Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
  • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
  • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
  • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
  • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
  • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
  • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
  • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
  • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
  • C10B53/07—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of solid raw materials consisting of synthetic polymeric materials, e.g. tyres
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
  • C10J3/005—Rotary drum or kiln gasifiers
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
  • C10J3/72—Other features
  • C10J3/721—Multistage gasification, e.g. plural parallel or serial gasification stages
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
  • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
  • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
  • C10K3/04—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment reducing the carbon monoxide content, e.g. water-gas shift [WGS]
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
  • C01B2203/02—Processes for making hydrogen or synthesis gas
  • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
  • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
  • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
  • C01B2203/02—Processes for making hydrogen or synthesis gas
  • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
  • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
  • C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
  • C01B2203/02—Processes for making hydrogen or synthesis gas
  • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2200/00—Details of gasification apparatus
  • C10J2200/15—Details of feeding means
  • C10J2200/158—Screws
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
  • C10J2300/0913—Carbonaceous raw material
  • C10J2300/0946—Waste, e.g. MSW, tires, glass, tar sand, peat, paper, lignite, oil shale
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
  • C10J2300/0953—Gasifying agents
  • C10J2300/0973—Water
  • C10J2300/0976—Water as steam
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/12—Heating the gasifier
  • C10J2300/1246—Heating the gasifier by external or indirect heating
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
  • C10J2300/1853—Steam reforming, i.e. injection of steam only
• • 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
  • Y02P20/141—Feedstock
• • 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
  • Y02P20/141—Feedstock
  • Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics

Definitions

• the present invention relates to a method for reducing the molecular weight of an organic substance by reforming it in order to convert the organic substance such as waste plastic into gaseous fuel or liquid fuel.
• Patent Document 1 a coke oven gas (COG) having a hydrogen concentration of 60 vol% or more, preferably 80 vol% or more and a temperature of 600 ° C or more is reacted with an organic material such as waste plastic, thereby hydrogenating the organic material with high efficiency.
• COG coke oven gas
• Patent Document 2 discloses a method for decomposing waste plastic and converting it to liquid fuel at a temperature of 350 to 500 ° C. using a fluidized fluid catalytic catalyst (FCC) as a heat medium and catalyst.
• FCC fluidized fluid catalytic catalyst
• Patent Document 3 when pyrolyzing RDF, wood, etc., the gas generated by pyrolysis is steam reformed, and the gas having a high hydrogen concentration by this steam reforming is circulated to the pyrolysis section to generate hydrogen.
• a method of performing pyrolysis in a gas atmosphere with a high concentration is disclosed.
• Patent Document 1 since the hydrogen concentration in COG is 60 vol% or more is limited to the end of the dry distillation in the coal dry distillation process, in the method of Patent Document 1, the gas flow path is opened at the end of the dry distillation. It is necessary to switch and supply COG of 600 ° C. or more containing a large amount of dust to a waste plastic hydrocracking reactor. However, it is difficult to stably operate the flow path switching valve for a long time under such a severe condition, and in this sense, it can be said that the technique is poor in feasibility. Furthermore, for efficient gasification of waste plastic, it is necessary to continuously supply COG containing 60 vol% or more of hydrogen to the hydrocracking reactor. In addition, it is necessary to install a hydrogen concentration meter and a flow path switching valve, which increases the equipment cost.
• the method of patent document 2 advances catalytic cracking and aromatization by FCC catalyst addition, since it reacts with an inert gas flow, 13 mass% of heavy oil and coke are produced
• the gas generated by the method of Patent Document 3 is mainly H 2 , CO, CO 2 , and the combustion heat is about 1800 kcal / Nm 3 that is slightly lower than that of the exhaust gas generated from the metallurgical furnace. Value is limited.
• an object of the present invention is to efficiently reform an organic substance using a gas that can be stably supplied when the organic substance such as waste plastic is reduced in molecular weight to be converted into gaseous fuel or liquid fuel.
• a method for reducing the molecular weight of an organic substance that can be reduced in molecular weight can be obtained with a modified product containing a small amount of heavy components and carbonaceous matter, and a large amount of light components, and can be implemented with relatively simple equipment. There is.
• the present inventors have mixed (i) water vapor into an exhaust gas containing carbon dioxide and hydrogen generated in a gasification melting furnace, and this mixed gas has a high molecular weight.
