WO2015151992A1 - 芳香族化合物の製造システム及びその製造方法 - Google Patents
芳香族化合物の製造システム及びその製造方法 Download PDFInfo
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- WO2015151992A1 WO2015151992A1 PCT/JP2015/059330 JP2015059330W WO2015151992A1 WO 2015151992 A1 WO2015151992 A1 WO 2015151992A1 JP 2015059330 W JP2015059330 W JP 2015059330W WO 2015151992 A1 WO2015151992 A1 WO 2015151992A1
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- Prior art keywords
- aromatic compound
- gas
- hydrogen
- production
- ammonia
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 364
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- 238000000034 method Methods 0.000 title claims description 120
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- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0838—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
- C01B2203/0844—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
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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
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1258—Pre-treatment of the feed
- C01B2203/1264—Catalytic pre-treatment of the feed
- C01B2203/127—Catalytic desulfurisation
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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
- C01B2203/1288—Evaporation of one or more of the different feed components
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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
- C01B2203/14—Details of the flowsheet
- C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
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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
- C01B2203/14—Details of the flowsheet
- C01B2203/148—Details of the flowsheet involving a recycle stream to the feed of the process for making hydrogen or synthesis gas
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Definitions
- the present invention relates to an aromatic compound manufacturing system and a manufacturing method thereof, and more particularly, to an aromatic compound manufacturing system and an aromatic compound manufacturing method in an ammonia manufacturing plant.
- a purge gas containing unreacted substances such as hydrogen (H 2 ) and methane (CH 4 ) has been generated.
- a method of using such a purge gas there is known a method in which a part of hydrogen is recovered from the purge gas and reused in a methanol production plant, and unrecovered hydrogen is reacted with sulfur to remove it as hydrogen sulfide. (Patent Document 1).
- Japanese Patent No. 4781612 Japanese Patent No. 4565277 Japanese Patent No. 5082254
- the present invention is used for regeneration of a catalyst used for synthesis of an aromatic compound by increasing the purity of hydrogen that becomes surplus purge gas generated in a plant for producing ammonia, methanol, etc.
- the unreacted gas is used in a plant for producing ammonia, methanol, etc., and the plant for producing ammonia, methanol, etc. and the aromatic compound production apparatus are installed side by side, so that the aromatic compound, ammonia, methanol, etc.
- an aromatic compound production system comprises a first production apparatus for synthesizing a target substance from natural gas, and an aromatic compound synthesized from natural gas by a catalytic reaction. Resulting from the synthesis reaction of the first production apparatus with a second production apparatus supplying a mixed gas of reaction methane and by-product hydrogen to the first production apparatus to produce the target substance
- a hydrogen separation device that separates hydrogen from the purge gas and supplies the second production apparatus with the catalyst to regenerate the catalyst used in the catalytic reaction.
- the purity of surplus hydrogen in the purge gas generated from the synthesis of the target substance from natural gas is increased to regenerate the catalyst used when synthesizing the aromatic compound.
- the unreacted gas accompanying the synthesis of the aromatic compound can be used for the production of the target substance. As a result, it is possible to efficiently produce both the target substance derived from natural gas and the aromatic compound.
- the present invention in another form, synthesizes methane by a methanation reaction from carbon dioxide recovered from the exhaust gas of the first production apparatus and the hydrogen supplied from the hydrogen separator, A third manufacturing apparatus that supplies the raw material to the second manufacturing apparatus can be further provided.
- methane is efficiently synthesized from carbon dioxide discharged into the atmosphere from a production device that synthesizes the target substance from natural gas and hydrogen that is surplus in addition to catalyst regeneration in the hydrogen separator.
- a production device that synthesizes the target substance from natural gas and hydrogen that is surplus in addition to catalyst regeneration in the hydrogen separator. Therefore, it can be used for the synthesis of aromatic compounds. Therefore, an aromatic compound and a target substance can be obtained efficiently while suppressing raw material costs.
- the target substance is ammonia
- the aromatic compound is one or more aromatic compounds selected from the group consisting of benzene, toluene, xylene and naphthalene
- the first production apparatus is installed in an ammonia production plant. It is preferable that the second production apparatus is installed in parallel in the ammonia production plant, and the aromatic compound is produced using an energy source of the plant.
- various energy sources generated on a large scale in an ammonia production plant can be used for the production of aromatic compounds.
- steam generated in the ammonia production process can be used as a power source for the shafts of rotating equipment such as heating media and compressors for the production of aromatic compounds, and the cold heat of ammonia can be used for the production of aromatic compounds.
- the combined efficiency of the aromatic compound and ammonia in the aromatic compound synthesizer and the ammonia production plant is improved.
- the second manufacturing apparatus further includes a compressor and a cooler for manufacturing the aromatic compound.
- the catalyst may be a ZSM-5 type zeolite catalyst
- the internal pressure of the second production apparatus may be 0.1 MPa or more and 3.0 MPa or less
- the internal temperature may be 700 ° C. or more and 900 ° C. or less. Is preferred.
- the conversion rate of methane can be improved with a low reaction pressure in the second production apparatus, and an aromatic compound can be obtained efficiently.
- the combined efficiency of the aromatic compound and ammonia in the aromatic compound synthesizer and the ammonia production plant is improved.
- the present invention in another aspect is a method for producing an aromatic compound.
- the method for producing an aromatic compound according to the present invention comprises a step of synthesizing a target substance from natural gas in a first production apparatus, and a synthesis of an aromatic compound by a catalytic reaction from natural gas in a second production apparatus, Supplying a mixed gas of mainly unreacted methane and by-product hydrogen to the first production apparatus to produce the target substance, and hydrogen from a purge gas generated from the first production apparatus. Separating and supplying to the second production apparatus in order to regenerate the catalyst used in the catalytic reaction.
- excess high-purity hydrogen separated from the purge gas generated in synthesizing the target substance from natural gas is used to regenerate the catalyst used when synthesizing the aromatic compound.
- a mixed gas composed of unreacted methane and hydrogen as a by-product accompanying the synthesis of the aromatic compound can be used for producing the target substance. As a result, it is possible to efficiently produce both the target substance derived from natural gas and the aromatic compound.
- the purity of hydrogen which is an excess of purge gas generated as a by-product of a plant, is used for regeneration of a catalyst used for synthesis of an aromatic compound, and is not yet obtained from the synthesis of the aromatic compound.
- the reaction gas and / or by-products are used in an ammonia or methanol production plant, and the ammonia or methanol production plant and the aromatic compound production apparatus are installed side by side to produce a product of the aromatic compound and ammonia or methanol production plant. And a method for synthesizing the aromatic compound.
- FIG. 1 is a conceptual diagram illustrating a first embodiment of an aromatic compound manufacturing system and a manufacturing method thereof according to the present invention.
- FIG. 2 is a conceptual diagram illustrating the aromatic compound manufacturing apparatus according to the first embodiment of the aromatic compound manufacturing system and method according to the present invention.
