WO2021246318A1 - Procédé de production de méthane à partir de co2 dans un gaz d'échappement de production de ciment et appareil de méthanation - Google Patents

Procédé de production de méthane à partir de co2 dans un gaz d'échappement de production de ciment et appareil de méthanation Download PDF

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WO2021246318A1
WO2021246318A1 PCT/JP2021/020406 JP2021020406W WO2021246318A1 WO 2021246318 A1 WO2021246318 A1 WO 2021246318A1 JP 2021020406 W JP2021020406 W JP 2021020406W WO 2021246318 A1 WO2021246318 A1 WO 2021246318A1
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exhaust gas
methane
cement
component
harmful
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PCT/JP2021/020406
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Japanese (ja)
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佳典 ▲高▼山
始 川崎
琢磨 高馬
卓哉 小松
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三菱マテリアル株式会社
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Priority claimed from JP2020097645A external-priority patent/JP2021187721A/ja
Priority claimed from JP2020097644A external-priority patent/JP7215462B2/ja
Priority claimed from JP2020101458A external-priority patent/JP7230885B2/ja
Application filed by 三菱マテリアル株式会社 filed Critical 三菱マテリアル株式会社
Publication of WO2021246318A1 publication Critical patent/WO2021246318A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/68—Halogens or halogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B01D53/78—Liquid phase processes with gas-liquid contact
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/50—Carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/36—Manufacture of hydraulic cements in general
    • C04B7/43—Heat treatment, e.g. precalcining, burning, melting; Cooling
    • C04B7/44—Burning; Melting
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C9/00—Aliphatic saturated hydrocarbons
    • C07C9/02—Aliphatic saturated hydrocarbons with one to four carbon atoms
    • C07C9/04—Methane
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/08—Production of synthetic natural gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D17/00—Arrangements for using waste heat; Arrangements for using, or disposing of, waste gases
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/20—Capture or disposal of greenhouse gases of methane
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • 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]
    • 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
    • Y02P10/25—Process efficiency
    • 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
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
    • 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
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
    • Y02P40/18—Carbon capture and storage [CCS]

Definitions

  • the present invention relates to a method for producing methane from CO 2 in cement production exhaust gas and a methaneization apparatus.
  • the methanation method described in Patent Document 1 is conventionally known. That is, it is a method of obtaining methane by separating carbon dioxide contained in combustion exhaust gas and reacting it with hydrogen. In this methanation method, a step of bringing the combustion exhaust gas into contact with a carbon dioxide absorber to absorb carbon dioxide in the combustion exhaust gas, and a gas containing carbon dioxide as a main component by heating the carbon dioxide absorber that has absorbed carbon dioxide.
  • carbon dioxide to which hydrogen is added is passed through a desulfurizer filled with a desulfurizing agent to remove sulfur compounds in the gas.
  • cement manufacturing exhaust gas contains a large amount of oxides other than sulfur compounds, for example, even if a desulfurizer as described in Patent Document 1 is used, the cement manufacturing exhaust gas can be appropriately used. It cannot be processed and methane cannot be produced properly.
  • the present invention has been made in view of such circumstances, and provides a methane production method and a methane conversion apparatus from CO 2 in cement production exhaust gas, which can appropriately treat cement production exhaust gas and appropriately produce methane.
  • the purpose is.
  • the dust such as halogen contained in the cement manufacturing exhaust gas may degrade the CO 2 absorption capacity affect the CO 2 absorbing material. Furthermore, the dust contained in the cement manufacturing exhaust gas (mainly the powder of the cement raw material) adheres to the inside of the equipment piping to form a scale, which increases the pressure loss of the piping and the amount of gas that can be processed by the CO 2 separation and recovery device. There is a risk of reducing the amount.
  • the present invention deterioration of the absorption capacity of the CO 2 absorber can be suppressed by removing the acidic component and the harmful component before separating and recovering the exhaust gas from the cement manufacturing facility. Therefore, CO 2 can be efficiently recovered from the cement manufacturing exhaust gas. Therefore, the efficiency of methanation is also improved.
