WO2024030014A1 - Process for converting carbon dioxide to carbon monoxide - Google Patents
Process for converting carbon dioxide to carbon monoxide Download PDFInfo
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- WO2024030014A1 WO2024030014A1 PCT/MY2022/050068 MY2022050068W WO2024030014A1 WO 2024030014 A1 WO2024030014 A1 WO 2024030014A1 MY 2022050068 W MY2022050068 W MY 2022050068W WO 2024030014 A1 WO2024030014 A1 WO 2024030014A1
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- Prior art keywords
- process according
- carbon
- feedgas
- carbon source
- catalyst
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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
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
-
- 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
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
-
- 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
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 Boudouard reaction is the redox reaction of a chemical equilibrium mixture of carbon monoxide and carbon dioxide at a given temperature. It is the disproportionation of carbon monoxide into carbon dioxide and graphite.
- Equation 1 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
- 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
- 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
- methane a fuel gas mixture which is of use in industry.
- the conversion is dependent on the reactivity of the carbon feedstock and purity of the carbon dioxide feedgas.
- the gasifier commonly requires operational
- An aim of the invention therefore is to provide a method for converting carbon dioxide to carbon monoxide which overcomes the above issues.
- a process for converting carbon dioxide to carbon monoxide comprising the steps of: introducing a feedgas, a carbon source, and a catalyst into a reactor, said feedgas comprising carbon dioxide; operating said reactor at a temperature of 700-1000°C to convert the feedgas and carbon source into a product comprising carbon monoxide; characterised in that the carbon source is high sulphur petroleum coke.
- the combination of the specified carbon source and catalyst means that the process can take place at a temperature less than 1000°C, which reduces the energy required (and therefore the costs) compared to prior art processes.
- a further advantage is that the process utilises the petroleum coke which is a waste material from refineries.
- 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 reactor operates at a temperature of around 900°C, typically at a pressure of less than 5 bar. Typically the reactor operates at a pressure of 1-3 bar. Advantageously less energy is required as the reactor also operates at a lower pressure than a conventional gasifier which may operated at 30-40 bar.
- the feedgas comprises methane.
- the resulting product comprises hydrogen, in accordance with Equation 2, which reduces the amount of hydrogen required to produce syngas: (Equation 2)
- the feedgas comprises up to 12% methane.
- the catalyst is an alkali metal salt. In one embodiment the catalyst is potassium carbonate, sodium carbonate, calcium carbonate, magnesium oxide, calcium oxide, calcium hydroxide, or combinations thereof.
- the catalyst is biomass such as ash/char derived from oil palm empty fruit bunches.
- Figure 1 is a schematic diagram of a reactor for gasifying petcoke in accordance with an embodiment of the invention.
- a reactor 2 comprising a carbon source inlet 6 for receiving high sulphur petroleum coke (petcoke) mixed with a catalyst such as potassium carbonate from a feeder 4, and a feedgas inlet 10 for receiving carbon dioxide 12, with or without methane impurities.
- a catalyst such as potassium carbonate from a feeder 4
- a feedgas inlet 10 for receiving carbon dioxide 12, with or without methane impurities.
- the reactor is supplied with fuel gas (a mixture of gas which normally contains methane and ethane) and air via fuel inlet 8 so that it can be heated to a temperature of at least 700°C.
- fuel gas a mixture of gas which normally contains methane and ethane
- air via fuel inlet 8 so that it can be heated to a temperature of at least 700°C.
- This allows the petcoke and carbon dioxide to be gasified to form the carbon monoxide product 16, together with hydrogen if methane was present in the feedgas, which can be collected at the outlet 14.
- the catalyst improves the reactivity of the petcoke. Any unreacted ashes can be removed via the ash outlet 18, although they can also be recycled as a carbon source.
- An operating temperature of 700°C is the minimum temperature required for the reaction thermodynamics, but at this temperature the product yield is only about 30- 40%. However at 900°C the product yield is much higher, at around 70%. Petcoke normally has a sulphur content of 1% or less, but when the sulphur content is higher, e.g. 4-6%, the aforementioned high product yield can be collected at a much lower temperature than the conventional gasifiers, where a temperature exceeding 1000°C is required. In addition, a high pressure is not required, as the reactor can be operated at less than 5 bar. The reduction in temperature and pressure leads to significant energy savings.
- a petcoke sulphur content of more than around 5-6% w/w tends not to be used in order to minimise the amount of hydrogen sulfide that may be produced.
