Method for producing c2-c8 unsaturated hydrocarbon, method for producing c2-c8 unsaturated hydrocarbon mixture, method for producing olefin-based polymer, method for producing compound, method for producing polymer, olefin-based polymer, and polymer

Abstract

A method for producing a C2-C8 unsaturated hydrocarbon according to the present invention comprises: a step (1) for sorting, from waste plastics, a plastic mixture (A) having a polyolefin-based plastic content of 50 mass% or more, and residues (B); a step (2) for decomposing the plastic mixture (A) to obtain a reaction product containing a C2-C8 unsaturated hydrocarbon; and a step (3) for cleaning and purifying the reaction product to separate the C2-C8 unsaturated hydrocarbon.

Description

Method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms, method for producing a mixture of unsaturated hydrocarbons having 2 to 8 carbon atoms, method for producing an olefin polymer, method for producing a compound, method for producing a polymer, olefin polymer and polymer CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority from Japanese Patent Application No. 2022-106346, the disclosure of which is incorporated herein by reference.

[0002] The present invention relates to a method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms, a method for producing a mixture of unsaturated hydrocarbons having 2 to 8 carbon atoms, a method for producing an olefin polymer, a method for producing a compound, a method for producing a polymer, an olefin polymer, and a polymer.

[0003] Plastics are produced in large quantities because they are easy to use, durable, and relatively inexpensive. However, most of them are disposable and discarded as waste, which has led to environmental problems such as microplastics, which are tiny pieces of plastic that have been broken down into small pieces.

[0004] Furthermore, the regeneration and reuse of plastics is important from the viewpoint of resource recycling. Therefore, processes such as reuse, material recycling, and chemical recycling are carried out to recycle waste plastics. In particular, chemical recycling has the potential to overcome the limitations of performance degradation due to recycling, as it chemically decomposes plastics and regenerates them into petrochemical raw materials. For example, Non-Patent Document 1 discloses a catalytic cracking method in which polyolefins are converted into lower olefins using a catalyst as one of the chemical recycling technologies.

[0005] Monthly Fine Chemical, Vol. 46 (No. 12), pp. 44-50 (2017)

[0006] In recent years, as the development of chemical recycling technologies has been actively pursued, there is a demand for technologies for more efficiently obtaining compounds such as petrochemical raw materials. In particular, since a wide variety of products are produced from unsaturated hydrocarbons with 2 to 8 carbon atoms, there is a demand for efficient production of unsaturated hydrocarbons with 2 to 8 carbon atoms.

[0007] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms, which allows compounds such as petrochemical raw materials to be efficiently obtained from waste plastics, a method for producing a mixture of unsaturated hydrocarbons having 2 to 8 carbon atoms using the production method, a method for producing an olefin polymer, a method for producing a compound, and a method for producing a polymer, an olefin polymer obtained by the method for producing an olefin polymer, and a polymer obtained by the method for producing a polymer.

[0008] A method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms according to a first aspect of the present invention includes the steps of: (1) separating a plastic mixture (A) containing 50% by mass or more of polyolefin-based plastics from waste plastics; and (2) decomposing the plastic mixture (A) to obtain a reaction product containing unsaturated hydrocarbons having 2 to 8 carbon atoms; and (3) washing and purifying the reaction product to separate the unsaturated hydrocarbons having 2 to 8 carbon atoms.

[0009] A method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms according to a second aspect of the present invention includes the steps of: (1) separating, from waste plastics, a plastic mixture (A) containing 50% by mass or more of polyolefin plastics, and a residue (B); (12) heating the residue (B) to obtain a mixed gas containing carbon monoxide, carbon dioxide, and hydrogen; (13) mixing the mixed gas with at least one gas selected from the group consisting of carbon monoxide, carbon dioxide, and hydrogen, or removing a portion of the at least one gas selected from the group consisting of carbon monoxide, carbon dioxide, and hydrogen from the mixed gas, to obtain an adjusted gas in which the ratio by volume of hydrogen to the total volume of carbon monoxide and carbon dioxide is 1.5 to 4.0; (14) reacting the carbon monoxide, carbon dioxide, and hydrogen contained in the adjusted gas to obtain an alcohol; and (15) obtaining unsaturated hydrocarbons having 2 to 8 carbon atoms using the alcohol as a raw material.

[0010] A method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms according to a third aspect of the present invention includes the steps of: (1) separating, from waste plastics, a plastic mixture (A) containing 50% by mass or more of polyolefin plastics, and a residue (B); (2) decomposing the plastic mixture (A) to obtain a reaction product containing unsaturated hydrocarbons having 2 to 8 carbon atoms; (3) washing and purifying the reaction product to separate the unsaturated hydrocarbons having 2 to 8 carbon atoms; (12) heating the residue (B) to obtain a mixed gas containing carbon monoxide, carbon dioxide, and hydrogen; (13) mixing the mixed gas with at least one gas selected from the group consisting of carbon monoxide, carbon dioxide, and hydrogen, or removing a portion of at least one gas selected from the group consisting of carbon monoxide, carbon dioxide, and hydrogen from the mixed gas, to obtain an adjusted gas in which the volume ratio of hydrogen to the total volume of carbon monoxide and carbon dioxide is 1.5 to 4.0; and (14) reacting the carbon monoxide, carbon dioxide, and hydrogen contained in the adjusted gas to obtain an alcohol. and step (15) of obtaining an unsaturated hydrocarbon having 2 to 8 carbon atoms using an alcohol as a raw material.

[0011] A method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms according to a fourth aspect of the present invention includes a step (21) of reacting carbon dioxide with hydrogen to obtain a reaction mixture containing an alcohol, carbon dioxide, and carbon monoxide, and a step (22) of obtaining unsaturated hydrocarbons having 2 to 8 carbon atoms from the alcohol and / or carbon monoxide contained in the reaction mixture.

[0012] The method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms according to the fifth aspect of the present invention includes the method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms according to any one of the first to third aspects, and the method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms according to the fourth aspect.

[0013] A method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms according to a sixth aspect of the present invention includes the method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms according to any one of the first to fourth aspects, and a method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms, the method including a step (31) of dehydrating at least one alcohol selected from the group consisting of ethanol, propanol, and butanol to obtain unsaturated hydrocarbons having 2 to 8 carbon atoms.

[0014] A seventh aspect of the present invention relates to a method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms, which includes the method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms according to the fifth aspect, and a step (31) of dehydrating at least one alcohol selected from the group consisting of ethanol, propanol, and butanol to obtain unsaturated hydrocarbons having 2 to 8 carbon atoms.

[0015] The method for producing a mixture of unsaturated hydrocarbons having 2 to 8 carbon atoms according to the present invention includes a step (41) of contacting the unsaturated hydrocarbons having 2 to 8 carbon atoms obtained by the method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms according to any one of the first to seventh aspects with unsaturated hydrocarbons having 2 to 8 carbon atoms derived from a fossil resource to obtain a mixture.

[0016] The method for producing an olefin polymer according to the present invention includes a step of polymerizing a monomer containing the unsaturated hydrocarbon having 2 to 8 carbon atoms obtained by the method for producing an unsaturated hydrocarbon having 2 to 8 carbon atoms according to any one of the first to seventh aspects, or the mixture of unsaturated hydrocarbons having 2 to 8 carbon atoms obtained by the method for producing a mixture of unsaturated hydrocarbons having 2 to 8 carbon atoms described above.