  • the acidic component contains any one of SOx, NOx and halogen.
  • the harmful components comprises H 2 O, a dust.
  • methane production method in the cement production exhaust gas it is preferable to generate methane after removing water from the separated and recovered CO 2.
  • the cement manufacturing facility is provided with a harmful component removing unit for removing acidic components and harmful components from the exhaust gas from the cement manufacturing facility, and the acidic components and the harmful components.
  • a harmful component removing unit for removing acidic components and harmful components from the exhaust gas from the cement manufacturing facility, and the acidic components and the harmful components.
  • the cement manufacturing exhaust gas CO 2 methane conversion apparatus further includes a dehumidifying section for removing water from the separated and recovered CO 2 , and the methane manufacturing section adds hydrogen to the water-removed CO 2. It is good to produce methane.
  • the cement manufacturing exhaust gas is appropriately treated to produce methane. It can be produced properly, which can reduce CO 2 from energy sources.
  • methane is generated, and the methane is used as a partial or total alternative fuel for fossil fuels for cement manufacturing facilities. This is an example of using it.
  • the CO 2 utilization system 100 includes a cement manufacturing facility 50 and an exhaust gas treatment facility 30 connected to and used in the cement manufacturing facility 50.
  • the exhaust gas treatment facility 30 adds hydrogen to the exhaust gas from the exhaust gas or CO 2 separated and recovered from the exhaust gas to generate methane, and the generated methane is used as fossil fuel for the cement production facility 50. Supplied as an alternative fuel in part or in whole.
  • the cement manufacturing facility 50 includes a raw material storage 1 for individually storing limestone, clay, silica stone, iron raw materials, etc. as cement raw materials, and a raw material mill and dryer for crushing and drying these cement raw materials. 2 and a preheater 3 that preheats the powdered cement raw material supplied through the raw material supply pipe 22 and obtained by this raw material mill, and a calcining furnace 4 that calcins the cement raw material preheated by the preheater 3.
  • a cement calcined kiln 5 for calcining a calcined cement raw material
  • a cooler 6 for cooling a cement clinker after being calcined by the cement calcined kiln 5, and the like.
  • the cement firing kiln 5 is a cylindrical rotary kiln that is slightly inclined sideways, and by rotating around the axis, the cement raw material supplied from the preheater 3 is sent to the kiln front portion 5b to the kiln tail portion 5a while being sent to the kiln front portion 5b.
  • the burner 8 of the front part 5b of the kiln heats and fires at about 1450 ° C. to form a cement clinker.
  • the generated cement clinker is sent from the kiln front portion 5b to the cooler 6.
  • a fuel supply line 15 for supplying fuel including fossil fuels such as coal and petroleum is connected to the burner 8.
  • a supply system (not shown) for an alternative heat source such as waste plastic or waste tire is also provided to supplement the heat energy.
  • the cement clinker is cooled to a predetermined temperature by the cooler 6 and then sent to the finishing process.
  • the preheater 3 is constructed in which a plurality of cyclones 13 (four in the example shown in FIG. 2) that circulate the exhaust gas generated in the cement firing kiln 5 are connected in the vertical direction.
  • a calciner 4 is connected between the cyclone 13 at the bottom and the cyclone 13 above it.
  • the cement raw material calcined by the combustion gas of the calcining furnace 4 is supplied from the lowermost cyclone 13 to the kiln tail portion 5a of the cement calcined kiln 5.
  • the calcining furnace 4 has a burner 41 inside, and by burning fuel such as coal supplied from the fuel supply line 42, the cement raw material sent from the upper cyclone 13 is calcined.
  • the calcined cement raw material is supplied to the lowermost cyclone 13 via the rising duct 25 together with the exhaust gas generated by the calcined.