- 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)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
A process for converting carbon dioxide to carbon monoxide comprising the steps of introducing a feedgas, a carbon source, and a catalyst into a reactor, said feedgas comprising carbon dioxide, operating said reactor at a temperature of 700-1000°C to convert the feedgas and carbon source into a product comprising carbon monoxide, wherein the carbon source is high sulphur petroleum coke.
Description
PROCESS FOR CONVERTING CARBON DIOXIDE TO CARBON
MONOXIDE
Field of Invention
The invention relates to process for converting carbon dioxide to carbon monoxide using the reverse Boudouard reaction.
Background
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 Boudouard reaction is the redox reaction of a chemical equilibrium mixture of carbon monoxide and carbon dioxide at a given temperature. It is the disproportionation of carbon monoxide into carbon dioxide and graphite.
Hence 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:
CO2 + C -> 2CO (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. However the conversion is dependent on the reactivity of the carbon feedstock and purity of the carbon dioxide feedgas. In addition the gasifier commonly requires operational temperatures of at least 1000°C, and is therefore expensive in terms of the energy needed.
An aim of the invention therefore is to provide a method for converting carbon dioxide to carbon monoxide which overcomes the above issues.
Summary of Invention
In an aspect of the invention, there is provided a process for converting carbon dioxide to carbon monoxide comprising the steps of: introducing a feedgas, a carbon source, and a catalyst into a reactor, said feedgas comprising carbon dioxide; operating said reactor at a temperature of 700-1000°C to convert the feedgas and carbon source into a product comprising carbon monoxide; characterised in that the carbon source is high sulphur petroleum coke.
Advantageously the combination of the specified carbon source and catalyst means that the process can take place at a temperature less than 1000°C, which reduces the energy required (and therefore the costs) compared to prior art processes. A further advantage is that the process utilises the petroleum coke which is a waste material from refineries.
In one embodiment 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.
In one embodiment the reactor operates at a temperature of around 900°C, typically at a pressure of less than 5 bar. Typically the reactor operates at a pressure of 1-3 bar. Advantageously less energy is required as the reactor also operates at a lower pressure than a conventional gasifier which may operated at 30-40 bar.
In one embodiment the feedgas comprises methane. Advantageously the resulting product comprises hydrogen, in accordance with Equation 2, which reduces the amount of hydrogen required to produce syngas:
(Equation 2)
In one embodiment the feedgas comprises up to 12% methane.
In one embodiment the catalyst is an alkali metal salt.
In one embodiment the catalyst is potassium carbonate, sodium carbonate, calcium carbonate, magnesium oxide, calcium oxide, calcium hydroxide, or combinations thereof.
In a further embodiment the catalyst is biomass such as ash/char derived from oil palm empty fruit bunches.
Brief Description of Drawings
It will be convenient to further describe the present invention with respect to the accompanying drawings that illustrate possible arrangements of the invention. Other arrangements of the invention are possible, and consequently the particularity of the accompanying drawings is not to be understood as superseding the generality of the preceding description of the invention.
Figure 1 is a schematic diagram of a reactor for gasifying petcoke in accordance with an embodiment of the invention.
Detailed Description
With regard to Figure 1, there is illustrated a reactor 2 comprising a carbon source inlet 6 for receiving high sulphur petroleum coke (petcoke) mixed with a catalyst such as potassium carbonate from a feeder 4, and a feedgas inlet 10 for receiving carbon dioxide 12, with or without methane impurities.
The reactor is supplied with fuel gas (a mixture of gas which normally contains methane and ethane) and air via fuel inlet 8 so that it can be heated to a temperature of at least 700°C. This allows the petcoke and carbon dioxide to be gasified to form the carbon monoxide product 16, together with hydrogen if methane was present in the feedgas, which can be collected at the outlet 14. The catalyst improves the reactivity of the petcoke.
Any unreacted ashes can be removed via the ash outlet 18, although they can also be recycled as a carbon source.
An operating temperature of 700°C is the minimum temperature required for the reaction thermodynamics, but at this temperature the product yield is only about 30- 40%. However at 900°C the product yield is much higher, at around 70%. Petcoke normally has a sulphur content of 1% or less, but when the sulphur content is higher, e.g. 4-6%, the aforementioned high product yield can be collected at a much lower temperature than the conventional gasifiers, where a temperature exceeding 1000°C is required. In addition, a high pressure is not required, as the reactor can be operated at less than 5 bar. The reduction in temperature and pressure leads to significant energy savings.