[0017] The method for producing a compound according to the present invention includes a step of synthesizing at least one compound selected from the group of compounds consisting of methyl methacrylate, propylene oxide, ethylene oxide, ethylene glycol, phenol, acetone, and isopropyl alcohol, using as a raw material the unsaturated hydrocarbon having 2 to 8 carbon atoms obtained by the method for producing an unsaturated hydrocarbon having 2 to 8 carbon atoms according to any one of the first to seventh aspects, or the unsaturated hydrocarbon mixture having 2 to 8 carbon atoms obtained by the method for producing a mixture of unsaturated hydrocarbons having 2 to 8 carbon atoms described above.

[0018] The method for producing a polymer according to the present invention includes a step of polymerizing a monomer produced using as a raw material the unsaturated hydrocarbon having 2 to 8 carbon atoms obtained by the method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms according to any of the first to seventh aspects, or the unsaturated hydrocarbon mixture having 2 to 8 carbon atoms obtained by the method for producing a mixture of unsaturated hydrocarbons having 2 to 8 carbon atoms described above, the monomer including at least one compound selected from the group of compounds consisting of methyl methacrylate, propylene oxide, ethylene oxide, and ethylene glycol.

[0019] The olefin polymer according to the present invention is obtained by the above-mentioned method for producing an olefin polymer, and has a plant-derived carbon concentration of 0.1 to 99.9 pMC.

[0020] The polymer according to the present invention is obtained by the above-mentioned method for producing a polymer, and has a plant-derived carbon concentration of 0.1 to 99.9 pMC.

[0021] According to the present invention, there are provided a novel and efficient method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms, which allows unsaturated hydrocarbons having 2 to 8 carbon atoms to be efficiently obtained from waste plastics, a method for producing a mixture of unsaturated hydrocarbons having 2 to 8 carbon atoms using the production method, a method for producing an olefin polymer, a method for producing a compound, and a method for producing a polymer, an olefin polymer obtained by the method for producing an olefin polymer, and a polymer obtained by the method for producing a polymer.

[0022] FIG. 1 is a diagram showing an example of a flow chart for producing an ethylene derivative using ethylene produced by the present invention as a starting material. FIG. 2 is a diagram showing an example of a flow chart for producing a propylene derivative using propylene produced by the present invention as a starting material. FIG. 3 is a diagram showing an example of a flow chart for producing a derivative using an unsaturated hydrocarbon having 4 carbon atoms produced by the present invention as a starting material. FIG. 4 is a diagram showing an example of a flow chart for producing a derivative using an unsaturated hydrocarbon having 5 carbon atoms produced by the present invention as a starting material. FIG. 5 is a diagram showing an example of an invention according to claim 1. FIG. 6 is a diagram showing an example of an invention according to claim 2. FIG. 7 is a diagram showing an example of an invention according to claim 5. FIG. 8 is a diagram showing an example of an invention according to claim 6. FIG. 9 is a diagram showing an example of an invention according to claim 7. FIG. 10 is a diagram showing an example of an invention according to claim 8.

[0023] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments.

[0024] [First embodiment of method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms] A first embodiment of the method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms includes a step (1) of separating a plastic mixture (A) containing 50 mass% or more of polyolefin plastics from waste plastics and a residue (B); a step (2) of decomposing the plastic mixture (A) to obtain a reaction product containing unsaturated hydrocarbons having 2 to 8 carbon atoms; and a step (3) of washing and purifying the reaction product to separate the unsaturated hydrocarbons having 2 to 8 carbon atoms.

[0025] Step (1) is a step of separating plastic mixture (A) and residue (B) from waste plastic. The waste plastic separated in step (1) mainly includes two types: general waste plastic and industrial waste plastic. General waste plastic is plastic waste mainly generated by households, such as used PET bottles, food trays, plastic bags, seasoning bottles, and hangers. On the other hand, industrial waste plastic is plastic waste mainly generated by factories, stores, and other business establishments, such as scrap and packaging materials generated during the manufacturing, processing, and distribution of plastic products, plastic bags discarded from offices, and food containers.

[0026] Examples of plastics contained in waste plastics include polyolefin plastics, polystyrene, polyamide, polycarbonate, polyurethane, polyester, polyethylene terephthalate (PET), polymethyl methacrylate, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), natural rubber, synthetic rubber, etc. In addition, waste plastics usually contain undesirable components other than plastics, such as foreign matter such as paper, glass, stone, wood, and metal.

[0027] Step (1) is a process for treating waste plastics to separate them into a plastic mixture (A) with an increased polyolefin content suitable for the decomposition reaction and a residue (B) that is other components undesirable for the decomposition reaction. Step (1) may use multiple devices performing different processes. Such devices may include one or more of a sorting device, a crushing device, a washing device, a dehydration device, and a drying device, as disclosed in, for example, JP 2022-2833 A and JP 2017-170653 A.

[0028] The sorting device is a device that separates polyolefin-based plastics from waste plastics using magnetic sorting, optical sorting, gravity separation, shaking sorter, centrifugal separator, etc.

[0029] For example, a rocking sorting machine can separate waste plastics into heavy materials (solid plastics), small-diameter materials (metal pieces, wood chips, etc.), and light materials (film-type plastics), thereby selecting film-type plastics and tray-type plastics, which are mainly made of polyolefins, as light materials, and removing solid plastics such as PET bottles and metals as heavy and small-diameter materials.Furthermore, wind separation, magnetic separation, gravity separation, etc. can be performed to increase the removal rate of foreign matter.

[0030] Furthermore, the centrifuge separates the types of plastic materials with high precision, separating chlorine-containing plastics such as polyvinyl chloride and polyvinylidene chloride, which generate chlorine gas when burned, from polypropylene. More specifically, the centrifuge separates light-density plastics and heavy-density plastics using water as a medium, for example, by rotating and centrifuging a container containing water and waste plastics, and can effectively separate PP, which has a specific gravity of about 0.9, from chlorine-containing plastics, which have a specific gravity of about 1.1 to 1.4.

[0031] The crushing equipment is a device that crushes plastics. The washing equipment is a device that washes the sorted and crushed plastics. The dehydrating equipment and drying equipment are devices that dehydrate and dry, for example, the washed plastics.

[0032] Step (1) can produce a plastic mixture (A) with an increased content of polyolefin-based plastics. The plastic mixture (A) contains polyolefins suitable for decomposition reactions. The content of polyolefin-based plastics is 50% by mass or more relative to the total mass of the plastic mixture (A). Examples of polyolefin-based plastics contained in the plastic mixture (A) include polyethylene, polypropylene, polybutene, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, and ethylene-α-olefin copolymer, with polyethylene, polypropylene, and ethylene-propylene copolymer being preferred. The polyolefin-based plastics contained in the plastic mixture (A) may be a mixture of two or more of these.

[0033] In the plastic mixture (A) having an increased content of polyolefin-based plastics, the total content of polyvinyl chloride (PVC) and polyvinylidene chloride (PVDC) is preferably 1 mass% or less, polyamide is preferably 4 mass% or less, and polyethylene terephthalate (PET) is preferably 5 mass% or less.

[0034] The residue (B) separated in step (1) is the remaining waste plastic other than the plastic mixture (A). Examples of residue (B) include highly contaminated polyolefins, films in which polyolefins and non-polyolefins are bonded together, non-polyolefin resins, paper, glass, wood, stone, and metal. Examples of non-polyolefin resins include polystyrene, polyamide, polycarbonate, polyurethane, polyester, polyethylene terephthalate (PET), polymethyl methacrylate, acrylonitrile-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), natural rubber, and synthetic rubber. The content of polyolefin-based plastics in residue (B) is lower than the content of polyolefin-based plastics in plastic mixture (A).