  • the cement raw material is supplied from the lowermost cyclone 13 to the kiln tail portion 5a of the cement firing kiln 5.
  • the rising duct 25 sends the exhaust gas from the kiln tail portion 5a of the cement firing kiln 5 to the lowermost cyclone 13, and the exhaust gas generated in the calcining furnace 4 is also supplied to the cyclone 13 through the rising duct 25.
  • the exhaust gas from the cement firing kiln 5 and the exhaust gas from the calcining furnace 4 are integrated and passed through the preheater 3 from the lower side to the upper side, and then introduced into the raw material mill and the dryer 2 through the exhaust pipe 9.
  • the raw material mill and the dryer 2 are adapted to crush and dry the cement raw material at the same time by introducing the exhaust gas from the calcining furnace 4 and the cement firing kiln 5.
  • An exhaust gas treatment line 12 including a dust collector 10, a chimney 11, and the like is connected to the raw material mill and the dryer 2.
  • the exhaust gas treatment facility 30 includes an exhaust gas collection line 311 that collects exhaust gas generated in the cement firing kiln 5 and the calcination furnace 4 and before being discharged from the chimney 11, and CO from the exhaust gas sent from the exhaust gas collection line 311. It is provided with a methaneization device 31 that separates and recovers 2 and adds hydrogen to the separated and recovered CO 2 to generate methane, and a methane supply device 32 that supplies the generated methane to the cement production facility 50.
  • the exhaust gas collection line 311 is connected between the dust collector 10 and the chimney 11 in the exhaust gas treatment line 12 of the cement manufacturing facility 50, and collects a part of the exhaust gas generated during cement firing. Since it is exhaust gas generated by cement firing, it includes some exhaust gas from combustion of fuel such as coal, but it also contains a large amount of exhaust gas derived from limestone.
  • Methanation apparatus 31 includes a CO 2 separation and recovery device 310 for separating and recovering CO 2 from flue gas, hydrogen mixed for mixing by supplying hydrogen (e.g. hydrogen gas) in the CO 2 separated recovered by CO 2 separation and recovery device 310 It includes a unit 316 and a methane production unit 317 that produces methane from CO 2 mixed with hydrogen.
  • hydrogen e.g. hydrogen gas
  • CO 2 separation and recovery device 310 as shown in FIG. 3, and acid components such as SOx and NOx from the exhaust gas collected by the exhaust gas collecting line 311, H 2 O, harmful component removing unit for removing harmful components such as dust and 312, and the CO 2 separation collector 313 for separating and recovering CO 2 from the harmful components have been removed exhaust gas, a compression unit 314 for compressing the recovered CO 2, to remove water from the compressed CO 2 It is provided with a dehumidifying unit 315.
  • the exhaust gas sent from the exhaust gas collection line 311 may include not only the combustion exhaust gas of fossil fuels such as coal, petroleum coke, and heavy oil, but also the combustion exhaust gas such as waste plastics and waste tires.
  • CO 2 for example, as would fall about 20 several percent, it is included gases and acidic components and harmful components other than CO 2. Therefore, the harmful component removing unit 312 removes acidic components (for example, acid gases such as nitrogen oxides (NOx) and sulfur oxides (SOx)) and harmful components from the exhaust gas, and is filled with an aqueous NaOH solution or the like. It is equipped with a scraper, a dehumidifier, an electrostatic dust collector, etc.
  • acidic components for example, acid gases such as nitrogen oxides (NOx) and sulfur oxides (SOx)
  • halogens fluorine (F), chlorine (Cl), bromine (Br), iodine (I), etc.
  • SOx removal method As a desulfurization method (SOx removal method), a wet limestone gypsum method, a magnesium hydroxide method, and a soda absorption method are known. These are methods of absorbing SOx with an alkaline solution, and there is a method of using coal ash as a dry method. Further, as a method for simultaneously treating desulfurization (SOx removal) and denitration (NOx removal), there are a dry method, an activated carbon method, and an electron beam method.