• the organic substance is modified to reduce the molecular weight, or (ii) the shift reaction is performed by adding excess steam to the exhaust gas containing carbon monoxide and hydrogen generated in the gasification melting furnace.
• a high-molecular-weight organic substance is reformed with a mixed gas containing hydrogen after the reaction, that is, hydrogen contained in the exhaust gas, carbon dioxide and hydrogen produced by the shift reaction, and water vapor not consumed in the shift reaction. It has been found that reducing the molecular weight is effective. Further, in the methods (i) and (ii) above, it was found that there is a suitable range for the composition of the mixed gas for organic substance modification.
• the present invention has been made on the basis of such findings and has the following gist.
• [1] Mixing water vapor with the exhaust gas (g 0 ) containing carbon dioxide and hydrogen generated in the gasification melting furnace, bringing the mixed gas (g) into contact with an organic substance, reforming the organic substance, and reducing the molecular weight
• a method for reducing the molecular weight of an organic substance characterized by comprising: [2] in the exhaust gas (g 1) containing carbon monoxide and hydrogen generated in the gasification and melting furnace with the addition of excess water vapor is possible to perform a shift reaction, hydrogen contained in the exhaust gas (g 1) And a mixed gas (g) containing carbon dioxide and hydrogen produced by the shift reaction and water vapor not consumed in the shift reaction.
• the mixed gas (g) is brought into contact with the organic substance to reform the organic substance. And reducing the molecular weight of the organic substance.
• [4] A method for reducing the molecular weight of an organic substance according to any one of the above [1] to [3], wherein the water vapor concentration of the mixed gas (g) is 5 to 70 vol%.
• the mixed gas (g) is characterized in that the water vapor concentration is 20 to 70 vol%, the hydrogen concentration is 10 to 40 vol%, and the carbon dioxide concentration is 10 to 40 vol%.
• a method for reducing the molecular weight of a substance is characterized in that the water vapor concentration is 20 to 70 vol%, the hydrogen concentration is 10 to 40 vol%, and the carbon dioxide concentration is 10 to 40 vol%.
• the organic substance when a high molecular weight organic substance such as waste plastic is reduced in molecular weight to be converted into gaseous fuel or liquid fuel, the organic substance is efficiently reformed using a gas that can be stably supplied.
• a gas that can be stably supplied there is no need for special measuring instruments or flow path switching valves, and the organic substance can be reformed even at a relatively low reaction temperature. it can.
• CO 2 produced by the shift reaction changes to CO by the carbon dioxide reforming reaction during the reforming of the organic substance, chemical recycling of the organic substance can be performed without increasing the amount of CO 2 generated. It becomes possible.
• an exhaust gas (g 0 ) containing carbon dioxide and hydrogen generated in a gasification melting furnace (hereinafter referred to as “gasification melting furnace generated exhaust gas”). Water vapor is mixed with the gas (g), and this mixed gas (g) is brought into contact with the organic substance to modify the organic substance to reduce the molecular weight.
• an exhaust gas (g 1 ) containing carbon monoxide and hydrogen generated in a gasification melting furnace (hereinafter referred to as “gasification melting furnace generated exhaust gas”).
• excess water vapor is added to cause the shift reaction to occur, so that hydrogen contained in the exhaust gas (g 1 ), carbon dioxide and hydrogen generated by the shift reaction, and the shift reaction are consumed.
• the mixed gas (g) containing the water vapor that has not existed is brought into contact with the organic substance, and the organic substance is modified to reduce the molecular weight. Note that adding excess water vapor to the exhaust gas (g 1 ) means adding water vapor so that excess water vapor that is not consumed in the shift reaction remains in the mixed gas (g).
• the gasification and melting furnace is a furnace facility that heats garbage in a low-oxygen state and pyrolyzes it, and burns or recovers the gas generated by this pyrolysis and melts ash and incombustibles at high temperatures.
• thermal decomposition and melting are performed integrally and a method in which they are performed separately.
• a gasification reforming system for example, a thermoselect system (see Patent Document 4 and Patent Document 5)
• a shaft furnace system for example, a coke bed system, an oxygen system, a plasma system, etc.
• a kiln furnace System fluidized bed system, semi-distillation and negative pressure combustion system.