- FIG. 3 is a conceptual diagram illustrating a second embodiment of the aromatic compound manufacturing system and the manufacturing method thereof according to the present invention.
- FIG. 4 is a conceptual diagram illustrating an aromatic compound manufacturing apparatus according to the second embodiment of the aromatic compound manufacturing system and method according to the present invention.
- FIG. 1 is a conceptual diagram illustrating a first embodiment of an aromatic compound manufacturing system according to the present invention.
- the aromatic compound manufacturing system 1 of the present embodiment includes a manufacturing apparatus 2 (first manufacturing apparatus), a hydrogen separator 3, and an aromatic compound manufacturing apparatus 4 (second manufacturing). Device).
- the production apparatus 2 is generally installed in an existing or newly established ammonia production plant, and includes a raw material supply line L 0 , an exhaust gas supply line L 2 , a synthetic product supply line L 4 , and an unreacted gas supply line. and L 5, a fuel supply line L 7, a mixed gas supply line L 10, are connected to.
- Manufacturing apparatus 2 the natural gas from the raw material supply line L 0 is supplied as raw materials to synthesize ammonia from predominantly methane contained, and is configured to supply the synthesized ammonia compound feed line L 4 .
- a purge gas mainly containing a large amount of surplus hydrogen, methane and nitrogen is generated as an unreacted substance.
- the manufacturing apparatus 2 is connected to the hydrogen separator 3 via the unreacted gas supply line L 5 and the purge gas supply line L 18 branched from the composite supply line L 4, and the purge gas is supplied to the hydrogen separator 3. It is configured to supply.
- Manufacturing apparatus 2 the carbon dioxide and water discharged in the production process of ammonia is configured to supply to the exhaust gas supply line L 2.
- the manufacturing apparatus 2 is linked to the aromatic production apparatus 4 via the mixed gas supply line L 10, mixed gas mainly containing methane and hydrogen from an aromatic compound production apparatus 4 is supplied as a fuel It is comprised so that.
- the production apparatus 2 includes a synthesis gas production apparatus 2a, a first compressor 2b, and a first synthesizer 2c.
- the production apparatus 2 can include a desulfurization apparatus (not shown). If there is such a desulfurization apparatus, the sulfur component contained in the natural gas as a raw material is adsorbed and removed in advance, and the raw material supply line L is supplied to both the synthesis gas production apparatus 2a and the aromatic compound production apparatus 4. 0 and via a material supply line L 8 can be supplied to low sulfur concentration methane gas.
- the manufacturing apparatus 2 includes a large-scale cooling system. With such a cooling system, the cooling system of the manufacturing apparatus 2 can be shared by both manufacturing processes of ammonia and aromatic compounds.
- the production apparatus 2 is configured to use the enormous energy source of the ammonia production plant for the aromatic compound production apparatus 4.
- An “energy source” is an energy source resulting from a large system of an ammonia production plant including the cooling system.
- Use of “energy source due to large system” means use as a heat source of a heat medium (for example, steam) or a refrigerant (for example, ammonia) used or generated in an ammonia production process by a large ammonia production plant, Use of a heat medium (for example, steam) as a power source for a rotating machine, use of unreacted materials and / or by-products as fuel, use of large-scale electric power, and the like.
- a heat medium for example, steam
- a refrigerant for example, ammonia
- Synthesis gas production unit 2a includes a known steam reformer and a secondary reformer, the raw material supply line L 0, the process line L 1, an exhaust gas supply line L 2, the fuel supply line L 7, mixed a gas supply line L 10, are connected to the steam supply line and air supply line (not shown).
- the steam reformer is configured to steam reform methane supplied from the raw material supply line L 0 with steam (H 2 O) supplied from the steam supply line.
- carbon monoxide CO
- carbon dioxide hydrogen
- the carbon monoxide is converted into carbon dioxide (hereinafter also referred to as a shift reaction).
- the shift reaction is an exothermic reaction, it becomes an endothermic reaction as a whole, and thus it is necessary to heat from the outside.
- unreacted gas generated in the aromatic compound synthesis process in the aromatic compound production apparatus 4 can be used. Therefore, the co-production efficiency of ammonia and aromatic compounds can be improved.
- the syngas production apparatus 2a is a process line that contains process gas mainly containing nitrogen supplied from an air supply line to synthesize ammonia and hydrogen, carbon monoxide and carbon dioxide generated in the reforming step.
- Combustion exhaust gas that is supplied to L 1 and mainly contains carbon dioxide and water is configured to be supplied to the exhaust gas supply line L 2 .
- the first compressor 2b is coupled to the process line L 1 and L 3.
- the first compressor 2b is a process gas supplied from the process line L 1, and compressed to a predetermined pressure suitable for the synthesis of ammonia, and is configured to supply the process line L 3.
- the process gas compressed by the first compressor 2b is by a heating device (not shown) disposed in the process line L 3, it may be preheated to a predetermined temperature suitable for the synthesis of ammonia.
- the process line L 3 and connects the unreacted gas supply line L 5, and is supplied for a predetermined amount of unreacted gas from unreacted gas supply line which L 5 of the synthesis of ammonia.
- First combiner 2c is coupled to the process line L 3 and synthetic feed line L 4.
- First combiner 2c combines the ammonia from the process gas and / or unreacted gas supplied from the process line L 3, and is configured to provide the composite supply line L 4.
- a gas mainly containing unreacted hydrogen, methane, and nitrogen is generated.
- the synthesis product supply line L 4 is connected to an unreacted gas supply line L 5 and a purge gas supply line L 18 for separating the unreacted gas from ammonia.
- the synthesis product supply line L 4 is configured to supply the unreacted gas to the unreacted gas supply line L 5 and supply the purge gas to the hydrogen separation device 3 via the purge gas supply line L 18. ing.
- the purge gas supply to the purge gas supply line L 18 can be adjusted by the supply amount adjusting valve (not shown) provided in the purge gas supply line.
- the hydrogen separator 3 is provided in parallel with the ammonia production plant, and is connected to the purge gas supply line L 18 , the hydrogen supply line L 6, and the fuel supply line L 7 .
- the hydrogen separator 3 is supplied with a purge gas supplied in a predetermined amount via a purge gas supply line L 18 in order to prevent accumulation of inert gas.
- Hydrogen separator 3 separates the hydrogen from the supplied purge gas from the purge gas supply line L 18, and is configured to supply to the aromatic compound production apparatus 4 via the hydrogen supply line L 6.
- the hydrogen separation device 3, a separate part of the hydrogen purge gas, and is configured to supply a fuel to the synthesis gas production unit 2a of the manufacturing apparatus 2 via the fuel supply line L 7.
- Unreacted gas supplied from the unreacted gas supply line L 5 represents, as compared with the gas mixture from an aromatic compound production apparatus 4, a high hydrogen partial pressure. For this reason, hydrogen can be efficiently separated from the unreacted gas having a high hydrogen partial pressure generated from the production apparatus 2 of the ammonia production plant and used for catalyst regeneration in the aromatic compound production apparatus 4.
