WO2005005901A1 - 焼成炉及び焼成方法 - Google Patents
焼成炉及び焼成方法 Download PDFInfo
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- WO2005005901A1 WO2005005901A1 PCT/JP2004/005538 JP2004005538W WO2005005901A1 WO 2005005901 A1 WO2005005901 A1 WO 2005005901A1 JP 2004005538 W JP2004005538 W JP 2004005538W WO 2005005901 A1 WO2005005901 A1 WO 2005005901A1
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- methane
- fuel
- hydrogen
- carbon dioxide
- firing
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B17/00—Furnaces of a kind not covered by any preceding group
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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
- 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
- C01B3/384—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 the catalyst being continuously externally heated
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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
- 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
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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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
- 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
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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
- 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
- C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
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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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/066—Integration with other chemical processes with fuel cells
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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
- 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
- C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
- C01B2203/0822—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel the fuel containing hydrogen
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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
- 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
- C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
- C01B2203/0827—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel at least part of the fuel being a recycle stream
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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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
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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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
- C01B2203/107—Platinum catalysts
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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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1076—Copper or zinc-based catalysts
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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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
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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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/16—Controlling the process
- C01B2203/1604—Starting up the process
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- 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
- Y02P10/00—Technologies related to metal processing
- Y02P10/10—Reduction of greenhouse gas [GHG] emissions
- Y02P10/143—Reduction of greenhouse gas [GHG] emissions of methane [CH4]
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- 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
Definitions
- the present invention relates to a firing furnace and a firing method. More specifically, the present invention relates to a combustion exhaust gas in which a combustion gas containing carbon dioxide obtained by burning a fuel containing methane is discharged as combustion exhaust gas. The present invention relates to a firing furnace and a firing method capable of significantly reducing the amount of carbon dioxide contained, effectively using and recovering the heat of combustion gas, and further reducing fuel costs.
- an industrial furnace is used as an apparatus for heating an object to be heated in various industrial fields.
- these industrial furnaces those that heat the object to be heated by burning a fuel containing carbon generate high-temperature combustion gas containing carbon dioxide at the same time as the heat generated by the combustion of the fuel.
- the generated combustion gas was discharged to the outside (hereinafter, the combustion gas discharged to the outside may be referred to as “combustion exhaust gas” or simply “exhaust gas”).
- combustion exhaust gas or simply “exhaust gas”.
- exhaust gas the combustion exhaust gas discharged to the outside
- adverse effects on the environment due to the discharge of such high-temperature exhaust gas have become a problem, and it has also become an issue to recover and reuse the heat of combustion exhaust gas effectively.
- the problem of the generation of exhaust gas containing carbon dioxide has been highlighted in recent years due to the problem of global warming, etc., and the amount of carbon dioxide contained in the exhaust gas from industrial furnaces should be reduced. Has been strongly demanded.
- the firing furnace and firing method of the present invention for solving the above problems are as follows.
- Combustion means for generating a combustion gas by combusting a fuel containing inflowing methane, and heating and firing the object to be fired carried therein by the combustion gas, and the combustion gas after firing And a reforming raw material consisting of reforming methane auxiliary fuel and steam mainly composed of methane that has flowed into the inside and filled with a methane reforming catalyst. Is brought into contact with the methane reforming catalyst while being heated by the combustion gas, thereby reacting the methane and the water vapor in the reforming raw material to generate a reformed gas containing hydrogen and carbon dioxide.
- a firing furnace further comprising a methane reformer.
- the methane reformer is disposed in a calcining furnace body, and the reforming raw material is heated by the combustion gas and brought into contact with the methane reforming catalyst to generate the reformed gas.
- the baking furnace as described in.
- the methane reformer is disposed outside the calcining furnace body, and contacts the methane reforming catalyst while heating the reforming raw material with the combustion gas discharged to the outside of the calcining furnace body.
- a fuel cell that generates electricity by reacting hydrogen with oxygen or air is further provided, wherein part or all of the hydrogen contained in the reformed gas is used as fuel cell hydrogen.
- a part of the hydrogen fuel is used as a fuel cell hydrogen for reaction with oxygen or air in the fuel cell, and the remainder is mixed with a methane main fuel for mixing mainly composed of methane.
- the volume ratio of the reforming methane auxiliary fuel to the mixing methane main fuel is 5:95 to 100: 0 [7] or [ [8] The firing furnace according to [8].
- the apparatus further includes a carbon dioxide fixing device for fixing carbon dioxide in the residual gas separated by the hydrogen separator so that the carbon dioxide is not released to the outside in a gas state.
- the carbon dioxide fixing device has sodium hydroxide as an immobilizing agent for fixing carbon dioxide, and sodium carbonate and carbon dioxide can be reacted to generate sodium carbonate.
- the baking furnace as described in.
- the firing furnace body is a continuous firing furnace body in which the body to be fired is continuously carried into the interior, and the body to be fired is heated inside and then continuously carried out to the outside.
- the baking furnace in any one of [12].
- the fired body is a honeycomb structure.
- Combustion gas is generated by injecting and burning a fuel containing methane into the combustion means, and the combustion gas generated by the combustion means is introduced into the inside of the calcining furnace body, and the combustion gas causes the combustion gas to enter the combustion means.
- a fired method in which the fired body to be fired is heated and fired, and the burned combustion gas is discharged to the outside of the main body of the firing furnace.
- the fired methane reformer is filled with a methane reforming catalyst.
- a reforming raw material consisting of reforming methane auxiliary fuel and steam, the main component of which is methane
- a firing method in which the methane in the reforming raw material and the water vapor are reacted to generate a reformed gas containing hydrogen and carbon dioxide.
- the methane reformer is disposed in the calcining furnace main body, and the reforming raw material is heated by the combustion gas and brought into contact with the methane reforming catalyst to generate the reformed gas.
- the baking method as described in.
- the methane reformer is disposed outside the calcining furnace body, and the reforming raw material is brought into contact with the methane reforming catalyst while being heated by the combustion gas discharged to the outside of the calcining furnace body.
- a part of or all of hydrogen contained in the reformed gas is used as fuel cell hydrogen, and electricity is generated by reacting with oxygen or air in the fuel cell. [17] to [19] Firing method.
- the reformed gas generated in the methane reformer is caused to flow into a hydrogen separator, and the hydrogen in the reformed gas is selectively separated to mainly contain hydrogen.
- the firing method according to any one of [17] to [20], wherein the fuel is separated into hydrogen fuel and residual gas containing carbon dioxide.
- the residual gas separated by the hydrogen separator is allowed to flow into a carbon dioxide fixing device, and carbon dioxide in the residual gas is fixed so as not to be released to the outside in a gas state.
- the firing method according to any one of the above.
- the carbon dioxide fixing device has sodium hydroxide as an immobilizing agent for fixing carbon dioxide, and reacts the sodium hydroxide with carbon dioxide to generate sodium carbonate.
- a continuous firing furnace body is used in which the body to be fired is continuously carried into the interior, the body to be fired is heated inside, and then continuously carried out to the outside.
- the firing method according to any one of [28].
- Liquefied natural gas is used as at least one of the reforming-medium auxiliary fuel and the mixing-medium main fuel. [17] to [29] Firing method.
- FIG. 1 is a block flow diagram schematically showing one embodiment of a firing furnace of the present invention.
- FIG. 2 is a block flow diagram schematically showing another embodiment of the firing furnace of the present invention. is there.
- FIG. 3 is a block diagram schematically showing still another embodiment of the firing furnace of the present invention.
- FIG. 4 is a block flow diagram schematically showing still another embodiment of the firing furnace of the present invention.
- FIG. 5 is a cross-sectional view schematically showing a firing furnace main body used in still another embodiment of the firing furnace of the present invention, cut along a plane perpendicular to the longitudinal direction.
- FIG. 6 is a cross-sectional view schematically showing a firing furnace main body used in still another embodiment of the firing furnace of the present invention, cut along a plane perpendicular to the longitudinal direction.
- the present invention effectively recovers the heat of combustion gas when exhausting the combustion gas containing carbon dioxide obtained by burning fuel containing carbon, particularly methane, to the outside, and further fuel
- An object of the present invention is to provide a firing furnace and a firing method capable of reducing costs.
- the amount of carbon dioxide contained in the combustion gas is fixed, the amount of carbon dioxide discharged to the outside can be greatly reduced.
- the amount of heat of the combustion gas is used as the amount of heat necessary for the endothermic reaction when the reforming raw material is reacted with the methane reforming catalyst.
- a part of the fuel can be effectively recovered as the combustion heat of the fuel, reducing the total amount of fuel used.
- a method of recovering the heat of the combustion gas a method of recovering from the combustion gas discharged to the outside of the firing furnace body (hereinafter sometimes referred to as “combustion exhaust gas”), There is a method using the heat of combustion gas, and both of them may be performed simultaneously. If the heat of the combustion gas is used in the main body of the firing furnace, it is possible to eliminate heat dissipation when the combustion exhaust gas moves, and to recover heat more efficiently. '
- methane main fuel for mixing mainly composed of methane methane auxiliary fuel for reforming mainly composed of methane, and water vapor Reacting raw material consisting of Since the hydrogen fuel obtained by mixing with the above is used, the carbon dioxide content in the combustion exhaust gas can be greatly reduced.
- the carbon dioxide produced when the reforming raw material is reacted with the methane reforming catalyst is fixed by the carbon dioxide fixing device, the carbon dioxide produced from the reforming raw material is in the state of gas in the external state. Will not be released.
- the carbon dioxide fixed here corresponds to the reduced carbon dioxide in the carbon dioxide in the combustion exhaust gas.
- the amount of heat necessary for the endothermic reaction when the reforming raw material is reacted with the methane reforming catalyst the amount of combustion gas in the firing furnace body or the amount of combustion exhaust gas discharged from the firing furnace body is used. Part of the heat of the combustion gas (part of the exhaust heat from the combustion exhaust gas) can be effectively recovered as the combustion heat of the fuel, and the total amount of fuel used can be reduced.
- the methane reformer using the calorific value of the combustion gas in the calcination furnace body or the heat of the combustion exhaust gas discharged from the calcination furnace body, Carbon dioxide (reformed gas) is generated, hydrogen is separated from the reformed gas by a hydrogen separator, hydrogen fuel is taken out, and the hydrogen fuel is used as fuel cell hydrogen to generate power in the fuel cell.
- the heat of combustion exhaust gas can be effectively recovered and used for power generation by the fuel cell.
- a part of the hydrogen fuel can be used as the mixed fuel, and the remaining part can be used as hydrogen for the fuel cell. Further, all of the hydrogen fuel may be used as the mixed fuel.
- the firing method of the present invention as in the case of firing using the firing furnace of the present invention described above, the amount of heat necessary for the endothermic reaction when the reforming raw material is reacted with the methane reforming catalyst, Since the calorific value of the combustion gas in the calcining furnace body or the calorific value of the combustion exhaust gas discharged from the calcining furnace body is used, a part of the heat of the combustion gas (combustion exhaust gas) will be recovered as the combustion heat of the fuel. The total amount of fuel used can be reduced. Further, by using the heat of the combustion gas instead of using the heat of the combustion exhaust gas, it is possible to eliminate heat dissipation when the combustion exhaust gas moves, and to recover the heat amount more efficiently.
- hydrogen and carbon dioxide are converted from methane and steam in a methane reformer using the heat of combustion exhaust gas discharged from the firing furnace body.
- hydrogen is separated from the reformed gas by a hydrogen separator and hydrogen fuel is taken out, and the hydrogen fuel is used as fuel cell hydrogen to generate power in the fuel cell. Heat can be effectively recovered and used for power generation by fuel cells.
- a mixing main fuel for mixing mainly composed of meven and a reforming mainly composed of methane As a fuel containing methane to be burned by the combustion means, a mixing main fuel for mixing mainly composed of meven and a reforming mainly composed of methane. Because a mixed fuel of hydrogen obtained by reacting a reforming raw material consisting of methane auxiliary fuel and steam with a methane reforming catalyst is used, the carbon dioxide content in the combustion exhaust gas is greatly increased. Can be reduced.
- the carbon dioxide generated when the reforming raw material is reacted with the methane reforming catalyst is fixed by the carbon dioxide fixing device, the carbon dioxide generated from the reforming raw material is in the state of gas in the external state. It is preferable because it can be prevented from being released to the surface.