[0035] Step (2) is a step of decomposing the plastic mixture (A) to obtain a reaction product containing unsaturated hydrocarbons having 2 to 8 carbon atoms. In one embodiment, the decomposition of the plastic mixture (A) in step (2) includes a thermal decomposition step in which decomposition is carried out by heating. In another embodiment, it includes a catalytic decomposition step in which a reaction is carried out in contact with a catalyst in addition to heating. In yet another embodiment, it includes a thermal decomposition step and a catalytic decomposition step. The product obtained in the thermal decomposition step and / or the catalytic decomposition step may be decomposed again in another thermal decomposition step to obtain a reaction product containing unsaturated hydrocarbons having 2 to 8 carbon atoms. In addition, when decomposition is carried out by combining multiple decomposition steps, the reaction product obtained in an earlier decomposition step may be directly supplied to a later decomposition step, or at least a portion of it may be purified and supplied to the later decomposition step.

[0036] First, an embodiment in which the decomposition of the plastic mixture (A) in step (2) includes a thermal decomposition step will be described below.

[0037] In the thermal decomposition step, the plastic mixture (A) is decomposed by heating. A thermal decomposition apparatus may be used for the thermal decomposition step, or a cracker apparatus using naphtha or ethane as a raw material may be used. In the thermal decomposition step, the plastic mixture (A) is decomposed to obtain a reaction product containing unsaturated hydrocarbons having 2 to 8 carbon atoms. By decomposing the plastic mixture (A), unsaturated hydrocarbons having 2 to 8 carbon atoms may be obtained directly, and / or saturated hydrocarbons and hydrocarbon components having 9 or more carbon atoms may be obtained. Alternatively, a mixture of both may be obtained.

[0038] Examples of pyrolysis equipment include one or more heated extruders, heated rotary kilns, heated vessel reactors, fixed-bed reactors, bubbling fluidized-bed reactors, internal circulating fluidized-bed reactors, circulating fluidized-bed reactors, devices for decomposing plastics by flowing them down the inner wall of a heated vessel, and microwave heating devices. The heat source for the pyrolysis step can be the combustion of pyrolysis residue generated in the pyrolysis device, or the hydrocarbon-containing gas and / or liquid hydrocarbons obtained by cleaning and refining in step (3) described below. Alternatively, electricity, microwaves, or a combination of electricity or microwaves and the combustion can be used. The pyrolysis step may also include a combustion device for burning the pyrolysis residue generated in the pyrolysis reaction. The required heat can also be supplied to the pyrolysis device from the combustion device using a heat transfer surface or heat transfer medium.

[0039] The thermal cracking process may be carried out under low or high severity conditions in the thermal cracker. A low severity thermal cracking reaction may be carried out at a temperature of, for example, 250 to 450°C, and may produce a thermal cracking oil rich in monoolefins and diolefins, as well as a significant amount of aromatic compounds, and the reaction products may contain chloride compounds. A high severity thermal cracking reaction may be carried out at a temperature of, for example, 450 to 750°C, and may produce a thermal cracking oil rich in aromatic compounds. The liquid product of a high severity thermal cracking reaction may contain chloride compounds. The residence time of the reaction product in the thermal cracking process is 0.1 to 100 seconds.

[0040] The pyrolysis apparatus may be equipped with a supply device for supplying the plastic mixture (A) selected in step (1). The supply device may be equipped with a constant volume supply device such as a rotary feeder, screw feeder, or table feeder, and may also be equipped with a double damper, lock hopper, or the like for sealing the apparatus and the supply device. The shape of the plastic mixture (A) to be pyrolyzed is not particularly limited, and may be, for example, fluff-like, compression-molded pellet-like, or pellet-shaped by semi-melting or full melting.

[0041] The pyrolysis equipment used in the pyrolysis process may include a devolatilizing extruder, which introduces a purge gas into the pyrolysis process and removes gaseous chlorides from the resulting reaction product. Devolatilizing extruders that can be used for mixed plastics pyrolysis and processing are described in further detail in U.S. Provisional Patent Application No. 62 / 369,379, filed August 1, 2016.

[0042] The reaction product containing unsaturated hydrocarbons having 2 to 8 carbon atoms decomposed in the thermal cracking step may be separated into a gaseous product and a liquid product. In this case, the gaseous product comprises at least a portion of the gas phase of the reaction product, and the liquid product comprises at least a portion of the liquid phase of the reaction product. In this case, the thermal cracking apparatus may be equipped with a device for separating the gaseous product from the liquid product. Examples of devices for separating the gaseous product from the liquid product include a vapor-liquid separator, an oil-gas separator, a gas-liquid separator, a degasser, a deliquifier, a scrubber, a trap, a flash drum, a compressor suction drum, a gravity separator, a centrifuge, a filter vane separator, a mist removal pad, a liquid-gas coalescer, a distillation column, or a combination thereof.

[0043] In one embodiment, the thermal cracking apparatus may be a condenser that operates under conditions in which a portion of the reaction product is condensed into a hydrocarbon liquid (e.g., a liquid product) while leaving hydrocarbon gases in the gas phase (e.g., a gaseous product). The gaseous reaction product may be cooled in a cooler or the like and separated into, for example, heavy oil equivalents, light oil equivalents, kerosene equivalents, etc., based on differences in boiling points, and then recovered.

[0044] The reaction product obtained in the thermal cracking step may be hydrogenated. Hydrogenation is carried out by hydrotreating the liquid product among the reaction products. Hydrotreating the liquid product can produce hydrocarbon products and gaseous products having 1 to 4 carbon atoms. Hydrogenation is carried out in a hydrotreating reactor, for example, a hydrocracker, a catalytic cracker, a fluid catalytic cracker, a hydrotreater, or a combination thereof. Hydrogenation of the reaction product from the thermal cracking step hydrocrackers and dechlorinates long-chain molecules with a large number of carbon atoms. Hydrogenation is carried out by gradually adding the liquid product, hydrogen, or a combination thereof to a hydrotreating catalyst in an upflow, downflow, radial flow, or a combination thereof and bringing them into contact.

[0045] The hydroprocessing reactor in which the hydrogenation occurs contains a hydroprocessing catalyst and can handle gas, liquid, gas-liquid, gas-liquid-solid, or slurry phases. The hydroprocessing reactor may contain one or more beds of hydroprocessing catalyst in a fixed bed, fluidized bed, moving bed, ebullated bed, slurry bed, or combinations thereof. The hydroprocessing reactor can be operated adiabatically, isothermally, non-adiabatically, non-isothermally, or combinations thereof. In one embodiment, the hydroprocessing reactor may include one or more vessels. The hydroprocessing reactor can also facilitate any reaction of components of the liquid product in the presence of or with hydrogen.

[0046] Hydrogenation reactions are reactions that add hydrogen atoms to double bonds of unsaturated molecules (e.g., olefins, aromatic compounds) resulting in saturated molecules (e.g., paraffins, i-paraffins, naphthenes). Additionally, hydrogenation reactions can cleave bonds in organic compounds, resulting in the cracking of hydrocarbon molecules into smaller hydrocarbon molecules with two or more carbon atoms, or the subsequent reaction and / or substitution of heteroatoms with hydrogen. Examples of reactions that may occur during hydrogenation include, but are not limited to, the hydrogenation of olefins, the removal of heteroatoms from heteroatom-containing hydrocarbons (e.g., dechlorination), the hydrocracking of large paraffins or i-paraffins into smaller hydrocarbon molecules, the hydrocracking of aromatic hydrocarbons into smaller cyclic or acyclic hydrocarbons, the conversion of one or more aromatic compounds to one or more cycloparaffins, the isomerization of one or more normal paraffins to one or more i-paraffins, the selective ring-opening of one or more cycloparaffins to one or more i-paraffins, or combinations thereof.