- Examples of the hydrogen separation method in the hydrogen separator 3 include a PSA (Pressure Swing Adsorption) type, a membrane separation type, and the like.
- FIG. 2 is a conceptual diagram illustrating the aromatic compound manufacturing apparatus 4 according to the first embodiment of the aromatic compound manufacturing system and method according to the present invention.
- an aromatic compound production apparatus (second production apparatus) 4 is provided in parallel with the ammonia production plant, and includes a heater 4a, a second synthesizer 4b, The compressor 4c, the cooler 4d, and the gas-liquid separator 4e are provided.
- the aromatic compound production apparatus 4 is made of a natural gas mainly containing methane, which is a lower hydrocarbon having 4 or less carbon atoms, from an aromatic compound having 6 or more carbon atoms, particularly benzene (C 6 H 6 ), toluene (C 7 H 8 ) and xylene (C 8 H 10 ) (hereinafter, one or more aromatic compounds selected from the group consisting of benzene, toluene, and xylene are referred to as BTX).
- the aromatic compound production apparatus 4 is configured to supply a mixed gas mainly containing unreacted methane and by-product hydrogen to the production apparatus 2 and use it as a fuel for an ammonia production process.
- the aromatic compound production device 4 is configured to remove deposits on the catalyst surface used for the aromatic compound using hydrogen supplied from the hydrogen separation device 3.
- Heater 4a is linked to the material supply line L 8 and process lines L 41 ⁇ L 43.
- Heater 4a is a natural gas supplied from the material supply line L 8, preheated to a predetermined temperature suitable for the synthesis of aromatic compounds, is configured to supply the process line L 41.
- the heater 4a from the viewpoint of production efficiency, and a heat and the natural gas of the second combiner 4b process gas temperature was raised is supplied via the process line L 42 from the later heat exchange, It is configured so as to be supplied to the process line L 43 using the remaining heat of the natural gas. This makes it possible to implement the remaining heat of the fuel supplied from the material supply line L 8 efficiently.
- Second combiner 4b is a process lines L 41 and L 42, a mixed gas supply line L 10, a hydrogen supply line L 6, are connected to.
- Second combiner 4b are aromatic compounds from the supplied methane hydrocarbons having 6 or more from the process line L 41, it is constituted particularly by combining the BTX, to supply to the process line L 42.
- the second combiner 4b is a part of a gas mixture of unreacted methane and by-product hydrogen supplied through the mixed gas supply line L 10, is configured so as to burn in a heating furnace (not shown) Yes.
- the second combiner 4b is a hydrogen gas supplied from the hydrogen supply line L 6, and is configured to provide a catalyst provided therein as a catalyst for regeneration.
- the reaction mechanism in the reaction for synthesizing BTX in the second synthesizer 4b, particularly the MTB (Methane To Benzen) reaction for synthesizing benzene from methane, is because the hydrocarbon dehydrogenation reaction is selectively performed.
- hydrogen gas for catalyst regeneration is supplied from the hydrogen separator 3 to the second synthesizer 4b.
- the catalyst regeneration may be carried out simultaneously with the synthesis of BTX, may be performed intermittently by the supply of raw materials from the raw material supply line L 8 stops supplying only hydrogen.
- the internal pressure of the second synthesizer 4b is preferably 0.1 MPa or more and 3.0 MPa or less, and the internal temperature is 600.
- the temperature is preferably from 1000 ° C. to 1000 ° C., more preferably from 700 ° C. to 900 ° C.
- the conversion rate of methane and the production efficiency of BTX can be improved at a low reaction pressure.
- a catalyst in which an active metal is supported on a support is disposed.
- the carrier zeolite, silica, alumina, titania, zirconia, ceria, or a combination thereof can be used.
- the active metal include molybdenum (Mo), cobalt (Co), zinc (Zn), gallium (Ga), iron (Fe), copper (Cu), silver (Ag), nickel (Ni), and tungsten (W).
- Rhenium (Re), barium (Ba), manganese (Mn), zirconium (Zr), platinum (Pt), ruthenium (Ru), rhodium (Rh), palladium (Pd), or a combination thereof can be used.
- the carrier is preferably zeolite, more preferably ZSM-5 type zeolite, and the active metal is more preferably molybdenum.
- the conversion rate of methane and the production efficiency of BTX can be improved at a low reaction pressure.
- the co-production efficiency of ammonia and BTX can be improved.
- Second compressor 4c is coupled to the process line L 43 and L 45.
- the second compressor 4c is preferably used from the process line L 43 in order to achieve a BTX recovery rate of about 80% or more. It boosts the supplied process gas and is configured to supply the process line L 45. Note that the process gas supplied from the process line L 43 is cooled in advance to a predetermined temperature by a cooler (not shown).
- Cooler 4d is a BTX from a process gas in the liquid phase by the gas-liquid separator 4e to separate and recover, further cooling the process gas supplied from the process line L 45, to supply to the process line L 46 It is configured.
- an energy source generated in the ammonia production plant can be used. That is, as the energy source, from the viewpoint of co-production efficiency, it is preferable to take out part of the steam generated in the above-described ammonia production plant and divert it with the second compressor 4c. Moreover, it is preferable to take out a part of the cold heat obtained by the large cooling system of the ammonia production plant described above and divert it with the second cooler 4d.
- refrigerant used in the cooler 4d examples include organic refrigerants such as methanol (CH 4 O), ethylene glycol (C 2 H 6 O 2 ), ammonia (NH 3 ), HFC-32 (CH 2 F 2 ), and the like.
- Flammable chlorofluorocarbon solvents HFC-23 (CHF 3 ), HFC-134a (CH 2 FCF 3 ), HCFC-22 (CHClF 2 ), HCFC-124 (CHClCF 3 ), PFC-14 (CF 4 ), PFC Non-flammable chlorofluorocarbon solvents such as ⁇ 116 (C 2 F 6 ) and PFC-218 (C 3 F 8 ) can be mentioned.
- the product of the plant installed in parallel can be utilized as a refrigerant
- ammonia is used as the refrigerant because it is installed in parallel in the ammonia production plant.
- Gas-liquid separator. 4e, the process line L 46, and BTX supply line L 9, a mixed gas supply line L 10, are connected to.
- the gas-liquid separator 4e gas-liquid-separates the process gas supplied from the process line L 46 into a liquid-phase BTX and a gas-phase mixed gas mainly containing unreacted methane and by-product hydrogen. supplying a BTX phase to BTX supply line L 9, and is configured to supply a mixture gas of vapor to the mixed gas supply line L 10.
- the mixed gas supply line L 10 is branched, a part of the mixed gas was supplied to the second combiner 4b, and is configured to supply the remainder to the synthesis gas production unit 2a.
- the supply amount of the second combiner 4b in supplying gas mixture can be adjusted by (not shown) provided on the mixed gas supply line L 10 supply amount adjustment valve.
- the second manufacturing apparatus 4 is configured to manufacture BTX and supply the first manufacturing apparatus 2 with the mixed gas generated by the synthesis reaction of BTX as fuel.