- the carbon dioxide fixed here corresponds to the carbon dioxide reduced in the carbon dioxide in the combustion exhaust gas.
- FIG. 1 is a block flow diagram schematically showing one embodiment of a firing furnace of the present invention.
- the arrows indicate the state in which each fuel, combustion exhaust gas, water vapor, and other substances move.
- the firing furnace 100 includes a combustion means 2 for burning the fuel 11 containing inflowing methane to generate combustion gas, and the combustion gas 2 is carried into the interior by the combustion gas.
- a firing furnace main body 1 for discharging the combustion gas after firing to the outside while heating the fired body to be fired, and the inside is filled with a methane reforming catalyst 6, and the methane flowing into it is mainly used.
- Reforming raw material 2 3 consisting of reforming methane auxiliary fuel 2 1 and steam 2 2 as components is heated by the combustion gas (combustion exhaust gas 1 2) discharged from the firing furnace body 1 to the outside, and methane reforming
- combustion exhaust gas 1 2 combustion exhaust gas 1 2
- methane reforming By contacting with catalyst 6, methane in reforming raw material 23 and water vapor 22 are reacted to contain hydrogen and carbon dioxide.
- a reformed gas 2 4 is generated (a methane reforming reaction is performed).
- a methane reformer 3 is further provided.
- the methane reforming reaction in the methane reformer 3 is performed while using the heat of the combustion exhaust gas 12, thereby effectively using the heat of the combustion exhaust gas 12. Can be reused.
- the firing furnace 100 of the present embodiment allows the reformed gas 24 generated in the methane reformer 3 to flow into the reformed gas 24 to cause hydrogen in the reformed gas 24 to flow.
- Hydrogen separator 4 that is selectively separated and separated into hydrogen fuel 25 containing hydrogen as a main component 25 and residual gas 26 containing carbon dioxide 6, and residual gas 26 6 separated by hydrogen separator 4
- a carbon dioxide fixing device 5 for fixing the carbon dioxide to prevent the carbon dioxide from being released to the outside in the state of gas.
- the firing furnace 100 of the present embodiment has a combusting means 2 that flows into the mixing methane main fuel 31 containing methane as a main component and the hydrogen fuel 25 separated by the hydrogen separator 4 (mixed) Combustion of mixed fuel 3 2 with hydrogen fuel 2 8), that is, by using mixed fuel 3 2 as fuel 11 containing methane and generating combustion gas,
- a combusting means 2 that flows into the mixing methane main fuel 31 containing methane as a main component and the hydrogen fuel 25 separated by the hydrogen separator 4 (mixed) Combustion of mixed fuel 3 2 with hydrogen fuel 2 8), that is, by using mixed fuel 3 2 as fuel 11 containing methane and generating combustion gas,
- This makes it possible to reduce the carbon dioxide content.
- the combustion exhaust gas 1 2 is used in the methane reformer 3
- the amount of carbon dioxide emitted to the outside as the reformer exhaust gas 4 3 is reduced.
- the carbon dioxide fixing device 5 allows sodium hydroxide to flow in as an immobilizing agent 4 1 for immobilizing carbon dioxide therein, and the immobilizing agent 4 1 and the residual gas 2 6 are brought into contact with each other to immobilize it.
- the agent 41 is made to absorb the carbon dioxide contained in the residual gas 26, produce sodium carbonate, and discharge the waste liquid 42 containing sodium carbonate to the outside.
- “mainly composed of methane” means that the content of methane is 80 (volume%) or more.
- the immobilizing agent 41 is not particularly limited as long as it can react with carbon dioxide or absorb carbon dioxide, and examples thereof include Na OH and Mg (OH) 2 .
- the specified piping is used between each device. Connected, each fuel, water vapor, etc. flow and move in the pipe.
- the methane main fuel 3 1 for mixing and the hydrogen fuel 2 5 (hydrogen fuel 2 for mixing 2 8) and mixed fuel 3 2 is used, so that the mixed fuel 3 2 (fuel 1 1) contains hydrogen (hydrogen fuel 2 5) that does not generate carbon dioxide even when burned. Can be reduced.
- the content of hydrogen contained in the mixed fuel 32 (hydrogen Z mixed fuel) is preferably 5 to 95 (volume%), and more preferably 25 to 75 (volume%). If it is less than 5 (volume%), the carbon dioxide reduction effect may not be sufficient. If it is more than 9 (volume%), not only the combustion exhaust gas but also other gases when the methane reforming reaction is performed.
- a heat source may be required.
- carbon dioxide produced when the reforming raw material 23 is reacted with the methane reforming catalyst 6 is fixed by the carbon dioxide fixing device 5, carbon dioxide produced from the reforming raw material 23 is gas. In this state, it is not released to the outside.
- the calorific value of the combustion exhaust gas 1 2 discharged from the calcining furnace body 1 is used as the amount of heat necessary for the endothermic reaction when the reforming raw material 2 3 is reacted with the methane reforming catalyst 6, the combustion exhaust gas A part of the exhaust heat of 1 and 2 can be effectively recovered as the heat of combustion of the fuel, which can reduce the total amount of fuel used.
- the heat source for the methane reforming reaction can use not only the combustion exhaust gas but also the heat dissipated from the furnace wall and the heat discarded when cooling the kiln tools used during ceramic firing.
- the firing furnace 100 of the present embodiment further includes a fuel cell 7.
- the fuel cell 7 generates electricity by reacting hydrogen (hydrogen for fuel cells) with oxygen or air.
- hydrogen hydrogen for fuel cells
- a portion of the hydrogen fuel 25 obtained by separation in the hydrogen separator 4 is branched as hydrogen 28 for fuel cells, and this can be used for the fuel cell 7 to generate electricity.
- the reformed gas 24 discharged from the reformer 3 may be used directly in the fuel cell 7 without passing through the hydrogen separator 4. Since the hydrogen fuel 25 obtained by separation with the hydrogen separator 4 has a high purity of hydrogen contained therein, the fuel cell 7 can efficiently generate power. For example, when the fuel cell is generated using normal hydrogen, the power efficiency is about 40%.
- the power efficiency is 60 to 70. It will be drastically higher with%.
- Hydrogen separator Part of the hydrogen fuel 25 obtained by separation in step 4 is finally burned by the combustion means 2 as hydrogen fuel 28 for mixing, and the remainder is used for power generation in the fuel cell 7 as hydrogen 27 for fuel cells.
- the amount of carbon dioxide contained in the combustion exhaust gas 12 can be reduced, and at the same time, the heat of the combustion exhaust gas 12 can be effectively recovered and used for power generation.
- the hydrogen in the reformed gas 24 is used for power generation.
- residual gas is discharged from the fuel cell 7.
- This residual gas is preferably mixed with fuel and burned by a combustion means.
- the residual gas is discharged from the fuel cell 7. It is preferable to mix them with the combustion means.
- the residual gas discharged from the fuel cell is passed through the carbon dioxide fixing device to remove carbon dioxide. Then, it is preferable that the fuel is mixed with fuel and burned by a combustion means.
- the total amount of the hydrogen fuel 25 may be used as the mixing hydrogen fuel 28, or may be divided into the mixing hydrogen fuel 28 and the fuel cell hydrogen 27.
- the ratio when dividing hydrogen for fuel 28 and fuel cell hydrogen 27 is not particularly limited, and the carbon dioxide emission and power generation amount should be balanced to an appropriate value as appropriate. That's fine.
- the firing furnace body 1 is not particularly limited, and ceramic or the like is carried inside as a body to be fired, and methane is burned by the burning means 2.
- a fired body such as ceramic is usually used to burn a fired body such as a ceramic with a combustion gas generated by burning a fuel containing 11.
- a ceramic honeycomb structure can be suitably fired.
- the ceramic honeycomb structure is a structure of a honeycomb structure having a plurality of cells, which are made of ceramic and serve as fluid flow paths partitioned by partition walls.
- the firing furnace body 1 is a bar that fires a predetermined amount of an object to be fired intermittently one time at a time.
- a fired body such as a ceramic honeycomb structure is continuously carried into the interior, the fired body is heated and fired inside, and then continuously carried out to the outside.
- a firing furnace body 1 of the formula is preferred.
- the combustion exhaust gas 12 can be discharged from the firing furnace body 1 stably and stably. Therefore, in the methane reformer 3, the heat of the combustion exhaust gas 12 is used for methane reforming.
- the reaction can be carried out stably, whereby the hydrogen fuel 25 can be supplied stably, and the mixed fuel obtained by mixing the hydrogen fuel 25 and the mixing methane main fuel 31 3 2 can be stably supplied to the combustion means 2.
- the combustion means 2 is not particularly limited as long as it can efficiently burn the fuel 11 containing methane and hydrogen. Absent.
- the combustion means 2 may be disposed outside the firing furnace body 1 so that the combustion gas flows into the firing furnace body 1 through a pipe, but the combustion means 2 may be disposed inside the firing furnace body 1. Good. Further, only one combustion means 2 or a plurality of combustion means 2 may be provided in the firing furnace main body 1 depending on its capacity, the size of the combustion furnace main body 1 and the like.
- the combustion means 2 is not particularly limited as long as it is a burner having a line for introducing air and fuel gas. A regenerative type panner or the like that preheats combustion air can also be suitably used.
- the methane reformer 3 is filled with a methane reforming catalyst 6 inside a vessel made of stainless steel or ceramics, and the methane flowing into the methane reformer 6
- the reforming raw material 2 3 comprising the reforming methane secondary fuel 21 and the steam 22 as the main components is brought into contact with the methane reforming catalyst 6 while being heated by the combustion exhaust gas 12 and the reforming raw material 23
- the reformed gas 24 containing hydrogen and carbon dioxide is generated by reacting the methane and steam 22 2 in the reactor (the methane reforming reaction is performed).
- hydrogen can be obtained by reacting methane, and carbon in methane can be finally fixed without being released to the outside. Anything is acceptable.
- the immobilization of carbon in methane may be performed in a subsequent process of the methane reformer 3, and in the present embodiment, the carbon dioxide fixing unit 5 fixes carbon dioxide.
- Reaction rate of methane and water in the methane reformer 3 hydrogen to be generated for the input raw materials (methane and water)
- the ratio of the amount of actually generated hydrogen to the theoretical value of the amount of hydrogen is preferably 50 (mol%) or more. If it is lower than 50 (mol%), the amount of fuel used may increase. Also, the higher the reaction rate of methane and water, the better.
- the reformed gas 24 produced in the methane reformer 3 preferably has a hydrogen content of 10 to 80 mol%, and a carbon dioxide content of 1 to 20 mol%. It is preferable.
- the shape and shape of the container filled with the methane reforming catalyst 6 is not particularly limited, and may be any shape such as a cylindrical shape or a box shape.
- methane reformer 3 for example, called “ICI method”, methane (1 mol) and water (2 mol) are heated to a temperature of 7 0 to 9 5 0 (° C) under a nickel-containing catalyst. ), Endothermic reaction under the conditions of pressure 1.0 1 X 1 0 5 to 4 0.5 2 X 1 0 5 (N / m 2 ), hydrogen (4 mol) and carbon dioxide (1 mol)
- nickel-containing catalyst for example, a Synyix catalyst manufactured by Johnson Matthey can be suitably used.
- effective catalysts include Ni-based, Cu-based, transition metal-based, and platinum-based catalysts.
- the temperature of the combustion exhaust gas 12 is preferably 2 00 to 9 50 (° C). If it is lower than 20 0 (° C), it may be difficult to react methane and water vapor, and if it is higher than 95 0 (° C), the durability of the members constituting the reactor may be lowered.
- the amount of heat of the combustion exhaust gas 12 is not particularly limited because it varies depending on the type and size of the firing furnace body 1.
- the hydrogen separator 4 is reformed by flowing the reformed gas 24 containing hydrogen and carbon dioxide generated in the methane reformer 3 into the interior. Hydrogen gas mainly containing hydrogen by selectively separating hydrogen in the gas 2 4 2 5 And residual gas 26 containing carbon dioxide.
- the hydrogen separator 4 is not particularly limited as long as it can selectively separate hydrogen from a mixed gas containing hydrogen.