[0047] In one embodiment, the liquid product is contacted with a hydrotreating catalyst in the presence of hydrogen to obtain gaseous products having 1 to 4 carbon atoms and liquid hydrocarbons having 5 or more carbon atoms. Here, the advantage of dechlorination using a hydrotreating catalyst is that it does not require a chlorine sorbent and requires an effective amount of Na to function as a dechlorinating agent. ２ CO ３ The advantage is that it is not necessary to add

[0048] The hydrotreating catalyst may be any catalyst (e.g., commercially available hydrotreating catalyst) for use in the hydrogenation of olefins and aromatic hydrocarbons, such as alumina-supported cobalt and molybdenum catalyst (Co—Mo catalyst), alumina-supported nickel and molybdenum catalyst (Ni—Mo catalyst), alumina-supported tungsten and molybdenum catalyst (W—Mo catalyst), alumina-supported cobalt oxide and molybdenum oxide, alumina-supported nickel oxide and molybdenum oxide, alumina-supported tungsten oxide and molybdenum oxide, alumina-supported cobalt and molybdenum sulfide, alumina-supported nickel and molybdenum sulfide, alumina-supported tungsten sulfide and molybdenum sulfide, alumina-supported zeolites containing one or more metals, or combinations thereof. Further suitable catalysts for use as hydrotreating catalysts include alumina-supported platinum and palladium catalysts (Pt-Pd catalysts) suitable for slurry processing, nickel sulfide suitable for slurry processing, molybdenum sulfide suitable for slurry processing, or combinations thereof. Zeolites include ZSM-5, ZSM-11, Y, high silica Y, USY, or combinations thereof. Each metal of the one or more metals in the zeolite can be independently selected from the group consisting of, for example, cobalt, molybdenum, tungsten, nickel, titanium, copper, magnesium, tin, iron, zinc, tungsten, vanadium, gallium, calcium, manganese, ruthenium, and rhenium.

[0049] The reaction product may also be introduced into a cracker, such as a naphtha cracker or an ethane cracker, for cracking. In some embodiments, the reaction product can be introduced into a cracker. In other embodiments, the reaction product can be introduced into a cracker after recovering aromatic compounds having 6 to 8 carbon atoms in an aromatic compound separation unit. At least a portion of the cracked reaction product and / or at least a portion of the gaseous product having 1 to 4 carbon atoms can be introduced into a separation unit to produce unsaturated hydrocarbon gases, saturated hydrocarbon gases, aromatic compounds, and heavy components. The unsaturated hydrocarbon gases include ethylene, propylene, butylenes, butadiene, or combinations thereof. The saturated hydrocarbon gases include methane, ethane, propane, butanes, hydrogen, or combinations thereof. The aromatic compounds include aromatic hydrocarbons having 6 to 8 carbon atoms. The heavy components include hydrocarbons having 5 or more carbon atoms other than aromatic hydrocarbons having 6 to 8 carbon atoms. In one embodiment, the separation unit may include multiple distillation columns.

[0050] Next, an embodiment in which the decomposition of the plastic mixture (A) in the step (2) includes a catalytic decomposition step will be described below.

[0051] In the catalytic cracking step, the plastic mixture (A) is heated and brought into contact with a catalyst to carry out a reaction. Any suitable known reactor can be used in the catalytic cracking step. Examples of materials for the reactor include quartz glass, carbon steel, stainless steel, Inconel alloy, Hastelloy alloy, Incoloy alloy, and Monel alloy.

[0052] Examples of catalysts used in the catalytic cracking process include unbound (unsupported) zeolite catalysts and zeolite catalysts combined with a binder or carrier. Any known suitable binder and carrier can be used. Examples of binders include silica, alumina, silica-alumina, silica-titania, silica-thoria, silica-magnesia, silica-zironia, silica-beryllia, and ternary compositions of silica and other refractory oxides. Examples of binders or matrix materials include clays such as montmorillonite, kaolin, bentonite, halloysite, dickite, nacrite, and anaxite.

[0053] As the catalyst used in the catalytic cracking step, an MFI zeolite catalyst is preferably used. The MFI zeolite catalyst may contain silicon atoms, aluminum atoms, oxygen atoms, and hydrogen atoms as atoms other than sodium atoms. The MFI zeolite catalyst may also contain atoms such as sodium atoms, titanium atoms, chromium atoms, manganese atoms, iron atoms, cobalt atoms, nickel atoms, copper atoms, ruthenium atoms, rhodium atoms, palladium atoms, silver atoms, iridium atoms, platinum atoms, boron atoms, nitrogen atoms, magnesium atoms, phosphorus atoms, zinc atoms, and gallium atoms. From the viewpoint of improving the yield of unsaturated hydrocarbons having 2 to 8 carbon atoms, the MFI zeolite catalyst preferably contains sodium atoms, silicon atoms, and aluminum atoms.

[0054] The ratio of the number of moles of silicon atoms to the number of moles of aluminum atoms (Si / Al ratio) of the MFI zeolite catalyst is preferably 50 or more, and more preferably 100 or more, from the viewpoint of improving the yield of unsaturated hydrocarbons having 2 to 8 carbon atoms.

[0055] The sodium content and Si / Al ratio of the zeolite catalyst can be calculated by analyzing the zeolite catalyst according to known ICP emission spectrometry.

[0056] Here, MFI zeolite means a crystalline aluminosilicate having an MFI structure according to the structure code of the International Zeolite Association (IZA). Specific examples of MFI zeolite include H＋ -ZSM-5, NH ４ ＋ -ZSM-5, Na ＋ -ZSM-5, Ca ２＋ MFI zeolite can be prepared by any suitable known method, and commercially available H ＋ ZSM-5 may also be used. The identity of the zeolite as an MFI type zeolite can be confirmed by X-ray diffraction analysis.

[0057] A method for producing an MFI zeolite catalyst is described below. The MFI zeolite catalyst can be produced by a production method including the steps of preparing a mixture containing a silicon source, an aluminum source, a template, and an alkali metal source, and crystallizing the mixture to obtain MFI zeolite. Here, the "template" refers to a substance that imparts a pore structure to the zeolite.

[0058] As the silicon source, known silicon sources used in the production of various zeolites can be used, such as tetraethyl orthosilicate, colloidal silica, silica gel dry powder, silica hydrogel, and sodium silicate.

[0059] As the aluminum source, known aluminum sources used in the production of various zeolites can be used. Examples of aluminum sources include aluminum nitrate, aluminum chloride, sodium aluminate, aluminum hydroxide, and aluminum alkoxide. Among these aluminum sources, aluminum nitrate or sodium aluminate is preferred.

[0060] As the template, known templates used in the synthesis of MFI zeolite can be used. Examples of the template include tetrapropylammonium salt, tetraethylammonium salt, propanolamine, ethanolamine, n-propylamine, morpholine, 1,5-diaminopentane, 1,6-diaminohexane, dipropylenetetramine, and triethylenetetramine. Among these templates, tetrapropylammonium salt (tetrapropylammonium hydroxide) is preferred.

[0061] The alkali metal source includes, for example, alkali metal hydroxides, alkali metal chlorides, alkali metal bromides, alkali metal sulfides, etc. The alkali metal includes, for example, sodium and potassium.

[0062] When the alkali metal is sodium, examples of the sodium source include sodium hydroxide, sodium nitrate, sodium chloride, sodium bromide, sodium sulfate, sodium silicate, sodium aluminate, and compounds containing sodium as a counter cation.

[0063] When the alkali metal is potassium, examples of potassium include potassium hydroxide, potassium nitrate, potassium chloride, potassium bromide, potassium sulfate, potassium silicate, potassium aluminate, and compounds containing potassium as a counter cation.

[0064] In the mixture containing the silicon source, the aluminum source, the template, and the alkali metal source, the ratio of the number of moles of silicon atoms to the number of moles of aluminum atoms (Si / Al ratio) is preferably not less than 50, more preferably not less than 100. The ratio may be not more than 10,000, and is preferably not more than 2,500.