• any type of gasification melting furnace generated exhaust gas may be used, or a mixture of two or more types of exhaust gas may be used.
• the exhaust gas generated in the gasification melting furnace may be an exhaust gas containing carbon dioxide and hydrogen, or carbon monoxide and hydrogen.
• an exhaust gas containing carbon dioxide and hydrogen having a carbon dioxide concentration of 20 to 60 vol% and a hydrogen concentration of 60 to 20 vol%, or a carbon monoxide concentration of 10 to 50 vol% and a hydrogen concentration of 50
• Exhaust gas containing 10% by volume of carbon monoxide and hydrogen can be exemplified as exhaust gas applicable to the method of the present invention.
• hydrogen is generated by a shift reaction.
• the composition is suitable as the mixed gas (g) of the present invention. Even if the pyrolysis gas is a gas generated by partial combustion in the furnace or a gas generated by partial combustion outside the furnace, the gas recovered as pyrolysis gas without burning It may be.
• steam reforming and carbon dioxide reforming can be regarded as oxidation of hydrocarbons by oxygen in H 2 O and CO 2 molecules, achieving low molecular weight and suppressing carbonaceous production with a small amount of hydrogen addition. it can. Furthermore, steam reforming and carbon dioxide reforming are characterized in that the reaction temperature decreases as the carbon chain of the organic molecule to be modified becomes longer. In the method of the present invention, the low molecular weight of an organic substance is efficiently promoted even at a relatively low reaction temperature, the amount of hydrogen consumption is small, and the generation of heavy components and carbonaceous matter is hardly recognized.
• the hydrogenation includes the following CO and CO 2 methanation reactions. CO + 3H 2 ⁇ CH 4 + H 2 O, CO 2 + 4H 2 ⁇ CH 4 + 2H 2 O
• the above hydrogenation and hydrocracking also proceed with H 2 produced by steam reforming or carbon dioxide reforming.
• the exhaust gas generated from the gasification melting furnace contains carbon monoxide and hydrogen as described above, and excess water vapor is added to the exhaust gas (g 1 ) containing carbon monoxide and hydrogen.
• CO can be converted into H 2 and CO 2, which is suitable as a mixed gas (g) for organic substance modification.
• Gasification melting furnace-generated exhaust gas has various compositions. According to this method, a suitable mixed gas (g) can be obtained by controlling the shift reaction corresponding to the exhaust gas composition.
• each concentration of water vapor, hydrogen, and carbon dioxide gas in the gas is controlled, and the organic substance is modified. It can be a quality mixed gas (g).
• the reaction rate of the shift reaction can be controlled by adjusting the residence time in the shift reactor. For example, in order to shorten the residence time, a method in which the shift reactor length is reduced or the catalyst charge amount is reduced is generally used. In this case, the shift reactor length and the catalyst charge amount are almost until equilibrium. What is necessary is just to be about 1/2 to 1/4 of the case of proceeding the reaction.
• the exhaust gas generated from Thermoselect gasification melting furnace typically, CO is 20 ⁇ 40vol%, CO 2 is 40 ⁇ 20vol%, H 2 is contained about 20 ⁇ 40 vol%.
• CO water vapor in the exhaust gas (g 0) containing such carbon dioxide and hydrogen
• CO 15 ⁇ 20vol%
• CO 2 35 ⁇ 10vol%
• H 2 15 ⁇ 20vol%
• H 2 O a composition of about 20 to 50 vol%, which is suitable as a mixed gas (g) for organic substance modification.
• the reason why the exhaust gas (g 0 ) generated from the gasification melting furnace is used as the exhaust gas containing carbon dioxide and hydrogen is that it contains carbon dioxide and hydrogen at a relatively high concentration, This is because the nitrogen concentration is low. Furthermore, the exhaust gas generated from the gasification melting furnace has a relatively high hydrogen concentration even when the secondary combustion rate (CO2 / (CO + CO2) ⁇ 100) exceeds 50%. 0 ).
• the gasification melting furnace generated exhaust gas (g 0 ) any of the exhaust gases generated in various gasification melting furnaces as described above may be used, or a mixed gas of two or more kinds of exhaust gases may be used. .
• a mixed gas (g) for organic substance reforming can be obtained simply by mixing water vapor into the gasification melting furnace-generated exhaust gas (g 0 ).