- palladium or an alloy containing palladium formed into a film The hydrogen separation membrane is formed in a cylindrical shape, and the hydrogen separation membrane is disposed in a cylindrical container made of stainless steel or the like, so that the space on the inner side of the cylinder of the hydrogen separation membrane and the space on the outer peripheral side are not connected.
- the mixed gas containing hydrogen is introduced into the cylindrical container, and introduced into the inner side of the cylinder of the hydrogen separation membrane, and only hydrogen is selectively passed from the inner side to the outer peripheral side of the hydrogen separation membrane.
- the hydrogen flowing out to the outer peripheral side of the hydrogen separation membrane cylinder is caused to flow out as hydrogen fuel 25 to the outside of the cylindrical container, and other gases are left as residual gas 26 inside the cylinder of the hydrogen separation membrane. Let it pass and let it flow out of the cylindrical container What was constituted in this way can be used conveniently.
- the mixed gas containing hydrogen may be introduced to the outside of the cylinder of the hydrogen separation membrane so that the hydrogen flows out to the inside of the cylinder of the hydrogen separation membrane.
- the separated hydrogen is used as a hydrogen fuel 25 containing hydrogen as a main component, and the remaining gas 26 containing other carbon dioxide is sent to the carbon dioxide fixing device 5.
- “Hydrogen-based” in the hydrogen fuel 25 mainly containing hydrogen means that the hydrogen content is 50 (volume%) or more.
- the cylindrical container does not need to be cylindrical, and may be, for example, a box shape as long as it has a space inside.
- the hydrogen separation membrane may be formed so as to be disposed on the surface or inside of a porous body made of ceramic or the like. The hydrogen separation membrane does not need to be cylindrical, and may be flat or any other shape.
- the hydrogen separator 4 is formed integrally with the methane reformer 3, and the methane reformer 3
- the hydrogen generated in the methane reformer 3 is selectively separated by the hydrogen separator 4 disposed in the methane reformer 3, and the hydrogen is discharged from the methane reformer 3 to be used as hydrogen fuel 25.
- a hydrogen separation membrane formed in a cylindrical shape is disposed in the methane reformer 3, and the methane reforming catalyst 6 is disposed inside the cylinder. Can be arranged.
- the hydrogen separation membrane functions as the hydrogen separator 4, and the hydrogen separator 4 is disposed in the methane reformer 3.
- the reforming raw material 23 is introduced into the hydrogen separation membrane cylinder and disposed inside the hydrogen separation membrane cylinder.
- the generated methane reforming catalyst 6 can generate hydrogen, and the generated hydrogen can flow out to the outer peripheral side of the cylinder of the hydrogen separation membrane.
- the outflowed hydrogen is used as hydrogen fuel 25.
- the hydrogen separation efficiency when hydrogen is separated from the reformed gas 24 by the hydrogen separator 4 is (the amount of hydrogen contained in the reformed gas 24: the amount of separated hydrogen) is 50. : 50-1: 99 (volume ratio) is preferable. If it is lower than 50:50 (volume ratio), fuel may not be used efficiently. The higher the separation efficiency, the better. However, 1:99 (volume ratio) is sufficient for the recovery efficiency of combustion hydrogen. In order to achieve higher separation efficiency, the cost becomes higher. There is.
- the carbon dioxide fixing device 5 releases the carbon dioxide in the residual gas 26 separated by the hydrogen separator 4 to the outside in the form of gas. It is fixed so that it is not done.
- the carbon dioxide fixing device 5 is not particularly limited as long as it can fix the carbon dioxide contained in the residual gas 26 and prevent the carbon dioxide from being released to the outside in a gas state.
- an aqueous solution of sodium hydroxide is placed as a fixing agent 41 for immobilizing carbon dioxide in a predetermined container, residual gas 26 is introduced into it, and aqueous sodium hydroxide solution is used as residual gas.
- immobilization of carbon dioxide means that carbon dioxide is not released in the form of gas by reacting with other substances or absorbing them into other substances. .
- sodium carbonate can be generated by the carbon dioxide fixing device 5.
- the waste liquid 42 discharged from the carbon dioxide fixing device 5 can be a sodium carbonate-containing solution, and the carbon dioxide fixing device 5 can be used as a sodium carbonate generator.
- the carbon dioxide fixing device 5 will be described in more detail with reference to the case where it is used as a sodium carbonate generator.
- the structure of the above-mentioned predetermined container constituting the carbon dioxide fixing device 5 is not particularly limited as long as sodium hydroxide can be put inside and reacted with carbon dioxide to generate sodium carbonate. .
- a cylindrical container having at least one introduction pipe for introducing residual gas and sodium hydroxide, and a discharge section for discharging waste liquid hereinafter sometimes referred to as “sodium carbonate-containing solution”.
- the shape of the container is not particularly limited, such as a cylindrical shape, a polygonal cylinder (including a box shape) with a rectangular bottom shape (including a box shape), a cylinder with an irregular bottom shape (including a box shape), etc. can do.
- the carbon dioxide fixing device 5 may be provided with a stirrer and a jacket coil for heating and cooling if necessary.
- the carbon dioxide fixing device 5 one container is provided, and when almost all of the sodium hydroxide has reacted, the inflow of residual gas is stopped, and the sodium carbonate-containing solution is discharged.
- a batch system in which residual gas starts to flow again, but when two or more of the above containers are installed and all of the sodium hydroxide has reacted in one container, The gas inflow is switched from one container to the other, and sodium carbonate production starts in the other container, while the sodium carbonate-containing solution in the container in which almost all sodium hydroxide has reacted is discharged. It may be a semi-batch type.
- a sodium hydroxide aqueous solution is used as the fixing agent 41, the sodium hydroxide aqueous solution is circulated, and the sodium hydroxide aqueous solution is circulated.
- Residual gas 26 may be introduced and mixed to react sodium hydroxide and carbon dioxide.
- sodium hydroxide aqueous solution is circulated in a container and sodium hydroxide aqueous solution discharged from the container through a pipe is pumped again using a pump. It can be returned to the container.
- sodium hydroxide and the aqueous solution containing sodium carbonate produced by the reaction are continuously fed into the circulation system of the aqueous solution containing sodium carbonate, and further the aqueous solution containing sodium carbonate continuously circulated from this circulation system. May be extracted as a sodium carbonate-containing solution (waste liquid) 4 2, and the carbon dioxide fixing device 5 may be operated continuously.
- the carbon dioxide fixing device 5 is used as a sodium carbonate generator, the carbon dioxide content in the residual gas 26 after separation of hydrogen from the reformed gas 24 by the hydrogen separator 4 is 15 to 99.9% by mass is preferable, and 60% by mass or more is more preferable.
- the content is lower than 5% by mass, the amount of impurities in the residual gas 26 increases, so it is difficult to increase the purity of the sodium carbonate containing the sodium carbonate-containing solution 42 discharged from the carbon dioxide fixing device 5.
- the carbon dioxide content in the residual gas 26 is low or if you want to make the carbon dioxide content in the residual gas 26 higher, you may install a transformer (carbon monoxide converter). .
- the residual gas 26 discharged from the hydrogen separator 4 flows into the transformer, and the residual gas 26, which has been transformed and has a high carbon dioxide content, flows into the carbon dioxide fixing device 5. .
- the residual gas 26 contains a large amount of carbon monoxide produced as a by-product in the methane reformer 3, a carbon monoxide converter is installed and the residual gas 26 is oxidized. You may make it flow into a carbon transformer.
- a carbon monoxide converter carbon monoxide is converted by bringing the residual gas 26 adjusted to 3500 ° C to 360 ° C inside it into contact with the Fe_Cr catalyst. A thing can be used conveniently.
- the carbon monoxide transformer generates carbon dioxide and hydrogen using carbon monoxide and water as raw materials. Thereby, carbon monoxide contained in the residual gas 26 is transformed into carbon dioxide, and the carbon monoxide content in the residual gas 26 can be reduced.
- the residual gas 26 having a reduced carbon monoxide content can be introduced into the carbon dioxide fixing device 5.
- hydrogen is generated in addition to carbon dioxide, so the residual gas 26 flowing out from the carbon monoxide converter is passed through the hydrogen separator to separate the hydrogen, and the hydrogen is mixed into the fuel 3 It may be used by mixing in 2.
- a new hydrogen separator may be installed to allow the entire residual gas 26 to flow in, or a part of the residual gas 26 may be withdrawn to the hydrogen separator 4 together with the reformed gas 2 4. A part of the residual gas 26 may be circulated by flowing it in.
- Residual gas 26, which has been transformed and has a high carbon dioxide content flows into the carbon dioxide fixing device 5. .
- residual gas 26 is converted by the carbon monoxide converter, if carbon monoxide still remains in the residual gas 26, or the residual gas 26 in which carbon monoxide remains is converted to the carbon monoxide converter. If it is not transformed by the above, the residual gas 26 flows into the carbon dioxide fixing device 5 and the exhaust gas (carbon dioxide fixing gas) 4 4 after the reaction of carbon dioxide reacts with the residual gas 26. The carbon monoxide remaining in is contained.
- the carbon dioxide fixing exhaust gas 44 As a method for treating carbon monoxide contained in the carbon dioxide fixing exhaust gas 44, it is preferable to mix the carbon dioxide fixing exhaust gas 44 into the mixed fuel 32 and burn it by the combustion means 2. At this time, if the carbon dioxide fixer exhaust gas 44 contains hydrogen, it is preferable because hydrogen is also burned by the combustion means 2 as fuel.
- the carbon dioxide fixator exhaust gas 4 4 may be dispersed with sodium hydroxide in the carbon dioxide fixator 5 and may contain droplets, the carbon dioxide fixer exhaust gas 4 4 is mixed into the mixed fuel 3 2.
- the contained sodium hydroxide may enter the firing furnace body 1 and corrode the firing furnace body 1. Therefore, when the carbon dioxide fixing exhaust gas 44 is mixed with the mixed fuel 32 and burned, it is preferable to remove sodium hydroxide before combustion.
- the sodium hydroxide can be removed before or after mixing the carbon dioxide fixer exhaust gas 44 with the mixed fuel 32.
- the sodium hydroxide can be removed by passing it through a sodium hydroxide remover (not shown).
- a sodium hydroxide remover a trap filled with water or the like can be used, and it is preferably installed in the middle of the piping.
- the carbon dioxide fixator It is preferable to extract a part of the exhaust gas 44 and flow it into the carbon dioxide fixing device 5 again. As a result, the remaining carbon dioxide can be reduced.
- another carbon dioxide fixing device may be provided, and the carbon dioxide fixing exhaust gas 44 may be caused to flow into the second carbon dioxide fixing device to generate sodium carbonate. As a result, the remaining carbon dioxide can be further reduced.
- carbon dioxide fixation Exhaust gas exhaust gas 4 4 is mixed with mixed fuel 3 2 and carbon dioxide fixer exhaust gas 4 4 is allowed to flow into the carbon dioxide fixer by the amount of carbon monoxide contained in residual gas 26 and carbon dioxide.
- carbon monoxide and carbon dioxide contained in the fixer exhaust gas 44 either of these operations may be used alone, or they may be used in combination to achieve optimum conditions.
- the sodium carbonate produced in the carbon dioxide fixing device 5 is discharged from the carbon dioxide fixing device 5 as a sodium carbonate-containing solution 42 and then purified in a sodium carbonate purification step (not shown) to obtain high-purity sodium carbonate. It is preferable to be taken out. Therefore, the content of sodium carbonate contained in the sodium carbonate-containing solution 4 2 generated in the carbon dioxide fixing device 5 with respect to the remaining substance excluding water from the sodium carbonate-containing solution 4 2 is 8 0-9 9. 9 Preferably, the content is set to 95% by mass, and more preferably 95% by mass or more. If it is lower than 80% by mass, the purity of sodium carbonate obtained by purification in the sodium carbonate purification step (not shown) is difficult to increase.
- the fixing agent 4 1 in order to obtain high purity sodium carbonate obtained by purification, it is preferable to use high purity sodium hydroxide that is reacted with carbon dioxide in the carbon dioxide fixing device 5. That is, the remaining substance of sodium hydroxide in the fixing agent 4 1 to be placed inside the carbon dioxide fixing device 5 except water from the fixing agent 4 1 (when the fixing agent 4 1 does not contain water)
- the content with respect to the fixing agent 4 1 as a whole is preferably 80 to 99.9% by mass, more preferably 95% by mass or more. If it is lower than 80% by mass, the purity of sodium carbonate obtained by purification may not be easily increased.