[0065] The ratio of the number of moles of each component in the mixture containing the silicon source, aluminum source, template, and alkali metal source to the number of moles of silicon atoms preferably satisfies the following requirements: Template: 0.02 or more and 5.0 or less Alkali metal source: 0.01 or more and 0.2 or less Water: 2 or more and 100 or less

[0066] Furthermore, it is more preferable that the ratio of the number of moles of each component in the mixture containing the silicon source, aluminum source, template, and alkali metal source to the number of moles of silicon atoms satisfies the following requirements: Template: 0.05 or more and 2.0 or less Alkali metal source: 0.04 or more and 0.3 or less Water: 5 or more and 50 or less

[0067] The catalytic cracking temperature in the catalytic cracking step is 400 to 700°C, preferably 450 to 600°C. The catalytic cracking pressure in the catalytic cracking step is 0 to 5 MPaG, preferably 0 to 0.5 MPaG. The gas residence time in the catalytic cracking step is 0.1 to 100 seconds.

[0068] In the catalytic cracking step, steam or an inert gas such as nitrogen gas or carbon dioxide gas may be present.

[0069] In the catalytic cracking process, in addition to heating, the reaction is carried out in contact with a catalyst. Therefore, the above-mentioned thermal cracking device may be used for the catalytic cracking process. In this case, the thermal cracking device may contain one or more beds of an inert material or a thermal cracking catalyst, including sand, zeolite, alumina, a catalytic cracking catalyst, or a combination thereof. The thermal cracking catalyst can transfer heat to the components subjected to the thermal cracking process. The thermal cracking device can be operated adiabatically, isothermally, non-adiabatically, non-isothermally, or a combination thereof.

[0070] The zeolite catalyst used in the catalytic cracking step may be a regenerated catalyst. That is, the first embodiment can be carried out by applying the plastic mixture (A) (which may further contain an organic chlorine compound) to the catalytic cracking step in the presence of a regenerated catalyst obtained by regenerating a used zeolite catalyst.

[0071] The method for regenerating a catalyst will be specifically described below. The method for regenerating a catalyst includes a step of calcining the catalyst in an atmosphere containing 1% to 50% by volume of oxygen to obtain a regenerated catalyst.

[0072] The step of obtaining the regenerated catalyst is preferably carried out in an atmosphere containing oxygen in the range of 1% by volume to 50% by volume, more preferably in an atmosphere containing oxygen in the range of 5% by volume to 30% by volume.

[0073] The step of obtaining the regenerated catalyst can be carried out, for example, in an air atmosphere, a nitrogen gas atmosphere, an argon gas atmosphere, a carbon dioxide gas atmosphere, or a mixed gas atmosphere thereof, while adjusting the oxygen concentration in the atmosphere by any suitable known method.

[0074] The temperature in the step of obtaining the regenerated catalyst is preferably in the range of 400 to 700°C, more preferably in the range of 450 to 600°C.

[0075] The treatment time in the step of obtaining the regenerated catalyst is preferably 30 minutes to 48 hours, more preferably 1 to 24 hours.

[0076] When applied to the first embodiment, the regenerated catalyst obtained by the catalyst regeneration method can be used in the same manner as an unused "zeolite catalyst" in a catalytic cracking step, without any particular adjustment of conditions such as temperature, treatment time, and atmosphere.

[0077] An embodiment in which the decomposition of the plastic mixture (A) in step (2) is carried out in multiple stages will be described. In this embodiment, the products obtained in the thermal decomposition step and / or catalytic decomposition step are decomposed again in another thermal decomposition step.

[0078] When step (2) is performed in multiple stages, for example, thermal crackers may be connected in series. When two thermal crackers are connected, the thermal cracking process can be divided into a first stage performed in a first thermal cracker and a second stage performed in a second thermal cracker that is fluidly connected downstream of the first stage. As will be understood by those skilled in the art, the second stage can enhance the thermal cracking of the intermediate pyrolysis product stream flowing from the first stage to the second stage to obtain a reaction product that flows from the second stage. In one embodiment, the first stage can perform thermal cracking of the plastic mixture (A), and the second stage can utilize thermal or catalytic cracking of the plastic mixture (A) to obtain a reaction product that flows from the second stage. Alternatively, the first stage can perform catalytic cracking of the plastic mixture (A), and the second stage can utilize thermal or catalytic cracking of the plastic mixture (A) to obtain a reaction product that flows from the second stage. In another embodiment, the thermal cracker may include one or more facilities configured to convert the plastic mixture (A) into gas-phase and liquid-phase products. One or more of the facilities may include the inert materials or pyrolysis catalysts described above.

[0079] Step (3) is a step of washing and purifying the reaction product to separate unsaturated hydrocarbons having 2 to 8 carbon atoms. The reaction product is washed and purified in step (3), and unsaturated hydrocarbons having 2 to 8 carbon atoms are separated. Washing and purification may be performed by known methods. Furthermore, the purification in step (3) may include purification by hydrogenation as described above.

[0080] The reaction product containing unsaturated hydrocarbons having 2 to 8 carbon atoms obtained in step (2) is washed in step (3) to remove chlorine compounds, sulfur compounds, nitrogen compounds, etc. These processes include solvent washing, washing with an alkaline solution, absorption and removal of ammonia components, and adsorption and removal using an adsorbent. Furthermore, the product is separated and purified into multiple products with different boiling points by purification. The washing and purification processes may be implemented within the process for producing unsaturated hydrocarbons having 2 to 8 carbon atoms according to the first embodiment, or may be shared within an industrial complex incorporating different technologies. When a naphtha cracker and an ethane cracker are adjacent to each other, the reaction product may be introduced into the distillation columns of the naphtha cracker and the ethane cracker for separation and purification. Furthermore, to increase the yield of unsaturated hydrocarbons having 2 to 8 carbon atoms, a portion of the separated and purified hydrocarbons may be recycled to the catalytic cracking process or the cracker.

[0081] The unsaturated hydrocarbons having 2 to 8 carbon atoms obtained in step (3) are olefins having 2 to 5 carbon atoms, such as ethylene, propylene, butene, and pentene; dienes having 4 or 5 carbon atoms, such as butadiene and pentadiene; and aromatic hydrocarbons having 6 to 8 carbon atoms, such as benzene, toluene, and xylene, and preferably olefins having 2 to 4 carbon atoms.

[0082] [Second Embodiment of Method for Producing Unsaturated Hydrocarbons Having 2 to 8 Carbon Aces] A method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms according to a second embodiment includes the steps of: (1) separating, from waste plastics, a plastic mixture (A) containing 50% by mass or more of polyolefin plastics; and (B); (12) heating the residue (B) to obtain a mixed gas containing carbon monoxide, carbon dioxide, and hydrogen; (13) mixing the mixed gas with at least one gas selected from the group consisting of carbon monoxide, carbon dioxide, and hydrogen, or removing a portion of the at least one gas selected from the group consisting of carbon monoxide, carbon dioxide, and hydrogen from the mixed gas to obtain an adjusted gas in which the ratio by volume of hydrogen to the total volume of carbon monoxide and carbon dioxide is 1.5 to 4.0; (14) reacting the carbon monoxide, carbon dioxide, and hydrogen contained in the adjusted gas to obtain an alcohol; and (15) obtaining unsaturated hydrocarbons having 2 to 8 carbon atoms using the alcohol as a raw material.

[0083] Step (1) of the second embodiment is the same as step (1) of the first embodiment described above. In the second embodiment, a raw material containing the residue (B) separated in step (1) is gasified in step (12) described below to obtain a mixed gas mainly composed of carbon monoxide, carbon dioxide, and hydrogen. The raw material may include waste materials containing organic matter from which a gas containing hydrogen and carbon oxide can be obtained, as shown below. Examples of the waste materials include food waste, paper waste, textile waste, plastic waste, biomass waste, food waste, construction materials, wood, wood chips, thinned wood, rice straw, wheat straw, rice husks, waste oil, rubber tires, and mixtures thereof.