- a large amount of surplus hydrogen contained in the purge gas that is an unreacted product of the ammonia synthesis reaction in the production apparatus 2 Is used for the regeneration of the catalyst used for the catalytic reaction in the aromatic compound production apparatus 4, and the unreacted gas in the aromatic compound production apparatus 4 is used as the fuel for the steam reforming reaction in the production apparatus 2.
- both ammonia and BTX can be synthesized and manufactured, and ammonia and BTX with reduced manufacturing costs can be efficiently obtained.
- the energy source generated in the ammonia production plant can be used for the second compressor 4c and / or the cooler 4d for the synthesis of the aromatic compound. Thereby, production cost can be suppressed and the co-production efficiency of BTX and ammonia can be improved.
- the large cooling system provided in the production facility 2 of the ammonia production plant can be used in the cooler 4d of the aromatic compound synthesizer 4.
- the production cost can be suppressed and the co-production efficiency of BTX and ammonia can be improved.
- a process for producing ammonia from natural gas will be described.
- natural gas mainly containing methane is supplied from the raw material supply line L 0 to the production apparatus 2 and unreacted from the aromatic compound production apparatus 4 installed in parallel in the ammonia production plant.
- the mixed gas mainly containing methane and by-product hydrogen is supplied to the manufacturing apparatus 2 as a fuel through a mixed gas supply line L 10.
- Ammonia synthesized in the production apparatus 2 is supplied to the synthesis product supply line L 4, and unreacted gas generated in the ammonia synthesis is supplied to the unreacted gas supply line L 5 branched from the synthesis product supply line L 4 .
- a predetermined amount of unreacted gas is returned from the unreacted gas supply line L 5 to the production apparatus 2 via the process line L 3 for recycling of the raw material, and the remainder is unreacted gas supply line to prevent accumulation of inert gas. supplied to the hydrogen separator 3 from L 5 through the purge gas supply line L 18.
- Natural gas contains a sulfur component, which has an adverse effect on the catalyst. For this reason, it is preferable to adsorb and remove such sulfur components in advance by using a desulfurization apparatus (not shown) before natural gas is supplied as a raw material.
- a desulfurization apparatus a natural gas having a low sulfur concentration as a raw material for ammonia synthesis and aromatic compound synthesis is produced on a large scale, and the aromatic compound production apparatus 4 installed in parallel with the production apparatus 2 and the ammonia production plant; Can be supplied to both.
- natural gas that has not been desulfurized is also used as fuel. For this reason, if the temperature of exhaust gas falls and an acid component condenses, it will cause a corrosion problem in a flue.
- the production process of ammonia will be described more specifically.
- the material supply line L 0 natural gas supplied to the synthesis gas production unit 2a from using the steam supplied from the steam supply line, not shown, is modified by the steam reforming reaction.
- the heat required for the reaction is obtained by burning unreacted gas supplied from the mixed gas supply line L 10.
- air is supplied to the first synthesizer 2c for synthesis of ammonia from an air supply line (not shown).
- Oxygen supplied from the air supply line is consumed as shown in the following formulas (1) to (3).
- the heat generated by these exothermic reactions is used for the generation of steam, and the steam is used for generating the raw material and energy source for the steam reforming reaction.
- the process gas mainly containing mainly hydrogen and nitrogen produced by the reforming reaction is supplied to the process line L 1, the carbon dioxide and water produced by the combustion of the unreacted gas, the exhaust gas supply line L 2 is supplied.
- Hydrogen is separated from the purge gas supplied from the purge gas supply line L 18 by the hydrogen separator 3 installed in parallel in the ammonia production plant.
- the separated hydrogen is supplied to the aromatic compound production device 4 for catalyst regeneration via the hydrogen supply line L 6 , and the purge gas from which a part of the hydrogen has been separated is supplied to the synthesis gas production device 2 a via the fuel supply line L 7. To be supplied as fuel.
- Hydrogen is separated from the purge gas by the hydrogen separator 3. Although hydrogen is separated from the purge gas, it is difficult to completely separate hydrogen. Unreacted gas supplied from the unreacted gas supply line L 5 represents a hydrogen partial pressure is high compared to the gas mixture from an aromatic compound production apparatus 4. For this reason, hydrogen can be efficiently separated from the unreacted gas having a high hydrogen partial pressure generated from the production apparatus 2 of the ammonia production plant and used for catalyst regeneration in the aromatic compound production apparatus 4.
- Examples of such a hydrogen separation method include a PSA method and a membrane separation method.
- An aromatic compound having 6 or more carbon atoms is produced from natural gas mainly containing methane, which is a lower hydrocarbon having 4 or less carbon atoms. Further, a mixed gas mainly containing unreacted methane and by-product hydrogen is supplied to the production apparatus 2 and used as a fuel for the ammonia production process. At this time, from the hydrogen separation device 3 through the hydrogen supply line L 6 the hydrogen supplied to the aromatics production apparatus 4 is used as a catalyst regeneration for removing deposits deposited on the catalyst.
- the heater 4a is a methane gas was supplied from the material supply line L 8, was preheated to a predetermined temperature suitable for the synthesis of aromatic compounds by the heater 4a, supplied to the process line L 41 To do.
- a second combiner 4b the heat of the process gas supplied through the process line L 42 from the methane gas heat exchanger, after using the residual heat of the methane supplied to the process line L 43. This makes it possible to implement the pre-heating of the fuel supplied from the material supply line L 8 efficiently.
- the methane supplied from the process line L 41 is synthesized in the second synthesizer 4 b by a catalytic reaction of a predetermined catalyst, and an aromatic compound having 6 or more carbon atoms, particularly BTX, is synthesized and supplied to the process line L 42 . .
- an aromatic compound having 6 or more carbon atoms, particularly BTX is synthesized and supplied to the process line L 42 .
- BTX aromatic compound having 6 or more carbon atoms
- the reaction mechanism in such a BTX synthesis reaction is a reaction mechanism in which carbon is generated as a by-product because a hydrocarbon dehydrogenation reaction is selectively performed. is doing.
- the carbon produced in this manner is mainly deposited and deposited on the catalyst surface, whereby the deterioration of the catalyst proceeds with time and the catalytic activity is lowered.
- hydrogen gas for catalyst regeneration is supplied from the hydrogen separator 3 to the second synthesizer 4b.
- the catalyst regeneration may be carried out simultaneously with the synthesis of BTX, may be performed intermittently by the supply of raw materials from the raw material supply line L 8 stops supplying only hydrogen.
- the reaction conditions are preferably a pressure of 0.1 MPa or more and 3.0 MPa or less, and a reaction temperature of 600 ° C. or more and 1000 ° C. or less, preferably 700 It is more preferable that the temperature is from 900C to 900C. Under such reaction conditions, the conversion rate of methane and the production efficiency of BTX can be improved at a low reaction pressure.
- the facility can be scaled up, and the combined production efficiency of ammonia and BTX can be improved.