- the fixing agent 41 an aqueous solution of sodium hydroxide may be used as described above, or molten sodium hydroxide may be used.
- the content of sodium hydroxide with respect to the entire aqueous solution is preferably 30 to 95% by mass. If it is lower than 30% by mass, the concentration of sodium hydroxide is low, so that it is difficult to efficiently react with carbon dioxide, and the content of carbon dioxide remaining in the carbon dioxide fixer exhaust gas 51 may increase. On the other hand, if it is higher than 95% by mass, the viscosity of the aqueous sodium hydroxide solution will be high and the fluidity will be poor, which may make it difficult to react efficiently with carbon dioxide.
- the purity of sodium carbonate taken out by purifying the sodium carbonate-containing solution 42 discharged from the carbon dioxide fixing device 5 in a purification step is preferably 98 to 99.9% by mass. More preferably, it is 99.0% by mass or more. 9
- the content of sodium carbonate with respect to the entire sodium carbonate-containing solution 42 is preferably 60 to 95% by mass. If it is lower than 60% by mass, the concentration of sodium carbonate is low, and it may be difficult to efficiently produce sodium carbonate crystals.
- a purification method for purifying the sodium carbonate-containing solution 42 discharged from the carbon dioxide fixing device 5 a sodium carbonate crystal is precipitated from the sodium carbonate-containing solution 42, and the precipitated sodium carbonate is separated from the mother liquor.
- a method of taking out sodium carbonate crystals is preferred.
- This purification method includes a crystallizer (not shown) for precipitating sodium carbonate crystals from a sodium carbonate-containing solution 42, and a filter (not shown) for separating sodium carbonate crystals precipitated by the crystallizer from the mother liquor. It is preferable to be carried out in a purification step (not shown).
- a crystallizer As a crystallizer, a crystallizer generally used in industry can be used. For example, a crystallizer can be crystallized by cooling the solution with a stirrer, a jacket, a coil, and the like. A cylindrical crystallizer can be used. If the temperature of the sodium carbonate-containing solution 42 is low and a portion of the sodium carbonate contained has already precipitated, filter directly with a filter without crystallization in the crystallizer, or After passing through a crystallizer formally, it may be filtered with a filter.
- a basket-type centrifugal filter, a gravity-type filter, a vacuum filter, or the like which is usually used industrially, can be used. Since sodium carbonate is dissolved in the mother liquor discharged from the filter, sodium carbonate is precipitated by lowering the temperature of the mother liquor by using another crystallizer to precipitate sodium carbonate. The crystal of the lithium may be separated by a filter. In addition, since the mother liquor discharged from the filter contains unreacted sodium hydroxide, in order to effectively use this sodium hydroxide, sodium hydroxide is further added by further adding sodium hydroxide. It is also possible to adjust the system concentration and return it to the carbon dioxide fixing device 5.
- a method for producing sodium carbonate a method of synthesizing by the Solvay method, a method of refining using a natural raw material represented by trona ash produced from the Green River deposit in Wiming, etc. are known.
- it is difficult to purify sodium carbonate and there is a problem that purification costs increase if it is attempted to purify this.
- sodium chloride is used as a raw material, so it is necessary to remove chlorine after producing sodium carbonate. If the removal of chlorine is insufficient, the purity of sodium carbonate will be low, and purification costs will increase if chlorine is sufficiently removed to increase the purity of sodium carbonate.
- a commercially available system can be used for the fuel cell 7. Any of a polymer type, a phosphoric acid type, a molten carbonate type, a solid electrolyte type, and the like may be used, but a phosphoric acid type, a molten carbonate type, or a solid electrolyte type is preferable because exhaust heat is high.
- the power capacity that can be generated is about 100 KW to 200 KW per system based on the performance of the current commercial system. However, if a method such as parallel installation is used, the power capacity can be designed freely. it can.
- a part of the hydrogen fuel 2 5 is sent as a fuel cell hydrogen 2 7 through a pipe, and in the fuel cell ⁇ , the fuel cell hydrogen 2 7 reacts with air (oxygen in the air) to generate power. Is done.
- methane main fuel 31 for mixing mainly composed of methane and hydrogen separated by the hydrogen separator 4 are used as fuel to be burned by the combustion means 2.
- Firing furnace 1 0 0 During combustion, the flue gas 1 2 is not being discharged regularly (if the flue gas 1 2 has not yet been generated, it is gradually increasing), so the reaction by the methane reformer 3 Is difficult to use while using the flue gas 1 2, the use of the mixed fuel 3 2 stabilizes the inside of the calcining furnace body 1, and the flue gas 1 2 is steadily discharged. (When a methane reformer, which will be described later, is disposed in the main body of the firing furnace, the temperature of the combustion gas may be stabilized). In this case, at the start of the operation of the firing furnace 100, firing is performed only with the methane main fuel 31 for mixing mainly composed of methane.
- the methane reformer 3 is connected with other materials such as steam and electricity.
- a heating device (not shown) may be provided, and the methane reformer 3 may be operated while using the heating device.
- the firing furnace 100 according to the present embodiment shown in FIG. 1 is suitably used as a firing furnace for firing ceramics having a calorific value required for firing of 100 million to 100 million (k J / H r). Can be.
- volume ratio of reforming methane secondary fuel 2 1 to mixing methane main fuel 3 1 is 5: 9 5-10 0 0: 0 ( Volume ratio). If the ratio of reforming methane secondary fuel 21 is less than 5 (volume ratio), carbon dioxide may not be sufficiently reduced. Further, at least one of the mixing methane main fuel 31 and the reforming methane secondary fuel 21 can be liquefied natural gas (LNG). By using LNG, it can be burned efficiently due to the good flammability of LNG, and because LNG is a clean and inexpensive fuel, combustion does not generate harmful substances such as sulfur oxides and dust. preferable.
- LNG liquefied natural gas
- the reaction rate of the methane reformer 3 is 100 (%) (4 moles of hydrogen is generated when 1 mole of methane and 2 moles of water are introduced into the methane reformer 3).
- the hydrogen separation efficiency in the reactor 4 is 100 (%) (all the hydrogen contained in the reformed gas 24 is separated in the hydrogen separator 4 to become hydrogen fuel 25), and the total amount of hydrogen fuel 25 is In this case, for example, if only 1 (NmVH r) of methane gas is used for combustion in Combustion Means 2, 39800 (k J / H r) In contrast to this, as an example of this embodiment, as an example of this embodiment, as an example of this embodiment, 0.5 (NmVHr) of methane gas is used as the methane main fuel for mixing, and as a methane secondary fuel for reforming. Assuming that 0.4 (NmVHr) of tongue gas is used, 1.6 (NmVHr) of hydrogen is generated from the main reformer 3.
- the hydrogen separator 4 it is separated by the hydrogen separator 4, and the separated hydrogen is mixed as the hydrogen fuel 25 with the reforming methane secondary fuel (methane gas) to obtain the mixed fuel 32 (methane gas 0.5 (NmVH r), hydrogen Is 1.6 (N mVHr).
- this mixed fuel 32 is burned by the combustion means 2, the amount of heat of 19900 (k J / H r) is generated from methane gas 0.5 (NmVH r), and from hydrogen 1.6 (NmVH r), 20480 (k J / H r) is generated. Therefore, the amount of heat obtained by burning the mixed fuel 32 is 40 380 (k J / H r).
- the amount of carbon dioxide generated is 0.5 (NmVH r). Therefore, when this embodiment is compared with the case of the comparative example, it is necessary to make the amount of heat generated by the combustion in the combustion means 2 almost equal (this embodiment is slightly larger).
- the amount of methane gas used is 10% compared to the comparative example in this embodiment. Further, the amount of carbon dioxide generated is reduced by 50% in the case of the present embodiment compared to the case of the comparative example.
- FIG. 2 is a block flow diagram schematically showing the firing furnace of the present embodiment.
- the arrows in Fig. 2 indicate the movement of fuel, combustion exhaust gas, water vapor, and other substances.
- the firing furnace 200 of the present embodiment includes a combustion means 52 that burns a fuel 61 containing inflowing methane to generate a combustion gas, and a combustion gas.
- the calcining furnace main body 51 which heats and calcinates the object to be fired, and discharges the burned combustion gas as combustion exhaust gas containing carbon dioxide (combustion gas discharged outside) 62
- a reforming raw material 7 3 consisting of methane auxiliary fuel 71 1 for reforming mainly composed of methane flowing therein and steam 7 2, and combustion exhaust gas.
- methane in reforming raw material 7 3 reacts with steam 7 2 to produce reformed gas 7 4 containing hydrogen and carbon dioxide (Methane reforming reaction) Methane reformer 5 3 and meta
- the reformed gas 7 4 generated in the reformer 53 is introduced into the interior to selectively separate the hydrogen in the reformed gas 74 and to remove hydrogen fuel 7 5 and carbon dioxide mainly composed of hydrogen.
- Hydrogen separator 5 4 to be separated into residual gas 7 6 contained therein, and carbon dioxide in residual gas 7 6 separated by hydrogen separator 5 4 to be fixed in a gas state so as not to be released to the outside.
- the firing furnace 200 of the present embodiment effectively uses the heat of the combustion exhaust gas 62 by performing the methane reforming reaction in the methane reformer 53 while using the heat of the combustion exhaust gas 62. Can be reused.
- the carbon dioxide fixing device 5 5 allows sodium hydroxide to flow in as a fixing agent 9 1 for fixing carbon dioxide inside, and the fixing agent 9 1 and the residual gas 7 6 are contacted and fixed inside.
- the carbon dioxide contained in the residual gas 76 is absorbed by the agent 91 to generate sodium carbonate, and the waste liquid 92 containing sodium carbonate is discharged to the outside.
- the unreacted gas is discharged to the outside as carbon dioxide fixing gas 94.
- the immobilizing agent 91 is not particularly limited as long as it can react with carbon dioxide or absorb carbon dioxide, and examples thereof include NaOH and Mg (OH) 2 .
- each equipment is connected by a predetermined pipe, and each fuel, water vapor, etc. flow and move in the pipe.
- the firing furnace 20 0 of the present embodiment includes the fuel cell 7 and generates power using the fuel cell hydrogen 7 7 containing the hydrogen fuel 75, so that the combustion exhaust gas 6 2 The thermal energy it has can be efficiently converted into electrical energy.
- the reformed gas 7 4 containing hydrogen is generated in the methane reformer 5 3 using the heat of the combustion exhaust gas 62, and the hydrogen separator 5 4 generates hydrogen fuel 7 5
- the heat energy of the combustion exhaust gas 62 is more highly used. It is efficiently converted to.
- the fuel cell 57 generates electricity by reacting hydrogen (hydrogen for fuel cells) with oxygen or air, but the hydrogen fuel 75 used as the fuel cell hydrogen 77 has a purity of hydrogen contained. Because it is expensive, it can generate electricity efficiently. For example, when the fuel cell is generated using normal hydrogen, the power efficiency is about 40%. However, in the fuel cell 7 used in this embodiment, the power efficiency is 60 to 70. % Dramatically increases. In the firing furnace of the present embodiment, the reformed gas 74 may be used directly in the fuel cell 57 without passing through the hydrogen separator 54. Regarding CO2 emissions, fuel cells are about twice as efficient in converting their thermal energy into electrical energy compared to thermal power generation.
- carbon dioxide produced when the reforming raw material 23 is reacted with the methane reforming catalyst 6 is fixed by the carbon dioxide fixing device 5. Carbon dioxide generated from the reforming raw material 2 3 is released to the outside in the form of gas It will never be done.
- the heat source for the methane reforming reaction can use not only the combustion exhaust gas but also the heat dissipated from the furnace wall and the heat discarded when the kiln tools used for ceramic firing are cooled. You can plan.
- the residual gas 76 may contain a combustible substance such as carbon monoxide.
- a combustible substance such as carbon monoxide.
- a part or all of the residual gas 76 may be burned by the combustion means 52. This is preferable because fuel is recovered.