• the mixing method is not particularly limited, and may be mixed on the upstream side of the organic material reforming reactor, or may be mixed in the reforming reactor.
• the reason why the exhaust gas (g 1 ) generated from the gasification melting furnace is used as the exhaust gas for the shift reaction is that it contains carbon monoxide at a relatively high concentration and usually has a low nitrogen concentration. Because.
• the gasification melting furnace generated exhaust gas (g 1 ) any of the exhaust gases generated in various gasification melting furnaces as described above may be used, or a mixed gas of two or more kinds of exhaust gases may be used. .
• An exhaust gas generated from a gasification reforming gasification melting furnace such as a thermoselect method is more preferable because it has a relatively high carbon monoxide concentration.
• the exhaust gas generated from the gasification melting furnace usually has a relatively stable exhaust gas composition, and the fact that the reforming reaction of the organic substance can be performed stably is also used as the exhaust gas (g 1 ) of the present invention. That is why.
• the exhaust gas (g 1 ) to be shift-reacted has no problem in obtaining a mixed gas (g) for organic substance reforming if it has a composition as follows.
• CO 80-10 vol% CO 2 : 10 to 50 vol% H 2 : more than 0 to 30 vol% N 2 : 0 to 30 vol%
• the CO concentration exceeds 80 vol%, the amount of water vapor added to make the mixed gas (g) after the shift reaction have a suitable composition becomes very large, which is not economical. If it is less than 10 vol%, the CO concentration is low, so the shift reaction rate is slow, the reactor becomes large, and it is not economical.
• a more preferable CO concentration is 10 to 60 vol%, and 10 to 50 vol% is particularly preferable.
• a CO 2 concentration exceeding 50 vol% is not preferable because the CO 2 concentration in the mixed gas (g) after the shift reaction becomes too high. Further, if it is less than 10 vol%, the CO 2 concentration in the mixed gas (g) becomes too low, which is not preferable. A more preferable CO 2 concentration is 10 to 40 vol%. If the H 2 concentration exceeds 30 vol%, the amount of steam added to make the mixed gas (g) after the shift reaction have a suitable composition becomes very large, which is not economical. A more preferable H 2 concentration is 20 vol% or less. It is preferable to control the CO concentration after the shift reaction to less than 10 vol%. If the CO concentration after the shift reaction exceeds 10 vol%, the efficiency of the organic substance modification in the subsequent process is lowered, which is not preferable. More preferably, it is controlled to be less than 5 vol%.
• nitrogen does not contribute at all to the chemical reaction (shift reaction, hydrogenation, hydrocracking, steam reforming, carbon dioxide reforming) occurring in the present invention, while diluting the gaseous fuel produced, Low combustion heat (hereinafter referred to as “LHV”) is reduced.
• LHV Low combustion heat
• the nitrogen concentration is preferably within the above composition range.
• the shift reaction in the method of the present invention may be carried out by a known method and is not particularly limited. In general, steam is added to the exhaust gas (g 1 ) in advance, and this is introduced into a fixed bed reactor filled with a catalyst to perform a shift reaction. Alternatively, the water vapor to be added in advance may be partially used, the catalyst may be packed in multiple stages in the reactor, and the remaining water vapor may be added between the catalyst layer and the catalyst layer.
• the present invention (the first and second inventions of the present application), it is obtained by mixing water vapor with exhaust gas (g 0 ), or obtained by adding water vapor to exhaust gas (g 1 ) to cause shift reaction.
• the organic gas reforming mixed gas (g) contains water vapor, hydrogen and carbon dioxide. There are no particular restrictions on the concentrations thereof, but the water vapor concentration is preferably 5 to 70 vol% for the following reasons. That is, when the water vapor concentration is low, the decomposition rate of organic substances such as waste plastics is low. However, by setting the water vapor concentration to 5 vol% or more, a certain level of organic material decomposition rate can be secured.
• both the hydrogen concentration and the carbon dioxide concentration of the mixed gas (g) are preferably 5 vol% or more.
• composition of the mixed gas (g) for organic substance reforming is: water vapor concentration: 20 to 70 vol%, hydrogen concentration: 10 to 40 vol%, carbon dioxide concentration: 10 to 40 vol%. It is. In addition, it does not prevent that other gas components (for example, nitrogen etc.) are contained in this mixed gas (g).