[0084] Step (12) is a step of heating the residue (B) to obtain a mixed gas containing carbon monoxide, carbon dioxide, and hydrogen, and is performed using a mixed gas acquisition apparatus. In step (12), the residue (B) is supplied to the mixed gas acquisition apparatus, and the residue (B) reacts in the mixed gas acquisition apparatus. As the mixed gas acquisition apparatus, for example, a known apparatus such as a fixed-bed furnace, a fluidized-bed furnace, a bubbling-type fluidized-bed furnace, a circulating fluidized-bed furnace, or a circulating moving-bed furnace can be used.

[0085] The residue (B) supplied to the mixed gas acquisition device may further contain waste plastics such as general waste plastics and industrial waste plastics. General waste plastics are plastic waste mainly generated from households, such as used PET bottles, food trays, plastic bags, seasoning bottles, hangers, etc. On the other hand, industrial waste plastics are plastic waste mainly generated from business establishments such as factories and stores, such as scrap generated during the manufacturing, processing, and distribution of plastic products, packaging materials, plastic bags discarded from offices, food containers, etc.

[0086] In the mixed gas obtaining device, it is assumed that the reactions represented by the following formulas (1) to (4) occur due to the reaction between hydrocarbons and water vapor or oxygen.

[0087] C ｎ H ２ｎ +nH ２ O → nCO + 2nH ２ (1) C ｎ H ２ｎ +2nH ２ O → nCO ２ +3nH ２ (2) C ｎ H ２ｎ +0.5nO ２ →nCO+nH ２ (3) C ｎ H ２ｎ +nO ２ →nCO ２ +nH ２ (4)

[0088] In the above formulas (1) and (3), carbon monoxide is produced together with hydrogen, but in the second embodiment, a step may be carried out in which carbon dioxide and hydrogen are obtained from the carbon monoxide and water as raw materials by the reaction of the following formula (5): Alternatively, a step may be carried out in which the thermal energy and carbon dioxide required for step (12) are obtained from the carbon monoxide and oxygen as raw materials by the reaction of the following formula (6):

[0089] CO + H ２ O → CO ２ +H ２ (5) CO+0.5O ２→CO ２ (6) In the reactions of the above formulas (1) to (6), 1 to 3 moles of hydrogen are obtained per mole of carbon atom.

[0090] On the other hand, if the residue (B) contains waste containing naturally occurring organic matter, it is thought that, for example, a reaction represented by the following formula (7) and / or a reaction represented by the following formula (8) will occur within the mixed gas acquisition device.

[0091] (C ６ H １２ O ６ ) ｎ → 6nCO + 6nH ２ (7) (C ６ H １２ O ６ ) ｎ +6nH ２ O→6nCO ２ +12nH ２ (8) In the above formula (7), carbon monoxide is produced together with hydrogen, but carbon dioxide and hydrogen may be obtained by the reaction of the above formula (5) using the carbon monoxide and water as raw materials. In the formulas (7) and (8), 1 to 2 moles of hydrogen are obtained per mole of carbon atom.

[0092] The reaction for obtaining carbon monoxide and hydrogen from the above-mentioned organic substances may require a reaction temperature higher than that for obtaining carbon dioxide and hydrogen, and in view of the energy cost involved in raising the temperature, it is expected that the method for obtaining carbon dioxide and hydrogen may be more advantageous.

[0093] The second embodiment may optionally include a step (12') of scrubbing the mixed gas after step (12).

[0094] Step (12') is a step of scrubbing the mixed gas by removing impurities from the gas mixture, and is carried out using a mixed gas scrubber. In step (12'), the mixed gas is supplied to the mixed gas scrubber. The mixed gas may contain impurities such as soot, fly ash, and other solid components that poison the catalyst. Furthermore, other impurities may include reaction inhibitors such as sulfur, chlorine, and nitrogen. In such cases, it is preferable to scrub the mixed gas before step (14), which will be described later. Step (12') can reduce, for example, the chloride and sulfide concentrations of the mixed gas. This allows the chloride and sulfide concentrations in the subsequent steps to be reduced to 1 ppm or less, preferably 100 ppb or less, respectively. Step (12') is usually carried out depending on the solid components or reaction inhibitors contained in the mixed gas. The scrubbing in step (12') is carried out by a known scrubbing method. Known devices such as a wet scrubber and an electrostatic precipitator can be used as the mixed gas scrubber.

[0095] By scrubbing the mixed gas in step (12') so that the concentrations of chlorides and sulfides in the mixed gas are each 1 ppm or less, preferably 100 ppb or less, the deterioration rate of the catalyst used in step (14) described below can be reduced, and the catalyst life can be extended.

[0096] Step (13) is a step of mixing the mixed gas with at least one gas selected from the group consisting of carbon monoxide, carbon dioxide, and hydrogen, or removing a portion of at least one gas selected from the group consisting of carbon monoxide, carbon dioxide, and hydrogen from the mixed gas to obtain an adjusted gas in which the ratio by volume of hydrogen to the total volume of carbon monoxide and carbon dioxide is 1.5 to 4.0. Step (13) is carried out using a gas composition adjuster, and if necessary, CO ２ This may be done using a separation device.

[0097] Hereinafter, the gas component adjusting device and CO ２ Step (13), which is carried out using a separation device, will now be described in detail.

[0098] In step (13), the mixed gas cleaned by the mixed gas cleaning device is supplied to a gas composition adjusting device. Hydrogen can be supplied to the gas composition adjusting device. As the gas composition adjusting device, for example, a known device such as a partial oxidation reactor, a steam reforming reactor, or a water gas shift reactor can be used.

[0099] The adjusted gas (hereinafter, sometimes referred to as primary adjusted gas) adjusted in the gas composition adjuster is CO ２ fed to the separation device. ２ The separation device selectively separates (removes) carbon dioxide from the supplied primary regulated gas to obtain regulated gas (hereinafter, also referred to as secondary regulated gas). ２ Examples of the separation device include a pressure swing adsorption device, an absorption / stripping tower, a cryogenic carbon dioxide separation device, and a carbon dioxide separation membrane facility.

[0100] Step (13) is to adjust the composition of the mixed gas in the gas component adjusting device, and ２ In the separator, CO is separated from the conditioned gas. ２ By passing through step (13), the mixed gas can be adjusted to a composition suitable for alcohol synthesis.

[0101] The hydrogen required to produce alcohol is 2 moles per mole of carbon monoxide (CO) and 1 mole of carbon dioxide (CO ２ Therefore, the volume fractions of hydrogen, carbon monoxide, and carbon dioxide in the adjusted gas supplied to the reactor where the reaction in step (14) described below takes place are ideally adjusted so that the index SN shown in the following formula (9) is 2 or more. In the following formula (9), yH ２ , yCO ２ and yCO are the volume fractions of hydrogen, carbon dioxide, and carbon monoxide in the conditioning gas.

[0102] SN = (yH ２ -yCO ２ ) / (yCO+yCO ２ ) (9)

[0103] In the second embodiment, when the mixed gas obtained in step (12) contains hydrogen, carbon dioxide, and carbon monoxide, it is desirable to use a regulated gas in which the carbon dioxide concentration is adjusted to preferably 0.1 to 20% by volume, more preferably 1 to 10% by volume. Therefore, when the value of the index SN is low, it is preferable to adjust the SN value in advance using the mixed gas as a regulated gas before step (14) described below.