- Each of the fuel cells 5 7 includes a firing furnace body 1, a combustion means 2, a methane reformer 3, a hydrogen separator 4 and carbon dioxide in the embodiment of the firing furnace of the present invention shown in FIG. 1 described above.
- the fixing device 5 and the fuel cell 7 are preferably configured in the same manner as the respective cases, whereby the same effect can be obtained.
- the fuel 61 containing methane preferably has a main component as a main component, and the combustion means 52 can efficiently burn the fuel 61 having the main component methane. It is preferable.
- “mainly composed of methane” means that the content of methane is 80 (volume%) or more.
- the firing furnace 200 of the present embodiment uses the entire amount of the hydrogen fuel 75 for power generation in the fuel cell 57, so that a branch for mixing part of the hydrogen fuel 75 with the fuel 61 is used. No piping is required.
- the firing furnace 200 according to the present embodiment shown in FIG. 2 is suitably used as a firing furnace for firing ceramics with a calorific value required for firing of 100 million to 100 million (kJ / Hr). Can be. Further, as the body to be fired, the ceramic honeycomb structure can be suitably fired as in the case of the embodiment of the firing furnace of the present invention. Next, still another embodiment of the firing furnace of the present invention will be described with reference to the drawings.
- FIG. 3 is a block flow diagram schematically showing the firing furnace of the present embodiment. In FIG. 3, the arrows indicate the movement of fuel, combustion exhaust gas, water vapor, and other substances.
- the firing furnace 300 of the present embodiment includes a combustion means 10 0 2 for burning a fuel 1 1 1 containing inflowing methane to generate combustion gas, and a combustion gas. Calcination is performed by heating and firing the object to be fired in the interior, and discharging the fired combustion gas to the outside as combustion exhaust gas containing carbon dioxide (combustion gas discharged outside) 1 1 2
- combustion exhaust gas containing carbon dioxide (combustion gas discharged outside) 1 1 2
- For reforming which is disposed in the combustion furnace body 101, filled with a methane reforming catalyst 106, and mainly contains methane flowing therein.
- the reforming raw material 1 2 3 consisting of methane auxiliary fuel 1 2 1 and steam 1 2 2 is modified by contacting it with the methane reforming catalyst 1 0 6 while being heated by the combustion gas generated by the combustion of the fuel 1 1 1.
- Methane in the raw material 1 2 3 reacts with water vapor 1 2 2 to produce reformed gas 1 2 4 containing hydrogen and carbon dioxide (Methane reforming reaction) Methane reformer 1 0 3
- the reformed gas 1 2 4 generated in the methane reformer 1 0 3 flows into the reformed gas 1 2 4
- Hydrogen separator 1 0 4 which selectively separates hydrogen in the fuel and separates it into hydrogen fuel 1 2 5 mainly composed of hydrogen and residual gas 1 2 6 containing carbon dioxide, and hydrogen separator 1 0
- a carbon dioxide fixing device 10 5 for fixing the carbon dioxide in the residual gas 1 2 6 separated in 4 so as not to be released to the outside in the state of gas.
- the methane reformer 10 3 is disposed in the firing furnace body 10 1, and the reforming raw material 1 2 3 is replaced with the combustion exhaust gas 1 1 2.
- the heat of the combustion gas can be used directly in the calcining furnace body 1 and combustion The heat of the gas can be used effectively with little loss. This is because, for example, compared to the case where the combustion gas is discharged from the firing furnace body 1 to the outside and then heat recovery is performed by equipment installed outside the firing furnace body 1, the thermal energy of the combustion gas is the same. Loss due to heat dissipation is significantly reduced. As a result, the total amount of fuel used can be reduced and energy resources can be used more efficiently.
- the combustion means 100 is a hydrogen fuel separated by a mixing methane main fuel 1 3 1 and a hydrogen separator 1 0 4 mainly containing inflowing methane.
- Combusting mixed fuel 1 3 2 with 1 2 5 (hydrogen fuel for mixing 1 2 8), that is, using mixed fuel 1 3 2 as fuel 1 1 1 containing methane, generating combustion gas By doing so, the carbon dioxide content in the combustion exhaust gas 1 1 2 can be reduced, and the amount of carbon dioxide emitted to the outside can be reduced.
- the carbon dioxide fixing device 10 5 allows sodium hydroxide to flow in as a fixing agent 1 4 1 for fixing carbon dioxide inside, and the fixing agent 1 4 1 and residual gas 1 2 6 So that the carbon dioxide contained in the residual gas 1 2 6 is absorbed by the immobilizing agent 1 4 1 to produce sodium carbonate, and the waste liquid 1 4 2 containing sodium carbonate is discharged to the outside. It is formed. Unreacted gas is discharged to the outside as carbon dioxide fixing exhaust gas 144.
- “mainly composed of methane” means that the content of methane is 80 (volume%) or more.
- the immobilizing agent 14 1 is not particularly limited as long as it can react with carbon dioxide or absorb carbon dioxide, and examples thereof include Na OH and Mg (OH) 2 .
- each equipment is connected by a predetermined pipe, and each fuel, water vapor, etc. flow and move in the pipe.
- the calorific value of the combustion gas in the firing furnace body 10 1 combustion heat of fuel 1 1 1 Therefore, a part of the calorific value of the combustion gas can be effectively recovered as the combustion heat of the fuel 11 1 and reused, thereby reducing the total fuel consumption.
- the heat of the combustion gas as a heat source for the methane reforming reaction is the combustion heat of the fuel 1 1 1, and the heat radiated from the furnace wall during the combustion of the fuel 1 1 1 included. It is also possible to use heat that is discarded when the kiln tools used during ceramic firing are cooled. As shown in FIG.
- the firing furnace 300 of the present embodiment further includes a fuel cell 107.
- a part of the hydrogen fuel 1 2 5 obtained by separation in the hydrogen separator 1 0 4 is branched as hydrogen 1 2 7 for the fuel cell, and this is used to generate electricity using the fuel cell 1 0 7 ing. Since the hydrogen fuel 1 25 has a high purity of hydrogen contained therein, the fuel cell 1 07 can efficiently generate power.
- the total amount of the hydrogen fuel 1 25 may be used as the mixing hydrogen fuel 1 28, or may be used separately for the mixing hydrogen fuel 1 28 and the fuel cell hydrogen 1 27.
- the ratio when dividing hydrogen fuel for mixing 1 2 8 and hydrogen for fuel cell 1 2 7 is not particularly limited, and the carbon dioxide emission amount and power generation amount are appropriately balanced to an appropriate value. What should I do?
- the reformed gas 1 2 4 may be used directly in the fuel cell 10 7 without passing through the hydrogen separator 10 4.
- FIG. 5 is a cross-sectional view schematically showing the firing furnace main body 101 constituting the firing furnace 300 of the present embodiment, cut along a plane perpendicular to the longitudinal direction thereof.
- the firing furnace main body 101 shown in FIG. 5 is a continuous firing furnace body 101, and the longitudinal direction thereof is the direction in which the object to be fired m is carried into the firing furnace body 101 and travels. It is.
- the body m to be fired is formed by the belt conveyor B so as to travel in the firing furnace body 101 along the longitudinal direction.
- the firing furnace main body 101 has a form in which the methane reformer 3 is disposed along the inner surface of the outer peripheral wall 101 a.
- the inner furnace wall may be disposed inside 10 lb, that is, in a space in which the object to be fired m is fired with combustion gas. Moreover, you may arrange
- the methane reformer 3 is disposed at a position where the temperature is optimal for performing the methane reforming reaction in the temperature distribution of the entire cross section. It is preferable.
- the position where the methane reformer 10 3 is arranged in the longitudinal direction of the firing furnace body 101 is a position where the temperature distribution in the firing furnace body 101 becomes a temperature suitable for the methane reforming reaction. It is preferable to do.
- the space where the methane reformer 10 3 is disposed and the body m to be fired are provided. It is preferable to partition the space to be fired by the combustion gas with the inner furnace wall 1 0 1 b. Inner furnace wall 1 0 1 b firing furnace body 1 0 1 By partitioning the inside, it is possible to prevent the combustion gas from coming into direct contact with the methane reformer 10 3 or make it difficult to make contact, so the amount of heat transferred to the methane reformer 10 3 is adjusted more appropriately. Therefore, the temperature of the methane reformer 10 3 can be made more appropriate. This is effective when the methane reformer 103 is disposed in the high temperature region of the firing furnace body 101.
- the methane reformer 10 3 is formed by filling a methane reforming catalyst 1 0 6 in a cylindrical reforming reaction tube 1 0 3 a.
- both ends of the reforming reaction tube 1 0 3 a communicate with the outside of the calcining furnace main body 1 0 1, and the reforming raw material flows in from one end, and the calcining furnace main body 1 0 1, the methane reforming reaction is performed by the heat of the combustion gas and the methane reforming catalyst, and the resulting reformed gas is fed from the other end of the reforming reaction tube 1 0 3 a to the calcining furnace body 1 0 1 It is formed to flow out.
- the tubular reforming reaction tube shown in FIG. 5 is used as the container for filling the methane reforming catalyst 106, but the shape of the container is tubular (tubular).
- the shape is not limited, and any shape can be used as long as it can be box-shaped or filled with the methane reforming catalyst 10 6 inside and placed in the calcining furnace body 10 1, and the methane reforming reaction can be performed by the combustion gas. But you can.
- the firing furnace body 1 0 1, combustion means 1 0 2, methane reformer 1 0 3, hydrogen separator 1 0 4 and carbon dioxide fixing device 1
- Each of the fuel cells 10 7 is one of the firing furnaces of the present invention shown in FIG. 1 described above except that the methane reformer 10 3 is arranged in the firing furnace body 10 1.
- it is preferably configured in the same manner as each of the firing furnace body 1, the combustion means 2, the methane reformer 3, the hydrogen separator 4, the carbon dioxide fixing device 5, and the fuel cell 7. Thereby, the same effect can be acquired.
- the methane reformer is disposed in the firing furnace body.
- a methane reformer disposed outside the calcining furnace main body such as a methane reformer in the above, may be further provided.
- a methane reformer is provided inside and outside the main body of the firing furnace. Inside, methane reforming is performed using the heat of the combustion gas, and outside, methane is reformed using the heat of the combustion exhaust gas. Modification may be performed.
- FIG. 4 is a block flow diagram schematically showing still another embodiment of the firing furnace of the present invention. In FIG. 4, the arrows indicate the movement of each fuel, combustion exhaust gas, water vapor, and other substances.
- the firing furnace 400 includes a combustion means 15 2 that burns a fuel 16 1 containing inflowing methane to generate combustion gas, and a combustion gas that A firing furnace main body 1 5 1 for heating and firing the object to be fired therein, and discharging the fired combustion gas to the outside as combustion exhaust gas 16 2 containing carbon dioxide.
- methane reforming catalyst 1 5 6 consisting of reforming methane secondary fuel 1 ⁇ 1 and steam 1 7 2 mainly composed of methane flowing into it
- the reformed raw material 1 7 3 is brought into contact with the methane reforming catalyst 1 5 6 while being heated by the combustion gas, whereby the methane and the steam 1 7 2 in the reformed raw material 1 3 are reacted to generate hydrogen and dioxide.
- Hydrogen separator 1 5 4 to be separated into hydrogen fuel 1 7 5 as component and residual gas 1 7 6 containing carbon dioxide, and residual gas 1 7 6 separated by hydrogen separator 1 5 4
- Carbon dioxide fixing device that fixes carbon dioxide so that it is not released to the outside in the form of gas 1 5 5 and hydrogen for fuel cells containing hydrogen fuel 1 7 5 separated by hydrogen separator 1 5 4 1 7
- a fuel cell 15 7 that generates electricity by reacting 7 with oxygen or air.
- Each device is connected by a predetermined pipe, and each fuel, water vapor, etc. flow and move in the pipe.
- the gas that has not been fixed by the carbon dioxide fixing device 1 5 5 is discharged to the outside as the carbon dioxide fixing device exhaust gas 1 94.
- the firing furnace 400 has the methane reformer 15 3 disposed in the firing furnace main body 15 1, so that the methane reforming reaction is performed in the firing furnace main body 1 51 1.