A petcoke sulphur content of more than around 5-6% w/w tends not to be used in order to minimise the amount of hydrogen sulfide that may be produced.
It will be appreciated that alternative catalysts may be used, and the empty fruit bunches from oil palms form a possible biomass source as they are high in potassium and are also a waste material.
Advantageously the invention allows waste from existing processes to be converted into useful materials, while also improving on the conventional methods of doing so.
It will be appreciated by persons skilled in the art that the present invention may also include further additional modifications made to the process which does not affect the overall functioning of the process.
Claims
1. A process for converting carbon dioxide to carbon monoxide comprising the steps of: introducing a feedgas, a carbon source, and a catalyst into a reactor, said feedgas comprising carbon dioxide; operating said reactor at a temperature of 700-1000°C to convert the feedgas and carbon source into a product comprising carbon monoxide; characterised in that the carbon source is high sulphur petroleum coke.
2. The process according to claim 1 wherein the carbon source has a sulphur content of 4% w/w or more.
3. The process according to claim 2 wherein the carbon source comprises 5-6% w/w sulphur.
4. The process according to claim 1 wherein the reactor operates at a temperature of around 900°C.
5. The process according to claim 1 wherein the reactor operates at a pressure of less than 5 bar.
6. The process according to claim 1 wherein the feedgas comprises methane such that the product comprises hydrogen.
7. The process according to claim 6 wherein the feedgas comprises up to 12% methane.
8. The process according to claim 1 wherein the catalyst is an alkali metal salt.
9. The process according to claim 8 wherein the catalyst is potassium carbonate, sodium carbonate, calcium carbonate, magnesium oxide, calcium oxide, calcium hydroxide, or combinations thereof 10. The process according to claim 1 wherein the catalyst is oil palm empty fruit bunch ash/char biomass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/MY2022/050068 WO2024030014A1 (en) | 2022-08-04 | 2022-08-04 | Process for converting carbon dioxide to carbon monoxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/MY2022/050068 WO2024030014A1 (en) | 2022-08-04 | 2022-08-04 | Process for converting carbon dioxide to carbon monoxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2024030014A1 true WO2024030014A1 (en) | 2024-02-08 |
Family
ID=89849680
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/MY2022/050068 Ceased WO2024030014A1 (en) | 2022-08-04 | 2022-08-04 | Process for converting carbon dioxide to carbon monoxide |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2024030014A1 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5068057A (en) * | 1989-06-12 | 1991-11-26 | Eastman Kodak Company | Conversion of carbon dioxide to carbon monoxide |
| US20130326953A1 (en) * | 2010-12-08 | 2013-12-12 | Sk Innovation Co., Ltd. | Gasification Method for Reducing Emission of Carbon Dioxide |
| WO2016114599A2 (en) * | 2015-01-14 | 2016-07-21 | 전북대학교산학협력단 | Petroleum coke desulfurization device and method using bubbling fluidized bed carbon dioxide gasification |
-
2022
- 2022-08-04 WO PCT/MY2022/050068 patent/WO2024030014A1/en not_active Ceased
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5068057A (en) * | 1989-06-12 | 1991-11-26 | Eastman Kodak Company | Conversion of carbon dioxide to carbon monoxide |
| US20130326953A1 (en) * | 2010-12-08 | 2013-12-12 | Sk Innovation Co., Ltd. | Gasification Method for Reducing Emission of Carbon Dioxide |
| WO2016114599A2 (en) * | 2015-01-14 | 2016-07-21 | 전북대학교산학협력단 | Petroleum coke desulfurization device and method using bubbling fluidized bed carbon dioxide gasification |
Non-Patent Citations (2)
| Title |
|---|
| LAHIJANI, POOYA ET AL.: "Ash of palm empty fruit bunch as a natural catalyst for promoting the CO2 gasification reactivity of biomass char", BIORESOURCE TECHNOLOGY, vol. 132, 2013, pages 351 - 355, XP028990263, DOI: 10.1016/j.biortech.2012.10.092 * |
| MALEKSHAHIAN MARYAM, HILL JOSEPHINE M.: "Potassium catalyzed CO2 gasification of petroleum coke at elevated pressures", FUEL PROCESSING TECHNOLOGY, ELSEVIER BV, NL, vol. 113, 1 September 2013 (2013-09-01), NL , pages 34 - 40, XP093134797, ISSN: 0378-3820, DOI: 10.1016/j.fuproc.2013.03.017 * |
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