[0104] Step (13) may be performed by at least one of (i) adding hydrogen to the mixed gas, (ii) a partial oxidation reaction of hydrocarbons contained in the mixed gas, (iii) a steam reforming reaction of hydrocarbons contained in the mixed gas, and (iv) a water-gas shift reaction of carbon monoxide contained in the mixed gas. As a result, the volumetric ratio of hydrogen to the total volumetric ratio of carbon monoxide and carbon dioxide in the adjusted gas (hereinafter referred to as H ２ / (CO + CO ２ ) can be preferably adjusted to 1.5 to 4.0.

[0105] In step (13), for example, hydrocarbons contained in the mixed gas may be reformed into carbon monoxide and hydrogen by a partial oxidation reaction or a steam reforming reaction, followed by a water gas shift reaction. ２ / (CO + CO ２ ) can be more easily adjusted to 1.5 or more and 4.0 or less.

[0106] Alternatively, in step (13), the hydrocarbons contained in the mixed gas may be reformed into carbon monoxide and hydrogen by a partial oxidation reaction or a steam reforming reaction, and then hydrogen (hydrogen gas) may be added (supplemented). ２ / (CO + CO ２ ) can be more easily adjusted to 1.5 or more and 4.0 or less. As a method for obtaining hydrogen, known techniques can be used, such as reforming of fossil resources, decomposition reaction, hydrocarbon decomposition reaction or dehydrogenation reaction, electrolysis of water or brine, water decomposition using a photocatalyst, and ammonia decomposition.

[0107] Examples of the hydrocarbon cracking reaction include a method for producing lower olefins by the cracking reaction of naphtha, a method for obtaining hydrogen by the thermal cracking of methane, etc. Examples of the hydrocarbon dehydrogenation reaction include a method for producing ethylene by the dehydrogenation reaction of ethane, a method for producing propylene by the dehydrogenation reaction of propane, a method for producing toluene by the dehydrogenation reaction of methylcyclohexane, a method for producing cyclohexanone by the dehydrogenation reaction of cyclohexanol, etc.

[0108] Another method for adjusting the value of the indicator SN in step (13) may involve reforming, decomposing, or the like at least a portion of the carbon oxides contained in the mixed gas to change the ratio of carbon monoxide to carbon dioxide contained in the mixed gas.

[0109] Another example of a method for adjusting the value of the index SN in step (13) is a method for removing at least a portion of carbon dioxide from the mixed gas. The carbon dioxide removed here may be used for another purpose. Specifically, for example, the mixed gas can be treated by a chemical adsorption method using an amine solution to remove carbon dioxide, which is an acidic gas, and obtain a gas containing hydrogen and carbon monoxide. In addition to the chemical adsorption method, carbon dioxide, which has the highest boiling point of the three components, can be separated by cryogenic separation to obtain a gas containing hydrogen and carbon monoxide. Carbon dioxide may also be separated by a membrane separation method using a separation membrane that selectively blocks carbon dioxide, or more preferably, a separation membrane that selectively allows carbon dioxide to pass through.

[0110] CO ２In the step of selectively separating the primary regulated gas, for example, carbon dioxide, an acidic gas, can be separated from the primary regulated gas by treating the primary regulated gas with a chemical absorption method using an amine solution. This allows for the production of a secondary regulated gas with a carbon dioxide concentration adjusted to 0.1 to 20% by volume, preferably 1 to 10% by volume. Alternatively, the primary regulated gas may be treated with a cryogenic separation method to separate carbon dioxide, which has the highest boiling point among hydrogen, carbon monoxide, and carbon dioxide, to obtain a secondary regulated gas. Alternatively, carbon dioxide may be separated by a membrane separation method using a separation membrane that selectively blocks carbon dioxide, or more preferably, a separation membrane that selectively allows carbon dioxide to pass through, to obtain a secondary regulated gas. The separated carbon dioxide may be used for another purpose.

[0111] In the above description, the case where hydrogen is supplied to the gas component adjusting device has been described, but carbon monoxide, carbon dioxide and / or hydrogen may be supplied to the gas component adjusting device. ２ Although the separation device has been described as selectively separating (removing) carbon dioxide from the supplied primary regulated gas, it may also selectively separate (remove) carbon monoxide, carbon dioxide, and / or hydrogen from the supplied primary regulated gas.

[0112] By adjusting the gas components in step (13), the raw material composition can be adjusted to a composition suitable for the reaction in step (14) described below, thereby improving the conversion rate to alcohol.

[0113] Step (14) is a step of reacting carbon monoxide, carbon dioxide, and hydrogen contained in the adjustment gas to obtain an alcohol. The alcohol obtained by the reaction in step (14) refers to any compound in which one or more hydrogen atoms of a hydrocarbon are substituted with a hydroxyl group (—OH). The alcohol may be linear, branched, or cyclic, but linear or branched saturated aliphatic alcohols are preferred. Furthermore, the alcohol is preferably a monohydric alcohol having one hydroxyl group. Furthermore, alcohols having 1 to 5 carbon atoms are preferred, and alcohols having 1 to 4 carbon atoms are more preferred. Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, and 2-methyl-2-propanol. Here, 1-propanol and 2-propanol may be collectively referred to as propanol, and 1-butanol, 2-butanol, 2-methyl-1-propanol, and 2-methyl-2-propanol may be collectively referred to as butanol.

[0114] The reaction of carbon monoxide, carbon dioxide, and hydrogen contained in the adjusted gas in step (14) is carried out in a reactor filled with a catalyst. In one embodiment, when methanol is to be obtained, the reactor may be, for example, a fixed-bed reactor. Various fixed-bed reactors for methanol synthesis have been designed for the purpose of increasing the size and saving energy (Reference: Mitsubishi Heavy Industries Techniques, Vol. 33, No. 5 (1996)). The reactor may also have a condensation surface for condensing the produced alcohol and high-boiling components, including water, within the reactor.

[0115] The reactor with a condensation surface includes a catalyst layer, a permeable wall, and a condensation surface disposed within the reactor vessel and separated from the permeable wall by a space. The reactor vessel is, for example, a pressure-resistant stainless steel container. The catalyst layer is a region where the conditioning gas comes into contact with the catalyst and the reaction proceeds. The catalyst layer is filled with a catalyst suitable for the reaction. The permeable wall is made of a porous material that allows gas to pass through. The permeable wall is made of a material that allows the alcohol-containing gas produced by the reaction in the catalyst layer to pass through but does not allow the catalyst to pass through. The space is formed between the permeable wall and the condensation surface. The condensation surface is a surface that cools the alcohol-containing gas that has passed through the permeable wall to a temperature below its dew point and condenses high-boiling components including methanol and water. Note that the term "high-boiling components" refers to components with a high boiling point, and in this specification, refers to components with a high boiling point among the components contained in the gas produced in the methanol conversion reaction. That is, in this specification, the term "high-boiling components" refers to components that condense at temperatures below the dew point of the gas produced in the methanol conversion reaction, including methanol and water.

[0116] The reactor may be provided with a first heat medium region through which a first heat medium flows to maintain the condensation surface at a temperature equal to or lower than the dew point, and a second heat medium region through which a second heat medium flows to recover heat generated by the reaction in the catalyst layer.

[0117] In another embodiment, when an alcohol having two or more carbon atoms is to be obtained, the reactor may be configured so that the catalyst is in a form other than a fixed bed, for example, a fluidized bed or a moving bed.

[0118] In one embodiment, the catalyst used in step (14) may be a catalyst for methanol production. Examples of catalysts for methanol production include catalysts containing copper and zinc. Copper may be in the form of copper oxide (CuO) or elemental copper (Cu). The components of the catalyst are not limited to the above components and may contain other elements.