• the water vapor concentration is 20 vol% or more, the decomposition rate of the organic substance can be sufficiently increased, and the LHV of the gaseous fuel can be increased.
• the reason why the water vapor concentration is 70 vol% or less is as described above.
• the hydrogen concentration By setting the hydrogen concentration to 10 vol% or more (more preferably 12 vol% or more), it is possible to suppress the CO 2 from remaining in the gaseous fuel even when the organic substance is reformed at a relatively low temperature. Can do.
• the carbon dioxide concentration By setting the carbon dioxide concentration to 10 vol% or more (more preferably 13 vol% or more), H 2 that is a low-calorie gas component is less likely to remain in the gaseous fuel as compared to hydrocarbons and CO.
• the decomposition rate of organic substances, such as a waste plastic can be made into a preferable level by making hydrogen concentration and carbon dioxide concentration into 40 vol% or less.
• more preferable gas composition of the mixed gas (g) is water vapor concentration: 25 to 65 vol%, hydrogen concentration: 15 to 35 vol%, carbon dioxide concentration: 15 to 35 vol%. In addition, it does not prevent that other gas components (for example, nitrogen etc.) are contained in this mixed gas (g).
• the ratio of the amount of gas fuel produced and the amount of liquid fuel produced in reforming the organic material can be controlled by the water vapor concentration of the mixed gas (g) for reforming the organic material. It is done. That is, when the water vapor concentration of the mixed gas (g) is 50 vol% or more, gaseous fuel is mainly produced (that is, gaseous fuel production amount> liquid fuel production amount), and when the water vapor concentration is 40 vol% or less, liquid fuel is mainly produced. (Ie, gaseous fuel production amount ⁇ liquid fuel production amount).
• the influence of hydrogen concentration and carbon dioxide concentration is not as remarkable as the influence of water vapor concentration, it may be within the preferable range of the present invention.
• the object plastics etc. which are an industrial waste type
• inorganic substances such as fillers are added to many plastics, but in the present invention, such inorganic substances are not involved in the reaction, and thus are discharged from the reforming (low molecular weight) reactor as solid residues.
• the waste plastic is preliminarily cut to an appropriate size as required, and then charged into the reforming reactor.
• the waste plastic contains a chlorine-containing resin such as polyvinyl chloride, chlorine is generated in the reforming reactor, and this chlorine may be contained in the gaseous fuel or liquid fuel. Therefore, when there is a possibility that the waste plastic contains a chlorine-containing resin, a chlorine absorbent such as CaO is introduced into the reforming reactor so that chlorine is not contained in the generated gaseous fuel or liquid fuel. It is preferable to make it.
• Oil-containing sludge is a sludge-like mixture generated in an oil-containing waste liquid treatment process and generally contains about 30 to 70% by mass of water.
• the oil in the sludge include, but are not limited to, various mineral oils, natural and / or synthetic oils and fats, and various fatty acid esters.
• a method such as centrifugation is used.
• the water in the sludge may be reduced to about 30 to 50% by mass.
• waste oil examples include, but are not limited to, various used mineral oils, natural and / or synthetic fats and oils, and various fatty acid esters. Moreover, the mixture of these 2 or more types of waste oil may be sufficient.
• waste oil generated in the steel mill rolling process it generally contains a large amount of water (usually more than about 80% by mass), but this water is also reduced in advance by a method such as specific gravity separation. It is advantageous in terms of handleability.
• the organic substance contains water, water vapor is generated in the reforming reactor. Therefore, the excess ratio of water vapor added in the shift reaction is determined in consideration of the amount.
• biomass examples include, but are not limited to, sewage sludge, paper, construction waste, thinned wood, and processed biomass such as solid waste fuel (RDF). Since biomass usually contains a large amount of water, it is preferable to dry it beforehand in view of energy efficiency. In addition, in the case of biomass containing a relatively high concentration of alkali metals such as sodium and potassium, there is a possibility that alkali metals may precipitate in the reforming reactor. It is preferable to keep it. In addition, large biomass such as construction waste is cut in advance and charged into the reforming reactor.
• RDF solid waste fuel
• the reaction temperature during organic substance modification is preferably as follows according to the type of organic substance.