  • the denitration method there are a catalytic reduction method (SCR method and the like) and a non-catalytic reduction method as a dry method, and an oxidation absorption method, an oxidation reduction method and an equimolar absorption method as a wet method.
  • the SOx of the exhaust gas from the cement manufacturing equipment is generally several tens of ppm or less because the suspension preheater functions as a desulfurization device.
  • the Ni catalyst which is widely used as a catalyst for methanation, removes harmful components because the sulfur compound reacts on the surface of the Ni catalyst under the sulfur compound mixed with H 2 and covers the surface to deteriorate the yield of methanation. It is necessary to remove the sulfur compound in the part 312. Similarly, NOx and halogens (Cl, F, etc.) may adhere to the surface of the Ni catalyst and deteriorate the yield of methanation, so it is necessary to remove them by the harmful component removing unit 312.
  • any of the above removal methods may be used as the desulfurization (SOx removal) and denitration (NOx removal) methods by the harmful component removing unit 312.
  • SOx removal desulfurization
  • NOx removal denitration
  • any of the above desulfurization methods and any of the above denitration methods are used to remove oxidizing gases such as nitrogen oxides (NOx) and sulfur oxides (SOx).
  • CO 2 separation collector 313 is made common CO 2 recovery apparatus, the inside absorbs CO 2 CO 2 absorbent (amine compound liquid absorbing material dissolved in water, the amine compound to the porous material A supported solid absorbent or the like) is provided, and the exhaust gas after the harmful components or the like are removed comes into contact with the solid absorbent, so that CO 2 in the exhaust gas is absorbed by the CO 2 absorbent. Then, such as by heating the CO 2 absorbing material that has absorbed CO 2, is recovered by extraction of CO 2 from the CO 2 absorber.
  • the CO 2 separation / recovery unit 313 discharges the exhaust gas after CO 2 has been removed to the outside.
  • the compression unit 314 compresses the recovered CO 2 by applying a pressure of 0.1 MPa or more, preferably 0.5 to 1.0 MPa.
  • Dehumidifying unit 315 by cooling the compressed CO 2, removing the moisture contained in the CO 2. This dehumidification is performed to remove the moisture before the methanation because it affects the oxidation of the Ni-based catalyst in the methan
  • the hydrogen mixing unit 316 supplies hydrogen to the dehumidified CO 2 to mix and pressurize it.
  • hydrogen hydrogen gas generated by artificial photosynthesis using renewable energy, decomposition of water, etc. can be used.
  • the amount of hydrogen added by the hydrogen mixing unit 316 is appropriately set so that the concentration of hydrogen in CO 2 (mixed gas) after the hydrogen is mixed becomes a concentration at which methane can be easily produced.
  • the methane production unit 317 produces methane from CO 2 mixed with hydrogen.
  • the methane production unit 317 is composed of a general methane production apparatus, and includes a plurality of reactors (not shown) filled with catalysts that are active in methaneization, and CO 2 in which hydrogen is mixed in these reactors.
  • Methane is produced by supplying and reacting.
  • Ni, Pt, Pd, and Cu are used as the hydrogenation catalyst, but in the methanation catalyst, in particular, Al 2 O 3 , Cr 2 O 3 , SiO 2 , Mg Al 2 O 4 , TiO 2 , and so on.
  • Supported Ni and Ni alloys such as ZrO 2 are used.
  • the conditions for a general methanation reaction are a temperature of 200 ° C. to 700 ° C., preferably 200 ° C. to 350 ° C., and a pressure of 0.1 to 3 MPa.
  • the reaction is carried out in multiple stages in order to improve the reaction yield of methane.
  • the methane supply device 32 is connected to a tank 322 that compresses and stores methane produced by the methaneization device 31 by a pump 321 and a tank 322, and stores methane in a burner 8 of the kiln front portion 5b.
  • a methane supply line 323 for sending to each of the burners 41 of the calcination furnace 4.