- a catalyst in which an active metal is supported on a support is disposed.
- the carrier zeolite, silica, alumina, titania, zirconia, ceria, or a combination thereof can be used.
- the active metal include molybdenum (Mo), cobalt (Co), zinc (Zn), gallium (Ga), iron (Fe), copper (Cu), silver (Ag), nickel (Ni), and tungsten (W).
- Rhenium (Re), barium (Ba), manganese (Mn), zirconium (Zr), platinum (Pt), ruthenium (Ru), rhodium (Rh), palladium (Pd), or a combination thereof can be used.
- the carrier is preferably zeolite, more preferably ZSM-5 type zeolite, and the active metal is more preferably molybdenum.
- the conversion rate of methane and the production efficiency of BTX can be improved at a low reaction pressure.
- the co-production efficiency of ammonia and BTX can be improved.
- process line L 43 The process gas supplied from the process line L 43, the BTX from a process gas in the liquid phase by the gas-liquid separator 4e for separating and recovering, preferably to above about 80% recovery of BTX, process line
- the process gas supplied from L 43 is boosted by the second compressor 4 c and supplied to the process line L 45 .
- process line L 43 processes the supplied to the second compressor 4c gas is cooled to a predetermined temperature beforehand by unillustrated cooler.
- the process gas supplied from the process line L 45 is further cooled by the cooler 4 d and supplied to the process line L 46 in order to facilitate the separation and recovery of the liquid phase BTX.
- the energy source generated in the ammonia production plant can also be used for the second compressor 4c and the cooler 4d. From the viewpoint of co-production efficiency, it is preferable to divert ammonia obtained by the above-described cooling system of the ammonia production plant as a cold heat source.
- an organic refrigerant such as methanol (CH 4 O), ethylene glycol (C 2 H 6 O 2 ), ammonia (NH 3 ), or a combustible substance such as HFC-32 (CH 2 F 2 ).
- Fluorocarbon solvents, HFC-23 (CHF 3 ), HFC-134a (CH 2 FCF 3 ), HCFC-22 (CHClF 2 ), HCFC-124 (CHClCF 3 ), PFC-14 (CF 4 ), PFC-116 ( Nonflammable chlorofluorocarbon solvents such as C 2 F 6 ) and PFC-218 (C 3 F 8 ) can be used.
- refrigerant coolant
- ammonia is preferable as the refrigerant because it is installed in parallel in an ammonia production plant.
- the mixed gas supply line L 10 is branched to supply a portion of the mixed gas containing the unreacted methane and by-product hydrogen primarily to the second combiner 4b, the synthesis gas production unit and the remaining portion 2a To be supplied as fuel.
- the supply amount of the second combiner 4b in supplying gas mixture can be adjusted by (not shown) provided on the mixed gas supply line L 10 supply amount adjustment valve.
- a large amount of surplus hydrogen contained in the purge gas that is an unreacted product of the ammonia synthesis reaction in the production apparatus 2 Is used for the regeneration of the catalyst used for the catalytic reaction in the aromatic compound production apparatus 4, and the unreacted gas in the aromatic compound production apparatus 4 is used as the fuel for the steam reforming reaction in the production apparatus 2.
- both ammonia and BTX can be synthesized and manufactured, and ammonia and BTX with reduced manufacturing costs can be efficiently obtained.
- the surplus energy source in the ammonia production plant can be used for the second compressor 4c and / or the cooler 4d for the synthesis of the aromatic compound.
- the energy source cost of an installation and its maintenance cost can be suppressed, and the co-production efficiency of BTX and ammonia can be improved.
- a large cooling system provided in the production facility 2 of the ammonia production plant can be used in the cooler 4d of the aromatic compound synthesizer 2.
- the production cost can be suppressed and the co-production efficiency of BTX and ammonia can be improved.
- FIG. 3 is a conceptual diagram for explaining a second embodiment of the aromatic compound production system according to the present invention.
- an aromatic compound manufacturing system 1A according to the present embodiment includes a manufacturing apparatus 2 (first manufacturing apparatus), a hydrogen separator 3A, and an aromatic compound manufacturing apparatus 4A (second manufacturing apparatus). Device), a carbon dioxide recovery device 5, and a methane production device 6 (third production device).
- the production apparatus 2 is provided in an ammonia production plant that synthesizes ammonia from methane mainly contained in natural gas.
- the hydrogen separation device 3A, the aromatic compound production device 4A, the carbon dioxide recovery device 5 and the methane production device 6 are juxtaposed with the ammonia production plant.
- Hydrogen separator 3A is provided in parallel in the ammonia production plant, the purge gas supply line L 18, and a fuel supply line L 7, a hydrogen supply line L 11 and L 12, are connected to.
- the hydrogen separator 3A, through the purge gas supply line L 18 is a purge gas supplied at a predetermined amount is supplied in order to prevent the accumulation of inert gas.
- Hydrogen separator 3 separates the hydrogen from the supplied purge gas from the purge gas supply line L 18, a part through the hydrogen supply line L 11 is supplied to the aromatics production apparatus 4A, the hydrogen supply line and the remainder It is configured to supply to the methane production apparatus 6 via L 12 and to the production apparatus 2 via the fuel supply line L 7 .
- hydrogen is separated from the purge gas, but it is difficult to completely separate the hydrogen.
- Unreacted gas supplied from the purge gas supply line L 18 through the unreacted gas supply line L 5 represents, as compared with the gas mixture from the aromatics production apparatus 4A, a high hydrogen partial pressure. For this reason, hydrogen is efficiently separated from the unreacted gas having a high hydrogen partial pressure generated from the production apparatus 2 of the ammonia production plant and used for catalyst regeneration in the aromatic compound production apparatus 4A. It can be used for methane synthesis.
- the hydrogen separation method in the hydrogen separator 3A can be the same method as in the first embodiment.
- FIG. 4 is a conceptual diagram illustrating an aromatic compound manufacturing apparatus 4A according to the second embodiment of the aromatic compound manufacturing system and the manufacturing method thereof according to the present invention.
- the aromatic compound production apparatus 4A (second production apparatus) includes a heater 4Aa, a second synthesizer 4Ab, a second compressor 4c, a cooler 4d, and a separation device. 4Ae.
- the aromatic compound manufacturing apparatus 4A is configured to generate an aromatic compound having 6 or more carbon atoms, particularly BTX, from natural gas mainly containing methane, which is a lower hydrocarbon having 4 or less carbon atoms.
- the aromatic compound production apparatus 4A is configured to supply a mixed gas mainly containing unreacted methane and by-product hydrogen to the production apparatus 2 and use it as a fuel for an ammonia production process.
- the aromatic compound manufacturing apparatus 4A is configured to remove deposits on the catalyst surface used for the aromatic compound using hydrogen supplied from the hydrogen separator 3A.
- Heater 4Aa is linked to methane gas supply line L 15 and process lines L 41 ⁇ L 43.