• the reaction temperature is suitably about 400 to 900 ° C.
• the reaction temperature is less than 400 ° C, the decomposition rate of waste plastics and biomass is low.
• the reaction temperature exceeds 900 ° C, the production of carbonaceous matter increases.
• the reaction temperature is suitably about 300 to 800 ° C.
• the reaction temperature is less than 300 ° C., the decomposition rate of oil-containing sludge and waste oil becomes low.
• reaction temperature is suitably about 400 to 800 ° C. from the above points.
• reaction temperature is suitably about 400 to 800 ° C. from the above points.
• the influence of reaction temperature with respect to the ratio of gaseous fuel production amount and liquid fuel production amount is hardly seen.
• pressure since the influence of pressure is hardly observed, it is economical to operate the reforming reactor at normal pressure or at a slight pressure of about several kg / cm 2 .
• the type of the reforming reactor is not particularly limited, but organic substances such as waste plastic move smoothly in the reactor and can be efficiently contacted with the mixed gas (g) for organic substance reforming.
• a horizontal moving bed reactor such as a rotary kiln is preferred.
• a catalyst is not particularly required for reforming the organic substance, but the reaction may be carried out by filling the catalyst.
• the catalyst one or more kinds of catalysts each having steam reforming activity, carbon dioxide reforming activity, hydrogenation activity, and hydrocracking activity can be used. Specific examples include Ni-based reforming catalysts, Ni-based hydrogenation catalysts, Pt / zeolite-based petroleum refining catalysts, and the like.
• converter-generated dust which is known to be composed of fine Fe particles, can be used as a reforming catalyst or a hydrocracking catalyst.
• a vertical reforming reactor is used instead of a horizontal moving bed reforming reactor such as a rotary kiln. May be adopted.
• the mixed gas (g) is supplied from the lower part and / or the side part rather than the upper part of the reforming reactor because the contact between the mixed gas (g) and the organic substance or catalyst is good.
• a general fixed bed reactor or fluidized bed reactor used in the chemical industry can be used.
• a mixed gas (g) is supplied from the lower part of the reforming reactor.
• a blast furnace, a shaft furnace, or a converter which is an iron manufacturing facility
• a blast furnace or shaft furnace is used as a reforming reactor
• an organic substance and a catalyst are supplied continuously from the top of the furnace, and a mixed gas (g) is continuously supplied from the bottom of the furnace to counter-current contact, and gas is supplied from the top of the furnace.
• a mixed gas (g) is continuously supplied from the bottom of the furnace to counter-current contact, and gas is supplied from the top of the furnace.
• the product is a moving bed type in which the liquid product and the catalyst are continuously extracted from the lower part of the furnace because the reaction efficiency becomes high.
• a converter When a converter is used as a reforming reactor, an organic substance and a catalyst are introduced into the furnace, then a mixed gas (g) is continuously supplied from the lower part of the furnace, and a gas product is continuously supplied from the upper part of the furnace.
• the liquid product and the catalyst can be extracted in a batch reaction system similar to steelmaking blowing, in which the furnace is tilted and extracted after a certain time of reaction.
• fluidized bed reactors are known to be excellent in heat conduction, but when fluidized bed reactors are employed in the present invention, the rate of molecular weight reduction of organic substances is low because of excellent heat conduction. There are advantages such as high, which is preferable.
• the reformed organic substance obtained by the method of the present invention is usually a gas and a liquid, which are suitable as a gaseous fuel and a liquid fuel, and are used in ironworks such as iron ore reducing agents. It can also be used as an agent.
• Combustible components of the gaseous fuel comprises a hydrocarbon of carbon monoxide and C1 ⁇ C4, the LHV of about 6 ⁇ 10Mcal / Nm 3.
• carbon monoxide concentration is high, it is characterized by higher combustibility than natural gas.
• it is safer to use it as a city gas alternative fuel in factories with metallurgical furnaces such as steelworks than to supply it as household city gas.
• it because of its high hydrocarbon content of carbon monoxide and C1 to C4, it can be used as a reducing agent for blast furnaces and as a coagulant for sinter ore production process as a substitute for natural gas.
• liquid fuel Since liquid fuel consists of C5 to C24 hydrocarbons, it is a mixture of naphtha (C5 to C8), kerosene (C9 to C12), and light oil (C13 to C24), and contains almost equivalent to heavy oil (C25 and above) There is no good quality light oil.