- the firing furnace 400 according to the present embodiment includes a fuel cell 1 5 7, and uses the fuel cell hydrogen 1 7 7 containing the hydrogen fuel 1 75 to generate power. Therefore, a part of the thermal energy of the combustion gas can be efficiently converted into electric energy.
- the methane reformer 1 5 3 uses the heat of the combustion gas, the methane reformer 1 5 3 generates hydrogen-containing reformed gas 1 7 4, and the hydrogen separator 1 5 4 converts the reformed gas 1 7 4 to hydrogen fuel 1 7 5 is separated, and the entire amount of the separated hydrogen fuel 1 75 is used as fuel cell hydrogen 1 7 7 for power generation in the fuel cell 1 5 7 to use part of the thermal energy of the combustion gas It is efficiently converted to higher value electric energy.
- Fuel cell 1 5 7 generates electricity by reacting hydrogen (hydrogen for fuel cell) with oxygen or air, but hydrogen fuel 1 7 5 used as fuel cell hydrogen 1 ⁇ 7 is contained Since the purity of hydrogen is high, power can be generated efficiently. For example, when the fuel cell is generated using normal hydrogen, the power efficiency is about 40%.
- the power efficiency is 60 to 7%. A dramatic increase of 0%.
- the reformed gas 1 74 may be used directly in the fuel cell 1 5 7 without passing through the hydrogen separator 1 5 4.
- fuel cells are about twice as efficient in converting thermal energy into electrical energy compared to thermal power generation. Therefore, to reduce carbon dioxide emissions, if electricity derived from fuel cells is used instead of electricity derived from thermal power generation, etc., the amount of carbon dioxide reduction for the same amount of electricity is reduced by half. Therefore, the generated carbon dioxide can be reduced without deliberately fixing the carbon dioxide. If carbon dioxide is fixed, a higher carbon dioxide reduction effect is produced.
- the firing furnace main body 1 5 1, combustion means 1 5 2, methane reformer 1 5 3, hydrogen separator 1 5 4, carbon dioxide fixing device 1 5 5 and the fuel cell 1 5 7 are each of the firing furnace of the present invention shown in FIG. 1 described above except that the methane reformer 15 3 is disposed in the firing furnace body 15 1.
- it is preferably configured in the same manner as each of the firing furnace body 1, the combustion means 2, the methane reformer 3, the hydrogen separator 4, the carbon dioxide fixing device 5, and the fuel cell 7. Thereby, the same effect can be acquired.
- the structure in which the methane reformer 15 3 is disposed inside the firing furnace body 15 1 can be configured in the same manner as the firing furnace body 10 1 shown in FIG. 5 or FIG. This is preferable because of the same effect. You can get fruits.
- the fuel 16 1 containing methane is preferably composed mainly of methane, and the combustion means 15 2 can efficiently burn the fuel 16 1 composed mainly of methane. Preferably there is.
- FIG. 1 showing one embodiment of the above-described firing furnace of the present invention.
- the embodiment of the firing furnace of the present invention described above with reference to FIG. 1 can be suitably used.
- the combustion gas is generated by injecting the fuel 11 containing methane into the combustion means 2 and burning it, and the combustion gas generated in the combustion means 2 is introduced into the interior of the firing furnace body 1.
- This is a firing method in which the fired body carried inside is heated and fired with combustion gas, and the fired combustion gas is discharged to the outside.
- a reforming raw material 2 3 composed of reforming methane auxiliary fuel 21 and steam 2 2 mainly containing methane is introduced into a methane reformer 3 filled with a methane reforming catalyst 6 inside,
- the reformed raw material 2 3 is brought into contact with the methane reforming catalyst 6 while being heated by the combustion exhaust gas 1 2 to react the methane and the steam 22 in the reformed raw material 2 3 to contain hydrogen and carbon dioxide. It produces the quality gas 24.
- the methane reforming reaction in the methane reformer 3 uses the heat of the combustion gas (combustion exhaust gas 1 2) discharged to the outside of the firing furnace body 1. By doing so, the heat of the flue gas 12 can be effectively reused.
- the reformed gas 24 generated in the methane reformer 3 is caused to flow into the hydrogen separator 4 to selectively separate hydrogen in the reformed gas 24. Then, the hydrogen fuel 25 containing hydrogen as a main component 25 and the residual gas 26 containing carbon dioxide are separated, and the residual gas 26 separated by the hydrogen separator 4 is introduced into the carbon dioxide fixing device 5. The carbon dioxide in the residual gas 2 6 is fixed by the fixing agent 4 1 so that it is not released to the outside in the form of gas, and the combustion means 2 is mixed with methane main fuel 3 1 containing methane as the main component.
- the combustion exhaust gas 12 used in the methane reformer 3 is then discharged to the outside as the reformer exhaust gas 4 3.
- the waste liquid 42 is discharged outside.
- methane main fuel 31 for mixing containing methane as a main component “mainly containing methane” means that the content of methane is 80 (volume%) or more.
- the term “having hydrogen as the main component” of the hydrogen fuel 25 having hydrogen as the main component means that the hydrogen content is 50 (volume%) or more.
- the mixed fuel 3 2 (fuel 1 1) does not generate carbon dioxide even if it is burned. Generation can be reduced.
- the content of hydrogen contained in the mixed fuel 32 (hydrogen Z mixed fuel) is preferably 5 to 95 (volume%), and more preferably 25 to 75 (volume%). If it is less than 5 (volume%), the carbon dioxide reduction effect may not be sufficient. If it is more than 9 (volume%), not only the combustion exhaust gas but also other gases when the methane reforming reaction is performed. In addition, a heat source may be required.
- carbon dioxide produced when the reforming raw material 23 is reacted with the methane reforming catalyst 6 is fixed by the carbon dioxide fixing device 5, carbon dioxide produced from the reforming raw material 23 is gas. In this state, it is not released to the outside. Further, since the calorific value of the combustion exhaust gas 1 2 discharged from the calcining furnace body 1 is used as the amount of heat necessary for the endothermic reaction when the reforming raw material 2 3 is reacted with the methane reforming catalyst 6, the combustion exhaust gas A part of the exhaust heat of 1 and 2 is recovered as the combustion heat of the fuel, and the total amount of fuel used can be reduced.
- the firing furnace 100 used in the firing method of the present embodiment further includes a fuel cell 7, and a part of the hydrogen fuel 25 is used as hydrogen 27 for the fuel cell. It is configured to be able to be electrified.
- the fuel cell 7 generates power by reacting hydrogen (hydrogen for fuel cells) with oxygen or air.
- the hydrogen obtained by separating with the hydrogen separator 4 A part of the fuel 25 can be separated as hydrogen 27 for a fuel cell, and this can be used for the fuel cell 7 to generate electricity. water Since the purity of hydrogen contained in the raw fuel 25 is high, the fuel cell 7 can efficiently generate power by using a part of it as the hydrogen 2 7 for the fuel cell.
- the power efficiency is about 40%.
- the power efficiency is 60 to 70%.
- a part of the hydrogen fuel 25 obtained by separation in the hydrogen separator 4 is finally burned by the combustion means 2 as the hydrogen fuel 28 for mixing, and the remainder is burned by the fuel cell 27 as fuel cell hydrogen 27.
- fuel cells are about twice as efficient in converting their thermal energy into electrical energy compared to thermal power generation. Therefore, if the power derived from the fuel cell is used instead of the power derived from thermal power generation for the reduction of carbon dioxide emissions, the amount of carbon dioxide reduction for the same amount of power is halved. Therefore, it is possible to reduce the generated carbon dioxide without deliberately fixing the carbon dioxide. If carbon dioxide is immobilized, a higher carbon dioxide reduction effect is produced.
- the total amount of the hydrogen fuel 25 may be used as the mixing hydrogen fuel 28, or may be divided into the mixing hydrogen fuel 28 and the fuel cell hydrogen 27.
- the ratio when dividing hydrogen for fuel 28 and fuel cell hydrogen 27 is not particularly limited, and the carbon dioxide emission and power generation amount should be balanced to an appropriate value as appropriate. That's fine.
- the firing furnace body 1 is preferably configured in the same manner as the firing furnace body in the firing furnace of the present invention, Thereby, the same effect can be acquired.
- the firing furnace main body 1 may be a batch type in which a predetermined amount of the objects to be fired are fired intermittently, but the objects to be fired such as a ceramic structure are continuously carried into the interior. It is preferable that the main body 1 is a continuous firing furnace 1 in which the object to be fired is heated and fired inside and then continuously taken out. By performing continuous firing, the combustion exhaust gas 1 2 can be discharged from the firing furnace body 1 stably and stably.
- the methane reforming reaction can be carried out stably by the heat of the combustion exhaust gas 1 2, whereby the hydrogen fuel 2 5 can be supplied stably, and the hydrogen fuel 2 5 and the methane main fuel 3 1 for mixing
- the fuel mixture 32 obtained by mixing the fuel can be stably supplied to the combustion means 2.
- the ceramic honeycomb structure is a structure having a plurality of cells made of ceramic and having a plurality of cells serving as fluid flow paths partitioned by partition walls.
- the combustion means 2, the methane reformer 3, the hydrogen separator 4 and the carbon dioxide fixing device 5 are the firing of the present invention described above. It is preferable to configure in the same manner as in the case of the combustion means 2, the methane reformer 3, the hydrogen separator 4 and the carbon dioxide fixing device 5 in one embodiment of the furnace, thereby obtaining the same effect. be able to. Even when the carbon dioxide fixing device is used as a sodium carbonate generator, in the above-described embodiment of the firing furnace of the present invention, the carbon dioxide fixing device is used in the same manner as when the carbon dioxide fixing device is used as a sodium carbonate generator. Is preferred.
- methane is used as a fuel to be burned by the combustion means 2 as a main component.
- Methane main fuel for mixing 3 1 and hydrogen fuel separated by hydrogen separator 4 is used as a fuel to be burned by the combustion means 2 as a main component.
- the firing method of the present embodiment can be suitably used when firing a ceramic with a heat amount of 1 million to 100 million (k J / Hr).
- k JZHr the present invention can be used by combining several small equipment.
- the present invention can be applied to equipment of 1 million (k J / Hr) or less, methane steam reforming equipment is expensive and is not economical.
- the reforming methane auxiliary fuel 121 and the mixing methane main fuel 131 It is preferable that the volume ratio of methane secondary fuel 121 for reforming: methane main fuel 13 1 for mixing is 5:95 to 100: 0 (volume ratio). If the ratio of reforming methane secondary fuel 121 is smaller than 5 (volume ratio), carbon dioxide may not be sufficiently reduced. Further, at least one of the mixing methane main fuel 131 and the reforming methane secondary fuel 121 may be liquefied natural gas (LNG).
- LNG liquefied natural gas
- the firing furnace 200 used in the firing method of the present embodiment is preferably the same firing furnace as the other embodiments of the firing furnace of the present invention described above with reference to FIG. Good.
- combustion gas is generated by injecting and burning a fuel 61 containing methane into the combustion means 52, and the combustion gas generated by the combustion means 52 is used as the main body of the firing furnace 5 1 is a firing method in which the object to be fired is introduced into the interior and heated by the combustion gas to be fired, and the fired combustion gas is discharged to the outside of the firing furnace body 51.
- a reforming raw material 7 3 consisting of reforming main fuel 7 1 and steam 7 2 mainly composed of methane is added to a methane reformer 5 3 filled with a methane reforming catalyst 56 inside.
- the reformed raw material 7 3 is brought into contact with the methane reforming catalyst 5 6 while being heated by the combustion gas (combustion exhaust gas 6 2) discharged from the calcining furnace body 5 1, so that the The methane and water vapor 72 are reacted to produce reformed gas 74 containing hydrogen and carbon dioxide.
- the firing method of the present embodiment by performing the methane reforming reaction in the methane reformer 53 while using the heat of the combustion exhaust gas 62, the heat of the combustion exhaust gas 62 is obtained. It can be reused effectively.
- the reformed gas 74 generated in the methane reformer 53 is caused to flow into the hydrogen separator 54 and the hydrogen in the reformed gas 74 is selected.
- the hydrogen gas is mainly separated into hydrogen fuel 7 5 and the residual gas 7 6 containing carbon dioxide, and the residual gas 7 6 separated by the hydrogen separator 5 4 is separated into the carbon dioxide fixing device 5 5.