- Heater 4Aa has a methane gas supplied from the methane gas supply line L 15, preheated to a predetermined temperature suitable for the synthesis of aromatic compounds, is configured to supply the process line L 41.
- the heater 4Aa from the viewpoint of production efficiency, and the second combiner 4Ab from the process line L 42 and the heat of the process gas heating is supplied through the said methane heat exchanger which will be described later, the The methane gas is configured to be supplied to the process line L 43 using the remaining heat of the methane gas. This makes it possible to implement the remaining heat of BTX in the raw material supplied from the methane gas supply line L 15 efficiently.
- Second combiner 4Ab is a process lines L 41 and L 42, a mixed gas supply line L 17, a hydrogen supply line L 11, are connected to.
- Second combiner 4Ab are aromatic compounds of hydrocarbons having 6 or more from the supplied methane from the process line L 41, it is constituted particularly by combining the BTX, to supply to the process line L 42.
- the second combiner 4Ab is a part of a gas mixture of unreacted methane and by-product hydrogen supplied through the mixed gas supply line L 17, is configured so as to burn in a heating furnace (not shown) Yes.
- the second combiner 4Ab is a hydrogen gas supplied from the hydrogen supply line L 11, and is configured to provide a catalyst provided therein as a catalyst for regeneration.
- the reaction mechanism in the reaction of synthesizing BTX in the second synthesizer 4Ab is because hydrocarbon dehydrogenation is selectively performed, so carbon is generated as a byproduct. There is a reaction mechanism to be performed.
- the carbon produced in this manner is mainly deposited and deposited on the catalyst surface, whereby the deterioration of the catalyst proceeds with time and the catalytic activity is lowered.
- hydrogen gas for catalyst regeneration is supplied from the hydrogen separator 3A to the second synthesizer 4Ab.
- the catalyst regeneration may be carried out simultaneously with the synthesis of BTX, may be performed intermittently by stopping the supply of raw materials from the methane gas supply line L 15 supplying only hydrogen.
- the catalyst arranged in the second synthesizer 4Ab can be the same catalyst as in the first embodiment.
- the conditions for the catalytic reaction in the second synthesizer 4Ab can be the same as those in the first embodiment.
- Gas-liquid separator 4Ae includes a process line L 46, and BTX supply line L 16, and the mixed gas supply line L 17, are connected to.
- the gas-liquid separator 4Ae gas-liquid-separates the process gas supplied from the process line L 46 into a liquid-phase BTX and a gas-phase mixed gas mainly containing unreacted methane and by-product hydrogen. supplying a BTX phase to BTX supply line L 16, and is configured to supply a mixture gas of vapor to the mixed gas supply line L 17.
- the mixed gas supply line L 17 is branched, a part of the mixed gas was supplied to the second combiner 4Ab, and is configured to supply the remainder to the synthesis gas production unit 2a.
- the supply amount of the second combiner 4Ab of supplying the mixed gas can be adjusted by (not shown) provided on the mixed gas supply line L 17 supply amount adjustment valve.
- the second manufacturing apparatus 4A is configured to manufacture BTX and to supply the mixed gas generated by the BTX synthesis reaction to the first manufacturing apparatus 2 as fuel.
- the carbon dioxide recovery device 5 a known recovery device arranged in parallel in an ammonia production plant can be used, and preferably a recovery device using a KM-CDR process (registered trademark).
- An exhaust gas supply line L 2, the carbon dioxide supply line L 13, and the processing gas supply line L 14, are connected to.
- the exhaust gas supplied from the gas supply line L 2, carbon dioxide, water, nitrogen and oxygen are mainly contained.
- Carbon dioxide recovery device 5, the exhaust gas carbon dioxide is separated and recovered from, and is configured to supply carbon dioxide supply line L 13. Further, the carbon dioxide recovery device 5, a process gas obtained by removing carbon dioxide from the exhaust gas, and is configured to supply a process gas supply line L 14.
- the methane production apparatus 6 is installed in parallel in the ammonia production plant, and the temperature and pressure inside thereof can be adjusted.
- the hydrogen supply line L 12 , the carbon dioxide supply line L 13, and the methane gas supply line L 15 are provided. It is connected.
- the catalyst provided in the methane production apparatus 6 can be a known catalyst that can be methanated from carbon dioxide and hydrogen.
- a catalyst made of nickel is preferable.
- methane is produced from carbon dioxide and hydrogen as shown in the following formula (7). Since the methanation reaction is an exothermic reaction, the catalyst temperature may be controlled by a cooler (not shown).
- hydrogen is generally insufficient, but in the ammonia production process of the present embodiment, natural gas is supplied from the outside as fuel, and unreacted gas of the aromatic compound production apparatus 4A is supplied as fuel. A large amount of hydrogen is generated as an unreacted substance. For this reason, methane synthesis can be performed without replenishing hydrogen from the outside.
- water is also generated in the reaction, water may be removed by a gas-liquid separator (not shown) in order to increase the methane purity of the methane-containing gas supplied to the aromatic compound production apparatus 4A.
- natural gas supplied to the synthesizer 2 can be supplied from the outside. According to the present embodiment, the same operational effects as those of the first embodiment can be obtained, and methane is synthesized from surplus hydrogen in the ammonia production plant and carbon dioxide released into the atmosphere as exhaust gas, It can be used for the production of BTX in the second synthesizer 4Ab of the group compound production apparatus 4A. Accordingly, it is possible to efficiently produce BTX and ammonia in parallel. In addition, carbon dioxide released into the atmosphere can be effectively used as a raw material, which is preferable from the viewpoint of preventing global warming.
- a process of separating hydrogen from the purge gas will be described.
- the purge gas supplied from the purge gas supply line L 18 via the unreacted gas supply line L 5 is separated from hydrogen by the hydrogen separator 3A installed in parallel in the ammonia production plant.
- Some of the separated hydrogen, via a fuel supply line L 7 is supplied to the synthesis gas production unit 2a, the remainder, supplies the aromatics production device 4A through the hydrogen supply line L 11, the hydrogen supply supplied to the methane production apparatus 6 via the line L 12.
- Hydrogen is separated from the purge gas by the hydrogen separator 3A.
- Unreacted gas supplied from the unreacted gas supply line L 5 represents a hydrogen partial pressure is high compared to the unreacted gas from the aromatics production apparatus 4A. For this reason, hydrogen is efficiently separated from the unreacted gas having a high hydrogen partial pressure generated from the production apparatus 2 of the ammonia production plant and used for catalyst regeneration in the aromatic compound production apparatus 4A. It can be used for methane synthesis.
- An aromatic compound having 6 or more carbon atoms is produced from natural gas mainly containing methane, which is a lower hydrocarbon having 4 or less carbon atoms. Further, a mixed gas mainly containing unreacted methane and by-product hydrogen is supplied to the production apparatus 2 and used as a fuel for the ammonia production process. At this time, from the hydrogen separation device 3 through the hydrogen supply line L 11 and hydrogen supplied to the aromatics production apparatus 4A, it is used as the catalyst for regeneration for removing deposits deposited on the catalyst.