  • the methane supply line 323 is a fuel supply line 15 that supplies fuel such as coal and petroleum to the burner 8 of the cement firing kiln 5, and a fuel supply line 42 that supplies fuel such as coal to the burner 41 of the calcination furnace 4. Connected to each. As a result, methane is supplied to each of the burners 8 and 41 together with the fuel.
  • a powdery cement raw material obtained by crushing and drying limestone, clay, silica stone, iron raw material, etc. as a cement raw material is preheated, and the preheated cement raw material is calcined and then fired. Then, by cooling this, a cement clinker is manufactured.
  • Exhaust gas generated in the cement firing kiln 5 and the calcining furnace 4 due to the production of this cement clinker is introduced into the raw material mill and the dryer 2 through the exhaust pipe 9 after passing through the preheater 3 from the lower side to the upper side, and is used as a cement raw material. After being used for drying, it is discharged from the chimney 11 via the dust collector 10.
  • the harmful component removing unit 312 removes the acidic component and the harmful component from the exhaust gas.
  • the nitrogen oxides (NOx) and sulfur oxides (SOx), halogen, and H 2 O, such as dust are removed.
  • the CO 2 separation and recovery unit 313 extracts CO 2 from the exhaust gas and separates and recovers it. At this time, the exhaust gas from which CO 2 has been removed is discharged to the outside.
  • the recovered CO 2 is compressed by applying a pressure of 0.1 MPa or more, preferably 0.5 to 1.0 MPa by the compression unit 314, and the water contained in the CO 2 is removed by the dehumidifying unit 315.
  • hydrogen is supplied to the dehumidified CO 2 by the hydrogen mixing unit 316, mixed, and pressurized.
  • the methane production unit 317 produces methane from CO 2 mixed with hydrogen.
  • the methane produced in this way is stored in the tank 322 of the methane supply device 32. Then, the methane stored in the tank 322 is supplied to the cement firing kiln 5 and the calcining furnace 4 via the methane supply line 323.
  • Fossil fuels such as oil and coal are supplied to the cement fired kiln 5 from the fuel supply line 15. By supplying methane, a part of the fossil fuel can be replaced with methane. Fossil fuels can be reduced. Similarly, in the calcination furnace 4, fossil fuels can be reduced because part or all of the fuel such as coal is replaced with methane.
  • the dehumidifying unit 315 by cooling the compressed CO 2, it is assumed that the removal of moisture contained in the CO 2, is not limited thereto, from the CO 2 separated recovered Any method can be used as long as the water can be removed.
  • the generated methane is supplied to both the cement firing kiln 5 and the calcining furnace 4, it may be supplied to either one.
  • methane was generated using the exhaust gas from both the cement firing kiln 5 and the calcining furnace 4, it can also be applied to cement manufacturing equipment that does not have a calcining furnace. In that case, the cement firing kiln can be used. Produces methane from the exhaust gas of the kiln.

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  • Gas Separation By Absorption (AREA)

Abstract

Dans la production de méthane à partir d'un gaz d'échappement provenant d'une installation de production de ciment, un composant acide tel que le SOx, le NOx et un halogène et un composant nocif tel que H2O et la poussière sont éliminés du gaz d'échappement, et le gaz d'échappement duquel le composant acide et le composant nocif ont été éliminés est mis en contact avec un matériau absorbant de CO2 pour séparer et collecter le CO2. De cette manière, la détérioration de la capacité d'absorption du matériau absorbant de CO2 peut être empêchée et le gaz d'échappement de production de ciment peut être traité correctement pour produire du méthane de manière appropriée. Par conséquent, le CO2 induit par l'énergie peut être réduit et l'effet de réduction d'émission de gaz à effet de serre peut être amélioré.
PCT/JP2021/020406 2020-06-04 2021-05-28 Procédé de production de méthane à partir de co2 dans un gaz d'échappement de production de ciment et appareil de méthanation WO2021246318A1 (fr)

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