- the hydrogen gas separated in the hydrogen separator 5 4 is fixed by the fixing agent 9 1 so that the carbon dioxide in the residual gas 7 6 is not released to the outside in the gas state.
- the fuel 7 5 is made to flow into the fuel cell 5 7 as hydrogen 7 7 for the fuel cell, and the hydrogen 7 7 for fuel cell reacts with oxygen or air to generate power, so that the combustion exhaust gas 62 has Using hydrogen, the reformed gas 7 4 containing hydrogen is generated in the methane reformer 5 3, and the hydrogen fuel 7 5 is separated from the reformed gas 7 4 by the hydrogen separator 5 -4.
- This is a firing method in which 5 is used for power generation in the fuel cell 57 as hydrogen 77 for a fuel cell, and the thermal energy of the combustion exhaust gas 62 can be converted into electric energy.
- the combustion exhaust gas 62 used in the methane reformer 53 is then discharged to the outside as the reformer exhaust 93. In addition, after carbon dioxide is fixed by the fixing agent 91, it is discharged to the outside as waste liquid 92.
- the entire amount of the hydrogen fuel 75 is used as the fuel cell hydrogen 77, and the fuel cell 57 generates power. It can be recovered and used for power generation, and electric energy with higher utility value can be obtained. Since the hydrogen fuel 75 has a high purity of hydrogen contained therein, the fuel cell 57 can efficiently generate electricity by using it as the fuel cell hydrogen 77. For example, when the fuel cell is generated using normal hydrogen, the power efficiency is about 40%, but when the fuel cell 57 generates power in the present embodiment, the power efficiency is 60 to 70. Improve dramatically with%.
- carbon dioxide produced when the reforming raw material 73 is reacted with the methane reforming catalyst 56 is fixed by the carbon dioxide fixing device 55, Carbon dioxide produced from the reformed raw material 73 is not released to the outside in the form of gas.
- the firing furnace body 51 is a firing furnace body in one embodiment of the firing furnace of the present invention shown in FIG. It is preferable to configure in the same manner as in the case of 1, so that the same effect can be obtained. Further, the firing furnace body 51 may be a batch type in which a predetermined amount of the fired bodies are fired intermittently, but the fired bodies such as ceramic structures are continuously carried into the interior. It is preferable that the main body is a continuous firing furnace body 51 in which the body to be fired is heated and fired inside and then continuously carried out to the outside. By continuously firing, the combustion exhaust gas 62 is discharged from the firing furnace body 51 stably and stably. Therefore, in the methane reformer 53, the methane reforming reaction can be stably carried out by the heat of the combustion exhaust gas 62, and the hydrogen fuel 75 can be stably supplied.
- the fuel cell 5 7 can generate electricity.
- the ceramic honeycomb structure is a structure having a plurality of cells made of ceramic and having a plurality of cells serving as fluid flow paths partitioned by partition walls.
- the combustion means 5 2, the methane reformer 5 3, the hydrogen separator 5 4 and the carbon dioxide fixing device 5 5 are shown in FIG.
- the fuel 61 containing methane has methane as a main component, and the combustion means 52 can efficiently burn the fuel 61 having methane as a main component.
- “mainly composed of methane” means that the content of methane is 80 (volume%) or more.
- the residual gas 76 may contain a combustible substance such as carbon monoxide.
- a combustible substance such as carbon monoxide.
- a part or all of the residual gas 76 may be combusted by the combustion means 1552. This is preferable because fuel is recovered.
- the firing method of the present embodiment can be suitably used when firing ceramic with a calorific value of 100 million to 100 million (kJ / Hr).
- kJ / Hr a calorific value of 100 million to 100 million
- the present invention can be used by combining several small equipment.
- the present invention can be applied to equipment with a capacity of 1 million (k J / H r) or less, it is not economical in the present situation where methane steam reforming equipment is expensive.
- FIG. 3 showing still another embodiment of the above-described firing furnace of the present invention.
- the firing furnace 300 used in the firing method of the present embodiment refer to FIG. It is preferable that the firing furnace is the same as that of the other embodiment of the firing furnace of the present invention described above.
- a combustion gas is generated by injecting and burning a fuel 11 1 containing methane into the combustion means 10 2, and the combustion gas generated by the combustion means 1 0 2 is generated in the main body of the firing furnace.
- This is a firing method in which a body to be fired is introduced into the interior and heated into the interior by combustion gas.
- a methane reforming catalyst 10 6 is further filled therein, and a methane secondary fuel for reforming 1 containing methane as a main component is added to a methane reformer 10 3 disposed in the calcining furnace body 10 1.
- the reforming raw material 1 2 3 composed of 2 1 and steam 1 2 2 is introduced, and the reforming raw material 1 2 3 is heated by the combustion gas and brought into contact with the methane reforming catalyst 1 0 6 to reform the raw material 1 2
- the methane in 3 and water vapor 1 2 2 are reacted to produce reformed gas 1 2 4 containing hydrogen and carbon dioxide.
- the amount of heat necessary for the endothermic reaction when the reforming raw material 1 2 3 is reacted with the methane reforming catalyst 1 06 is calculated as follows. In order to use the calorific value of the combustion gas, a part of the heat of the combustion gas is recovered and reused as the combustion heat of the fuel, thereby reducing the total amount of fuel used.
- the reformed gas 1 2 4 generated in the methane reformer 10 3 is further caused to flow into the hydrogen separator 1 0 4 so that the reformed gas 1 2 4 Hydrogen is selectively separated and separated into hydrogen fuel 1 2 5 containing hydrogen as the main component and residual gas 1 2 6 containing carbon dioxide, and the residual gas separated by hydrogen separator 1 0 4 1 2
- Combustion exhaust gas 1 1 2 is discharged outside.
- the waste liquid 1 4 2 is discharged to the outside.
- methane main fuel for mixing 13 1 which is mainly composed of methane
- “mainly composed of methane” means that the content of methane is 80 (volume%) or more.
- the term “having hydrogen as the main component” in the hydrogen fuel 1 25 whose main component is hydrogen means that the hydrogen content is 50 (volume%) or more.
- the methane main fuel 1 3 1 for mixing and the hydrogen fuel 1 2 5 are used as the fuel 1 1 1 containing methane to be combusted by the combustion means 1 0 2.
- Fuel 1 2 8) and mixed fuel 1 3 2 are used, so hydrogen does not generate carbon dioxide when mixed fuel 1 3 2 (fuel 1 1 1) burns (hydrogen fuel for mixing 1 2 8)
- the generation of carbon dioxide can be reduced by the amount that contains.
- the hydrogen content (hydrogen / mixed fuel) contained in the mixed fuel 13 2 is preferably 5 to 95 (volume%), more preferably 25 to 75 (volume%). If it is less than 5 (volume%), the effect of reducing carbon dioxide may not be sufficient.
- the firing furnace 300 used in the firing method of the present embodiment further includes a fuel cell 10 07, and a part of the hydrogen fuel 1 2 5 is used as fuel cell hydrogen 1 2 7. It can be used to generate electricity.
- the fuel cell 10 7 generates electricity by reacting hydrogen (hydrogen for fuel cells) with oxygen or air.
- the hydrogen separator 10 0 A part of the hydrogen fuel 1 2 5 obtained by separation in 4 can be separated as hydrogen 1 2 7 for a fuel cell, and this can be used for the fuel cell 1 0 7 to generate electric power. Since the hydrogen fuel 1 25 has a high purity of hydrogen contained therein, by using a part of it as the fuel cell hydrogen 1 27, the fuel cell 1 07 can efficiently generate power.
- the power efficiency is about 40%.
- the power efficiency is 60 to Dramatically improved to 70%.
- a part of the hydrogen fuel 1 2 5 obtained by separation in the hydrogen separator 10 4 is mixed with hydrogen.
- fuel cells are about twice as efficient in converting their thermal energy into electrical energy compared to thermal power generation. Therefore, if the power derived from the fuel cell is used instead of the power derived from thermal power generation for the reduction of carbon dioxide emissions, the amount of carbon dioxide reduction for the same amount of power is halved. Therefore, it is possible to reduce the generated carbon dioxide without deliberately fixing the carbon dioxide. If carbon dioxide is immobilized, a higher carbon dioxide reduction effect is produced.
- the total amount of the hydrogen fuel 1 25 may be used as the mixing hydrogen fuel 1 28, or may be used separately for the mixing hydrogen fuel 1 28 and the fuel cell hydrogen 1 27.
- the ratio when dividing hydrogen fuel for mixing 1 2 8 and hydrogen for fuel cell 1 2 7 is not particularly limited, and the carbon dioxide emission amount and power generation amount are appropriately balanced to an appropriate value. What should I do?
- the firing furnace body 101 is an embodiment of the firing furnace of the present invention described with reference to FIG.
- a structure similar to that in the case of the firing furnace body 1 in a certain firing furnace 100 is preferable.
- the methane reformer 10 3 is disposed in the firing furnace body 10 1, FIG.
- it is preferably configured in the same manner as the firing furnace main body 101 shown in FIG. As a result, the same effect can be obtained.
- the firing furnace main body 101 may be a batch type in which a predetermined amount of the objects to be fired are fired intermittently, but the objects to be fired such as a ceramic structure are continuously carried into the interior,
- the continuous firing furnace body 101 is preferably a continuous firing furnace body that is heated and fired inside the fired body and then continuously taken out of the fired body. By continuously firing, the temperature of the combustion gas can be constantly stabilized. Therefore, the methane reforming reaction is performed by the heat of the combustion gas in the methane reformer 10 3 in the firing furnace body 10 1.
- the hydrogen fuel 1 2 5 can be stably supplied, and the hydrogen fuel 1 2 5 and the methane main fuel for mixing 1 3 1
- the mixed fuel 13 2 obtained by mixing can be stably supplied to the combustion means 10 2.
- the ceramic honeycomb structure is a structure having a plurality of cells made of ceramic and having a plurality of cells serving as fluid flow paths partitioned by partition walls.
- the fuel cell 10 7 shown in FIG. 1 in the above-described firing furnace 100 (first invention) of the present invention, combustion means 2, methane reformer 3, hydrogen separator 4, carbon dioxide fixing device 5
- the same configuration as that of the fuel cell 7 is preferable, and the same effect can be obtained.
- the main component of methane for mixing is methane as a main component.
- a mixed fuel 1 3 2 is used which is composed of the fuel 1 3 1 and the hydrogen fuel 1 2 5 (hydrogen fuel for mixing 1 2 8) separated by the hydrogen separator 1 0 4.
- the temperature of the combustion gas is not stable (if the combustion gas has not yet been generated, it is gradually increasing), so the methane reformer It is difficult to carry out the reaction according to 10 3 while using the combustion gas, and the mixed fuel 1 3 2 may be used even after the combustion gas is steadily discharged.
- firing is performed only with the methane main fuel 13 1 for mixing mainly composed of methane.
- another heating device (not shown) using steam or electricity is connected to the methane reformer 10 3. It is also possible to arrange and operate the methane reformer 103 while using the heating device.
- the firing method of this embodiment can be suitably used when firing a ceramic with a calorific value of 100 million to 100 million (kJ ZHr).
- kJ ZHr a ceramic with a calorific value of 100 million to 100 million
- the present invention can be used in combination with several small equipment. You can also.
- the present invention can be applied to facilities of 1 million (k J / Hr) or less, methane steam reforming facilities are expensive and are not economical.
- the methane main fuel 131) for mixing is preferably 5:95 to 100: 0 (volume ratio). If the ratio of reforming methane auxiliary fuel 121 is smaller than 5 (volume ratio), carbon dioxide may not be sufficiently reduced.
- at least one of the mixing main fuel 131 and the reforming main fuel 121 can be liquefied natural gas (LNG).
- LNG liquefied natural gas
- the mixed fuel 132 of the methane main fuel 131 for mixing and the hydrogen fuel 125 (hydrogen fuel 128 for mixing) is burned by the combustion means 102 (this embodiment).
- methane gas (a gas with a methane content of 100 (%)) is used as the fuel 1 1 1 and burned by the calcination means 102 (comparative example).