- the heater 4Aa has a methane gas was supplied from the material supply line L 15, it was preheated to a predetermined temperature suitable for the synthesis of aromatic compounds in heater 4Aa, supplied to the process line L 41 To do.
- the supplied methane from the process line L 41 supplies the catalytic reaction of a given catalyst at the second combiner 4Ab, 6 or more aromatic compounds carbide, in particular combining a BTX, the process line L 42 .
- a part of the mixed gas of unreacted methane and by-product hydrogen supplied via the mixed gas supply line L 17 is burned in a heating furnace (not shown).
- a second combiner 4Ab the heat of the process gas supplied through the process line L 42 from the methane gas heat exchanger, after using the residual heat of the methane supplied to the process line L 43. This makes it possible to implement the pre-heating of the raw material supplied from the material supply line L 8 efficiently.
- the reaction mechanism in such a BTX synthesis reaction is a reaction mechanism in which carbon is generated as a by-product because a hydrocarbon dehydrogenation reaction is selectively performed. is doing.
- the carbon produced in this manner is mainly deposited and deposited on the catalyst surface, whereby the deterioration of the catalyst proceeds with time and the catalytic activity is lowered.
- hydrogen gas for catalyst regeneration is supplied from the hydrogen separator 3A to the second synthesizer 4Ab.
- the catalyst regeneration may be carried out simultaneously with the synthesis of BTX, may be performed intermittently by the supply of raw materials from the raw material supply line L 15 is stopped to supply only hydrogen.
- the same catalyst as in the first embodiment can be used.
- reaction conditions using such a catalyst the same conditions as in the first embodiment can be used.
- the process gas supplied via the process lines L 43 to L 46 , the second compressor 4c and the cooler 4d is gas-liquid separated into a liquid-phase BTX and a gas-phase mixed gas by the gas-liquid separator 4Ae. .
- the mixed gas supply line L 17 is branched to supply a portion of the mixed gas containing the unreacted methane and by-product hydrogen primarily to the second combiner 4Ab, synthesis gas production unit and the remaining portion 2a To be supplied as fuel.
- the supply amount of the second combiner 4Ab of supplying the mixed gas can be adjusted by (not shown) provided on the mixed gas supply line L 17 supply amount adjustment valve.
- the exhaust gas supplied from the gas supply line L 2 in addition to carbon dioxide, water, hydrogen and oxygen are mainly contained. Therefore, supplied from the exhaust gas, the carbon dioxide in the carbon dioxide recovery unit 5 to separate and recover, carbon dioxide supply line L 13. Further, the process gas to remove carbon dioxide from the flue gas, supplied into the processing gas supply line L 14.
- the carbon dioxide recovery device 5 it is preferable to use a KM-CDR process (registered trademark).
- the catalyst used in the methanation reaction can be a known catalyst that can be methanated from carbon dioxide and hydrogen.
- a catalyst made of nickel is preferable.
- methane is produced from carbon dioxide and hydrogen as shown in the following formula (7). Since the methanation reaction is an exothermic reaction, the catalyst temperature may be controlled by a cooler (not shown).
- hydrogen is generally insufficient, but in the ammonia production process of the present embodiment, natural gas is supplied from the outside as fuel, and unreacted gas of the aromatic compound production apparatus 4A is supplied as fuel. A large amount of hydrogen is generated as an unreacted substance. For this reason, methane synthesis can be performed without replenishing hydrogen from the outside.
- water is also generated in the reaction, water may be removed by a gas-liquid separator (not shown) in order to increase the methane purity in the gas supplied to the aromatic compound manufacturing apparatus 4A.
- natural gas supplied to the synthesizer 2 can be supplied from the outside. According to the present embodiment, the same operational effects as those of the first embodiment can be obtained, and methane is synthesized from surplus hydrogen in the ammonia production plant and carbon dioxide released into the atmosphere as exhaust gas, It can be used for the production of BTX in the second synthesizer 4Ab of the group compound production apparatus 4A. Accordingly, it is possible to efficiently produce BTX and ammonia in parallel. In addition, carbon dioxide released into the atmosphere can be effectively used as a raw material, which is preferable from the viewpoint of preventing global warming.
- the hydrogen separation devices 3 and 3A and the aromatic compound manufacturing devices 4 and 4A arranged in parallel in the ammonia production plant are illustrated, but the present invention is not limited to this.
- the hydrogen separation devices 3 and 3A and / or the aromatic compound production devices 4 and 4A may be arranged in the ammonia production plant. Even in such a case, the energy source of the ammonia production plant can be used.
- the hydrogen separators 3 and 3A and / or the aromatic compound production apparatuses 4 and 4A may be provided in a separately installed or newly installed aromatic compound production plant.
- a part of the energy source generated in the ammonia manufacturing plant is used for the hydrogen separators 3 and 3A and / or the aromatic compound manufacturing devices 4 and 4A, or the energy source generated in the aromatic compound manufacturing plant.
- a part of can be used for the manufacturing apparatus 2.
- the carbon dioxide recovery device 5 and the methane production device 6 installed in parallel in the ammonia production plant are illustrated, but the present invention is not limited to this.
- the carbon dioxide recovery device 5 and / or the methane production device 6 may be arranged in an ammonia production plant from the viewpoint of production investment cost and power and maintenance cost. Even in such a case, the energy source of the ammonia production plant can be used.
- the production apparatus 2 for synthesizing the target substance from natural gas is provided in the ammonia production plant, but the present invention is not limited to this. Any plant that has the same production equipment or production method as a plant for producing a target substance from natural gas may be used, and for example, it can be applied to a production apparatus such as a methanol production plant, a hydrogen production plant, or a urea production plant.
- natural gas is exemplified as a raw material, but the present invention is not limited to this.
- the raw material may be any raw material containing a lower hydrocarbon, and can be applied to, for example, coal gasification gas, biomass gasification gas, coke oven gas (COG: Coke Oven Gas) and the like. Even from such raw materials, it is possible to co-produce synthetic products and aromatic compounds.
- COG Coke Oven Gas
- the purity of hydrogen that becomes surplus purge gas generated as a by-product of the plant is increased for catalyst regeneration used for synthesis of the aromatic compound.
- unreacted gas from the synthesis of aromatic compounds can be utilized in ammonia or methanol production plants.
- an ammonia or methanol production plant and an aromatic compound production apparatus in parallel, the aromatic compound and the product of the ammonia or methanol production plant can be efficiently produced together.