• This liquid fuel may be used separately as naphtha, kerosene, or light oil by distillation separation, but it remains as a mixture and is used as a fuel for factories with metallurgical furnaces such as ironworks, or as a heavy oil substitute reducing agent for blast furnaces. May be.
• Oil obtained by removing hydrocarbons having a relatively high vapor pressure such as naphtha from liquid fuel can also be used as a reducing agent for a blast furnace as an alternative to heavy oil. Since the content of naphtha (C5 to C8) is large, it can be used as a raw material for chemical industry after distilling and separating naphtha in addition to use as a light liquid fuel. For example, the naphtha fraction separated by distillation can be contact-modified and converted to benzene, toluene, xylene, or the like.
• the reformed product of the organic substance obtained by the method of the present invention can be separated into gaseous fuel and liquid fuel by cooling the reforming reaction product gas and then performing gas-liquid separation.
• naphtha, kerosene, and light oil can be separated from the liquid fuel by performing distillation separation as necessary.
• the cooling method, the gas-liquid separation method, and the distillation separation method of the reforming reaction product gas can be performed by known methods, and there is no particular limitation.
• a branch pipe is provided in the discharge pipe for the exhaust gas (hereinafter referred to as "Purified synthesis gas") generated from the refined Thermoselect Waste Gasification and Reforming Process after removing impurities such as hydrogen chloride.
• a part of the thermogas can be extracted through this branch pipe.
• a gas cooler for cooling the reforming reaction product gas equipped with a flow control valve, a steam mixer, a gas preheater, a reforming reactor (externally heated rotary kiln), and a liquid fuel collector on the downstream side of the branch pipe Were arranged in this order.
• a screw conveyor type waste plastic quantitative charging device was installed on the inlet side of the reforming reactor.
• a sampling port and a flow meter were installed in the gas outlet piping after cooling of the gas cooler.
• the average composition of Samogasu is, H 2: 31vol%, CO : 33vol%, CO 2: 30vol%, H 2 O: ⁇ 1vol%, N 2: was 6 vol%.
• a steam gas of 108 Nm 3 / h and steam at a pressure of 10 kg / cm 2 G as steam were supplied to the steam mixer at 64 Nm 3 / h, and the temperature was raised to 430 ° C. with a preheater.
• the gas composition after steam mixing was H 2 : 20 vol%, CO: 21 vol%, CO 2 : 19 vol%, H 2 O: 37 vol%, and N 2 : 4 vol%.
• This mixed gas for organic substance decomposition had a flow rate of 172 Nm 3 / h (mass flow rate of 171 kg / h).
• the externally heated rotary kiln which is a reforming reactor, is preheated to 500 ° C. in advance.
• the mixed gas is introduced into the reforming reactor, and 880 kg / kg of polyethylene that has been crushed into granules as a model material for waste plastics.
• the temperature was raised to 800 ° C., which is the planned reaction temperature.
• the liquid product collected in the liquid fuel collector was discharged, and then the reforming reaction of the waste plastic was continued for 1 hour.
• the amount of gas fuel is determined from the gas analysis results after cooling by the gas cooler, and the amount of liquid fuel is determined from the analysis results of the liquid product collected in the liquid fuel collector. LHV was calculated
• thermogas, water vapor, and polyethylene supplied as raw materials was 1050 kg / h
• the production rate relative to the total amount of the raw materials supplied was 32% for gas fuel and 60% for liquid fuel. Since it is difficult to directly measure the amount of unreacted polyethylene, the total yield of gaseous fuel (340 kg / h) and liquid fuel (630 kg / h) with respect to the total amount (1050 kg / h) of the supplied thermogas, water vapor, and polyethylene is When defined as the polyethylene decomposition rate, in this invention example 1, since the polyethylene decomposition rate is a sufficiently high value of 92% and the generation of hydrocarbons of C25 or higher is hardly observed, polyethylene is effectively a low molecular weight It is clear that H 2 O, CO 2 and H 2 are completely consumed by the reforming reaction of the organic substance, and it is considered that four reactions of steam reforming, carbon dioxide reforming, hydrogenation, and hydrocracking proceeded simultaneously. .
• the LHV of the produced gaseous fuel was

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