Inc. Procédés à micro-ondes pour convertir des déchets à base d'hydrocarbures en carburants à base d'huile et de gaz

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5266175A (en) * 1990-07-31 1993-11-30 Exxon Research & Engineering Company Conversion of methane, carbon dioxide and water using microwave radiation
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
US20160340195A1 (en) * 2011-12-20 2016-11-24 CCP Technology GmbH Process and system for conversion of carbon dioxide to carbon monixide
WO2016114599A2 (fr) * 2015-01-14 2016-07-21 전북대학교산학협력단 Dispositif et procédé de désulfuration de coke de pétrole faisant appel à la gazéification du dioxyde de carbone en lit fluidisé bouillonnant
WO2020006512A1 (fr) * 2018-06-28 2020-01-02 Resynergi, Inc. Procédés à micro-ondes pour convertir des déchets à base d'hydrocarbures en carburants à base d'huile et de gaz

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