- Aromatic compound production system 2 Production equipment (first production equipment) 2a: Steam reformer 2b: First compressor 2c: First synthesizer 3, 3A: Hydrogen separator 4, 4A: Aromatic compound production apparatus (second production apparatus) 4a, 4Aa: heater 4b, 4Ab: second synthesizer 4c: second compressor 4d: Cooler 4e, 4Ae: Gas-liquid separator 5: Carbon dioxide recovery device 6: Methane production device (third production device)
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Abstract
Description
2 :製造装置(第一の製造装置)
2a :水蒸気改質器
2b :第一の圧縮機
2c :第一の合成器
3、3A :水素分離装置
4、4A :芳香族化合物製造装置(第二の製造装置)
4a、4Aa:加熱器
4b、4Ab:第二の合成器
4c :第二の圧縮機
4d :冷却器
4e、4Ae:気液分離器
5 :二酸化炭素回収装置
6 :メタン製造装置(第三の製造装置)
Claims (10)
- 天然ガスから対象物質を合成する第一の製造装置と、
天然ガスから触媒反応により芳香族化合物を合成し、主に未反応のメタンと副生物の水素との混合ガスを、前記対象物質を製造するために前記第一の製造装置へ供給する第二の製造装置と、
前記第一の製造装置の合成反応から生じたパージガスより水素を分離し、前記触媒反応で用いられる触媒を再生するために前記第二の製造装置へ供給する水素分離装置と
を備えている芳香族化合物の製造システム。 - 前記第一の製造装置の排ガスから回収された二酸化炭素と、前記水素分離装置から供給された前記水素と、からメタネーション反応によりメタンを合成して、原料として前記第二の製造装置へ供給する第三の製造装置を更に備えている請求項1に記載の芳香族化合物の製造システム。
- 前記対象物質がアンモニアであり、
前記芳香族化合物がベンゼン、トルエン、キシレン及びナフタレンからなる群より選ばれた1種以上の芳香族化合物であり、
前記第一の製造装置がアンモニア製造プラントに設置され、
前記第二の製造装置が前記アンモニア製造プラントに並設されて、前記プラントのエネルギー源を利用して前記芳香族化合物を製造することを特徴とする請求項1又は2に記載の芳香族化合物の製造システム。 - 前記第二の製造装置が、前記芳香族化合物を製造するための圧縮機及び冷却器を更に備えていることを特徴とする請求項3に記載の芳香族化合物の製造システム。
- 前記触媒がZSM-5型のゼオライトからなる触媒であり、
前記第二の製造装置の内部圧力が0.1MPa以上3.0MPa以下であり、その内部温度が700℃以上900℃以下であることを特徴とする請求項1から請求項4のいずれか一項に記載の芳香族化合物の製造システム。 - 天然ガスから第一の製造装置にて対象物質を合成する工程と、
天然ガスから第二の製造装置にて触媒反応により芳香族化合物を合成し、主に未反応のメタンと副生物の水素との混合ガスを、前記対象物質を製造するために前記第一の製造装置へ供給する工程と、
前記第一の製造装置から生じたパージガスより水素を分離し、前記触媒反応で用いられる触媒を再生するために前記第二の製造装置へ供給する工程と
を備えている芳香族化合物の製造方法。 - 前記第一の製造装置の合成工程の排ガスから回収した二酸化炭素と、前記対象物質の合成反応から生じたパージガスより分離した水素とから第三の製造装置にてメタネーション反応によりメタンを合成して、原料として前記芳香族化合物の合成反応へ供給する工程を更に備えている請求項6に記載の芳香族化合物の製造方法。
- 前記対象物質をアンモニアとし、
前記芳香族化合物がベンゼン、トルエン、キシレン及びナフタレンからなる群より選ばれた1種以上の芳香族化合物であり、
前記第一の製造装置をアンモニア製造プラントとし、
前記第二の製造装置を前記アンモニア製造プラントに並設させ、前記プラントのエネルギー源を利用して前記芳香族化合物を製造することを特徴とする請求項6又は7に記載の芳香族化合物の製造方法。 - 前記芳香族化合物を合成する工程が圧縮工程及び冷却工程を更に備え、
前記圧縮工程及び冷却工程が前記アンモニア製造プラントのエネルギー源を利用して行われることを特徴とする請求項8に記載の芳香族化合物の製造方法。 - 前記芳香族化合物の合成反応が、ZSM-5型のゼオライトからなる触媒を用いて行われ、前記芳香族化合物の合成反応が、0.1MPa以上3.0MPa以下の圧力、且つ、700℃以上900℃以下の温度で実施されることを特徴とする請求項6から請求項9のいずれか一項に記載の芳香族化合物の製造方法。
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US15/300,009 US20170137345A1 (en) | 2014-03-31 | 2015-03-26 | System for manufacturing aromatic compound and method for manufacturing same |
EP15772991.4A EP3127892A4 (en) | 2014-03-31 | 2015-03-26 | System for manufacturing aromatic compound and method for manufacturing same |
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EP4067308A1 (en) * | 2021-03-29 | 2022-10-05 | Yara International ASA | Use of the purge gas of a first ammonia converter for reducing the catalyst of a second ammonia converter and method and system thereof |
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JPH06234517A (ja) * | 1993-02-09 | 1994-08-23 | Toyo Eng Corp | アンモニア及びメタノールの併産方法 |
JP2007099748A (ja) * | 2005-02-18 | 2007-04-19 | Mitsubishi Chemicals Corp | 芳香族化合物の製造方法及び水素化芳香族化合物の製造方法 |
WO2010092849A1 (ja) * | 2009-02-12 | 2010-08-19 | 株式会社明電舎 | 芳香族炭化水素製造方法及び芳香族炭化水素製造装置 |
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RU2458899C2 (ru) * | 2006-06-23 | 2012-08-20 | Эксонмобил Кемикэл Пейтентс Инк. | Получение ароматических углеводородов и синтез-газа из метана |
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2014
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2015
- 2015-03-26 US US15/300,009 patent/US20170137345A1/en not_active Abandoned
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JPH06234517A (ja) * | 1993-02-09 | 1994-08-23 | Toyo Eng Corp | アンモニア及びメタノールの併産方法 |
JP2007099748A (ja) * | 2005-02-18 | 2007-04-19 | Mitsubishi Chemicals Corp | 芳香族化合物の製造方法及び水素化芳香族化合物の製造方法 |
WO2010092849A1 (ja) * | 2009-02-12 | 2010-08-19 | 株式会社明電舎 | 芳香族炭化水素製造方法及び芳香族炭化水素製造装置 |
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Cited By (2)
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CN108726477A (zh) * | 2018-06-15 | 2018-11-02 | 上海理工大学 | 一种热平衡紧凑固定床化学链制氢脱碳一体化装置及方法 |
CN108726477B (zh) * | 2018-06-15 | 2021-08-03 | 上海理工大学 | 一种热平衡紧凑固定床化学链制氢脱碳一体化装置及方法 |
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RU2016138631A (ru) | 2018-04-02 |
EP3127892A4 (en) | 2017-12-06 |
EP3127892A1 (en) | 2017-02-08 |
RU2016138631A3 (ja) | 2018-04-02 |
AU2015239360B2 (en) | 2017-08-03 |
US20170137345A1 (en) | 2017-05-18 |
JP2015193571A (ja) | 2015-11-05 |
RU2650513C2 (ru) | 2018-04-16 |
AU2015239360A1 (en) | 2016-10-20 |
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