- methane gas a gas with a methane content of 100 (%)
- the difference in the amount of carbon dioxide and the difference in the amount of generated carbon dioxide are shown, the same result as that obtained when the same comparison is made in the firing furnace 100 of the present invention shown in FIG. 1 described above can be obtained. That is, if only methane gas is burned as fuel 1 1 1, 39800 for the use of methane gas 1 (Nm 3 ZH r)
- the total amount of methane gas used (total of methane main fuel 131 for mixing and sub fuel 121 for reforming) Is 0.9 (NmVH r), the amount of heat obtained is 40380 (k J / Hr).
- the amount of carbon dioxide generated when 1 mol of methane gas is burned is 1 mol (theoretical amount)
- 1 (Nm 3 Z Hr) of carbon dioxide is generated.
- 0.5 (NmVHr) of carbon dioxide is generated.
- this embodiment when this embodiment is compared with the case of the comparative example, the use of methane gas necessary to make the amount of heat generated by the combustion in the combustion means 102 almost equal (this embodiment is slightly larger).
- the dose is reduced by 10% in this embodiment compared to the comparative example, and the amount of carbon dioxide generated is reduced by 50% compared to the comparative example in the present embodiment. It will be done.
- the methane reformer is disposed in the firing furnace main body.
- one embodiment of the firing method of the present invention described above with reference to FIG. 1 is performed.
- a methane reformer disposed outside the calcining furnace main body such as a main body reformer used in this form, may be further provided.
- a methane reformer is provided inside and outside the main body of the firing furnace, and methane reforming is performed using the heat of the combustion gas inside, and methane reforming is performed using the heat of the combustion exhaust gas outside. May be performed.
- FIG. 4 showing still another embodiment of the above-described firing furnace of the present invention.
- the firing furnace 400 used in the firing method of the present embodiment is the same firing furnace as in the other embodiments of the firing furnace of the present invention described above with reference to FIG. preferable.
- a combustion gas is generated by injecting and burning a fuel 16 1 containing methane into the combustion means 15 2, and the combustion gas generated by the combustion means 15 2 1 5 1
- This is a firing method in which the object to be fired is introduced into the interior and heated by the combustion gas, and then fired.
- a methane reforming catalyst 15 6 is further filled therein, and a methane auxiliary fuel 1 for reforming mainly composed of methane is added to a methane reformer 15 3 disposed in the calcining furnace main body 15 1.
- the amount of heat necessary for the endothermic reaction when the reforming raw material 1 7 3 is reacted with the methane reforming catalyst 1 5 6 is calculated as follows. In order to use the calorific value of the combustion gas, a part of the heat of the combustion gas is recovered and reused as the combustion heat of the fuel, thereby reducing the total amount of fuel used.
- the firing method of the present embodiment further includes the reforming produced by the methane reformer 15 3
- Gas 1 7 4 flows into the hydrogen separator 1 5 4 to selectively separate the hydrogen in the reformed gas 1 7 4 to contain hydrogen fuel consisting mainly of hydrogen 1 7 5 and carbon dioxide
- the residual gas 1 7 6 separated into the hydrogen gas separator 1 5 4 is allowed to flow into the carbon dioxide fixing device 1 5 5 and the CO 2 in the residual gas 1 7 6 Carbon is fixed with a fixing agent 1 9 1 so that it is not released to the outside in the form of gas, and hydrogen fuel 1 7 5 separated by hydrogen separator 1 5 4 is used as fuel cell hydrogen 1 7 7, fuel cell 1 5 7, fuel cell hydrogen 1 7 7 reacts with oxygen or air to generate electricity, and the hydrogen in the methane reformer 1 5 3 using the heat of the combustion gas Reformed gas 1 7 4 is generated, hydrogen fuel 1 7 4 is separated from reformed gas 1 7 4 by hydrogen separator 1 5 4, and hydrogen fuel 1 7 5 is Charge as the battery hydrogen 1 7 7 used in power generation in the fuel cell
- the entire amount of hydrogen fuel 1 75 is used as fuel cell hydrogen 1 7 7, and power is generated by fuel cell 1 5 7. It can be effectively recovered and used for power generation, and electric energy with higher utility value can be obtained. Since the hydrogen fuel 1 75 has a high purity of hydrogen contained therein, the fuel cell 1 5 7 can efficiently generate power by using it as the hydrogen 1 7 7 for fuel cells. For example, when the fuel cell is generated using ordinary hydrogen, the power efficiency is about 40%. However, when the fuel cell 1 5 7 generates power in this embodiment, the power efficiency is 60 to 7%. A dramatic improvement of 0%.
- the carbon dioxide produced when the reforming raw material 1 7 3 is reacted with the methane reforming catalyst 1 5 6 is fixed by the carbon dioxide fixing device 1 5 5. Therefore, the carbon dioxide generated from the reforming raw material 17 3 is not released to the outside in the form of gas.
- the firing furnace body 15 1 is fired in the embodiment of the firing furnace of the present invention shown in FIG. 1. It is preferable to configure in the same manner as in the case of the furnace body 1, and the firing furnace body 1 5 1 has methane
- the structure in which the reformer 15 3 is disposed is preferably configured in the same manner as the firing furnace main body 101 shown in FIG. 5 or FIG. As a result, the same effect can be obtained.
- the firing furnace main body 15 1 may be a batch type in which a predetermined amount of the fired body is fired intermittently, but the fired body such as a ceramic structure is continuously carried into the interior.
- the main body is a continuous firing furnace main body 15 1 which is heated and fired inside and then continuously taken out of the fired body.
- the temperature of the combustion gas can be steadily stabilized in the firing furnace main body 15 1, so the methane reformer 1 5 3
- the reforming reaction can be performed stably, whereby hydrogen fuel 1 75 can be stably supplied, and the fuel cell 1 5 7 can stably generate power.
- the ceramic honeycomb structure is a structure having a plurality of cells made of ceramic and having a plurality of cells serving as fluid flow paths partitioned by partition walls.
- combustion means 1 5 2, methane reformer 1 5 3, hydrogen separator 1 5 4, carbon dioxide fixing device 1 5 5 , And fuel cell 15 7 are shown in FIG. 1.
- the fuel 16 1 containing methane preferably contains methane as the main component, and the combustion means 15 2 can efficiently burn the fuel 16 1 containing methane as the main component.
- “mainly composed of methane” means that the content of methane is 80 (volume%) or more.
- the residual gas 1 76 may contain a combustible substance such as carbon monoxide. Therefore, such a combustible substance is contained. In this case, a part or all of the residual gas 1 76 may be burned by the combustion means 15 2. This is preferable because fuel is recovered.
- the firing method of the present embodiment can be suitably used when firing a ceramic with a heat amount of 1 million to 100 million (kJ / Hr). In the case of equipment smaller than 1 million (k JZHr), the present invention can be used by combining several small equipment. Although the present invention can be applied to facilities of 1 million (kJ / Hr) or less, methane steam reforming facilities are expensive and are not economical. Industrial applicability
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- General Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
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- Hydrogen, Water And Hydrids (AREA)
- Industrial Gases (AREA)
- Waste-Gas Treatment And Other Accessory Devices For Furnaces (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP04728256A EP1650518B1 (en) | 2003-07-15 | 2004-04-19 | Firing furnace and method for firing |
CA2531286A CA2531286C (en) | 2003-07-15 | 2004-04-19 | Firing furnace and method for firing |
PL04728256T PL1650518T3 (pl) | 2003-07-15 | 2004-04-19 | Piec do wypalania i sposób wypalania |
JP2005511457A JPWO2005005901A1 (ja) | 2003-07-15 | 2004-04-19 | 焼成炉及び焼成方法 |
Applications Claiming Priority (8)
Application Number | Priority Date | Filing Date | Title |
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JP2003-197289 | 2003-07-15 | ||
JP2003197289 | 2003-07-15 | ||
JP2003-325402 | 2003-09-18 | ||
JP2003325402 | 2003-09-18 | ||
JP2003339999 | 2003-09-30 | ||
JP2003-339999 | 2003-09-30 | ||
JP2004-020397 | 2004-01-28 | ||
JP2004020397 | 2004-01-28 |
Publications (1)
Publication Number | Publication Date |
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WO2005005901A1 true WO2005005901A1 (ja) | 2005-01-20 |
Family
ID=34069243
Family Applications (1)
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PCT/JP2004/005538 WO2005005901A1 (ja) | 2003-07-15 | 2004-04-19 | 焼成炉及び焼成方法 |
Country Status (6)
Country | Link |
---|---|
US (1) | US6997703B2 (ja) |
EP (2) | EP2444766B1 (ja) |
JP (1) | JPWO2005005901A1 (ja) |
CA (1) | CA2531286C (ja) |
PL (2) | PL2444766T3 (ja) |
WO (1) | WO2005005901A1 (ja) |
Cited By (1)
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JP2015113265A (ja) * | 2013-12-13 | 2015-06-22 | 三菱日立パワーシステムズ株式会社 | 水素製造装置および水素製造方法 |
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PL1816101T3 (pl) * | 2004-10-26 | 2013-01-31 | Ngk Insulators Ltd | Piec przemysłowy z urządzeniem do reformingu parowego i stosujący go sposób reformingu parowego |
US20100136441A1 (en) * | 2006-03-28 | 2010-06-03 | Mitsubishi Heavy Industries, Ltd. | Energy supplying system and hydrogen-producing material |
US20080016768A1 (en) | 2006-07-18 | 2008-01-24 | Togna Keith A | Chemically-modified mixed fuels, methods of production and used thereof |
JPWO2008136087A1 (ja) * | 2007-04-23 | 2010-07-29 | 三菱重工業株式会社 | エネルギー供給システム |
FR2937404A1 (fr) * | 2008-10-21 | 2010-04-23 | Jacques Raphael Benzaria | Procede et dispositif permettant de reutiliser une partie du co2 contenu dans les gaz brules issus de la combustion du gaz utilise comme combustible dans les chaudieres industrielles ou domestiques |
US8632922B2 (en) * | 2009-06-16 | 2014-01-21 | Shell Oil Company | Systems and processes for operating fuel cell systems |
US8563186B2 (en) | 2009-06-16 | 2013-10-22 | Shell Oil Company | Systems and processes of operating fuel cell systems |
EP2443689A4 (en) * | 2009-06-16 | 2013-10-23 | Shell Oil Co | SYSTEMS AND PROCESSES FOR OPERATING FUEL CELL SYSTEMS |
US8795912B2 (en) * | 2009-06-16 | 2014-08-05 | Shell Oil Company | Systems and processes for operating fuel cell systems |
JP5787143B2 (ja) * | 2011-06-22 | 2015-09-30 | Toto株式会社 | 固体酸化物形燃料電池装置 |
JP5787144B2 (ja) * | 2011-06-22 | 2015-09-30 | Toto株式会社 | 固体酸化物形燃料電池装置 |
US8820312B2 (en) * | 2011-12-06 | 2014-09-02 | King Fahd University Of Petroleum And Minerals | Oxygen transport reactor-based oven |
WO2014138015A1 (en) * | 2013-03-08 | 2014-09-12 | Corning Incorporated | Fast firing method for ceramics |
CN114303266A (zh) * | 2019-07-19 | 2022-04-08 | 博隆能源股份有限公司 | 集成发电、二氧化碳分离以及下游处理系统及方法 |
CA3238998A1 (en) * | 2021-11-26 | 2023-06-01 | Topsoe A/S | Improving the energy efficiency of a process and plant for producing hydrogen |
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- 2004-04-19 EP EP12151264.4A patent/EP2444766B1/en not_active Expired - Lifetime
- 2004-04-19 PL PL04728256T patent/PL1650518T3/pl unknown
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Also Published As
Publication number | Publication date |
---|---|
PL1650518T3 (pl) | 2013-01-31 |
US6997703B2 (en) | 2006-02-14 |
EP2444766B1 (en) | 2014-04-09 |
US20050014104A1 (en) | 2005-01-20 |
CA2531286C (en) | 2011-10-04 |
EP1650518A1 (en) | 2006-04-26 |
PL2444766T3 (pl) | 2014-09-30 |
EP1650518A4 (en) | 2009-11-11 |
EP2444766A1 (en) | 2012-04-25 |
EP1650518B1 (en) | 2012-08-22 |
JPWO2005005901A1 (ja) | 2006-08-24 |
CA2531286A1 (en) | 2005-01-20 |
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