[0119] The catalyst for methanol production may also contain an alkali metal. The lower limit of the alkali metal content in the catalyst is 0% by mass or more, 0.001% by mass or more, 0.01% by mass or more, or 0.015% by mass or more. The upper limit of the alkali metal content in the catalyst is 0.05% by mass or less, 0.04% by mass or less, or 0.03% by mass or less. If the alkali metal content is too high, aggregation of Cu crystals may occur easily, which may lead to a rapid decrease in activity. The alkali metal content in the catalyst may be 0% by mass.

[0120] Examples of alkali metals include Na, K and Rb. In one embodiment, the alkali metal is Na.

[0121] The method for producing the catalyst for methanol production is not particularly limited, and may be a known method. For example, the catalyst can be produced by precipitating an aqueous solution of an acid salt of each metal element constituting the catalyst with a precipitant, followed by drying and calcining (see JP 2010-194421 A).

[0122] The reaction conditions in the method for producing a catalyst for methanol production can be, for example, a reaction temperature of 150 to 300° C. and a reaction pressure (gauge pressure) of 0.5 to 10 MPa-G.

[0123] The catalyst for methanol production may be used as it is, or may be used after being reduced with a reducing gas (hydrogen, a mixed gas of hydrogen and nitrogen, a gas containing carbon monoxide, etc.). For example, when the catalyst is a CuO-ZnO catalyst, it is preferable to bring the CuO-ZnO catalyst into contact with a gas containing hydrogen to convert it into a reduced Cu-ZnO catalyst, and then bring it into contact with the adjusting gas.

[0124] In another embodiment, the catalyst used in step (14) may be a catalyst for producing an alcohol having two or more carbon atoms. The catalyst for producing an alcohol having two or more carbon atoms may be an aggregate of catalytic metals or a supported catalyst in which the catalytic metal is supported on a carrier, with a supported catalyst being preferred. By using a supported catalyst, the contact efficiency between the adjustment gas and the catalytic metal is increased.

[0125] As the carrier, a carrier conventionally used in catalysts can be used, for example, a porous carrier is preferable. The material of the porous carrier is not particularly limited, and examples thereof include silica, zirconia, titania, magnesia, alumina, activated carbon, and zeolite. Also, known catalysts can be used. For example, references such as Catalyst 2022, 64, 33, Catalyst 2020, 62, 133, Chem. Soc. Rev. 2017, 46, 1358, and Journal of the Petroleum Society of Japan 1990, 33, 1 can be used.

[0126] The form of the catalyst is not particularly limited, and may be a powder or a molded body. The shape of the molded body may be granular, cylindrical, ring-shaped, etc., and is not particularly limited. Methods for molding the catalyst include tablet molding, compression molding, extrusion molding, etc., but are not particularly limited.

[0127] When the catalyst is packed into the reactor, it may be mixed with various diluents that are inactive to the raw material gas and reaction products. Examples of diluents include copper, alumina, zirconia, quartz, glass, silicon carbide, etc. The shape of the diluent may be granular, spherical, cylindrical, or amorphous.

[0128] The amount of catalyst used is not particularly limited and may be appropriately adjusted in consideration of other reaction conditions. The catalyst may be used alone or in combination of two or more. When two or more types are used in combination, the combination and ratio thereof may be appropriately adjusted depending on the purpose.

[0129] The conditioning gas in step (14) contains carbon oxide and hydrogen. The carbon oxide is at least one of carbon monoxide and carbon dioxide. When both carbon monoxide and carbon dioxide are used as the carbon oxide, they may be contained in any ratio.

[0130] The conditioning gas may contain components other than carbon oxides and hydrogen, as long as the components do not affect the production of alcohol. Examples of such components include saturated and unsaturated hydrocarbons such as methane, ethane, propane, ethylene, and propylene, nitrogen, and rare gas elements.

[0131] The conditioning gas may further contain water. In the production of methanol, the less water in the feed gas, the better. However, even if a conditioning gas containing a certain amount of water is used in step (14), the catalyst stability is maintained.

[0132] From the viewpoint of obtaining alcohol more efficiently, the total content of carbon oxides and hydrogen in the adjusted gas is preferably 50% by volume or more, more preferably 80% by volume or more, and even more preferably 90% by volume or more, and may be 100% by volume.

[0133] H of the adjustment gas in step (14) ２ / (CO + CO ２ ) is preferably 1.5 or more and 4.0 or less from the viewpoint of further increasing the space-time yield of the alcohol.

[0134] The reaction in step (14) is preferably carried out under pressure, with the pressure during the reaction preferably being 1 to 12 MPa. The reaction is also preferably carried out under heating, with the temperature during the reaction preferably being 150 to 500°C, more preferably 200 to 400°C.

[0135] When step (14) is carried out using, for example, a fixed-bed reactor, the reaction is carried out by supplying a conditioning gas as the raw material from the inlet side of the reactor while controlling the temperature, and recovering the reaction product and unreacted raw materials from the outlet side of the reactor. The target product and unreacted raw materials are usually recovered as a mixed gas, and the target alcohol can be separated, for example, by cooling the gas.

[0136] The alcohols obtained in step (14) may be separated and then used in the next step, or the mixture may be used as is.

[0137] Furthermore, in step (14), products other than alcohols (e.g., oxygenates such as acetic acid and acetaldehyde, and esters such as ethyl acetate, methyl acetate, and methyl formate) are also produced. Therefore, the second embodiment may include step (14') (alcoholization step) in which products other than alcohols are hydrogenated to convert them into alcohols. Examples of step (14') include a method in which oxygenates including acetaldehyde, acetic acid, and the like are brought into contact with a hydrogenation catalyst to convert them into alcohols.

[0138] As the hydrogenation catalyst in step (14'), known catalysts can be used. Examples include copper, copper-zinc, copper-chromium, copper-zinc-chromium, iron, rhodium-iron, rhodium-molybdenum, palladium, palladium-iron, palladium-molybdenum, iridium-iron, rhodium-iridium-iron, iridium-molybdenum, rhenium-zinc, platinum, nickel, cobalt, ruthenium, rhodium oxide, palladium oxide, platinum oxide, and ruthenium oxide. These hydrogenation catalysts may be supported on a carrier similar to the carriers used for the above-mentioned catalysts.

[0139] Step (14) may also include contacting at least a portion of the alcohol-containing product with an aqueous sodium hydroxide solution to remove acidic substances.

[0140] Step (15) is a step of obtaining unsaturated hydrocarbons having 2 to 8 carbon atoms using the alcohol obtained in step (14) as a raw material. As described above, the unsaturated hydrocarbons having 2 to 8 carbon atoms obtained in step (15) are olefins having 2 to 5 carbon atoms such as ethylene, propylene, butene, and pentene, dienes having 4 or 5 carbon atoms such as butadiene and pentadiene, and aromatic hydrocarbons having 6 to 8 carbon atoms such as benzene, toluene, and xylene, and preferably olefins having 2 to 4 carbon atoms.

[0141] In step (15), the unsaturated hydrocarbon having 2 to 8 carbon atoms can be obtained by a known method.

[0142] The temperature in the step of obtaining olefins from an alcohol-containing raw material is not particularly limited as long as it is in the range of 300 to 700°C, but is preferably 350 to 600°C. By carrying out the reaction at a temperature in this range, it is possible to prevent a decrease in olefin selectivity. The pressure in the step of obtaining olefins from an alcohol-containing raw material is preferably 50 kPa or more in gauge pressure, more preferably 150 kPa or more in gauge pressure, even more preferably 150 to 20,000 kPa in gauge pressure, and particularly preferably 450 to 1,000 kPa in gauge pressure.

[0143] As a first method for obtaining olefins from an alcohol-containing raw material, for example, the method described in JP-A-02-000121 can be used, in which a non-zeolite molecular sieve is used as a catalyst. Examples of non-zeolite molecular sieves include SAPO-34, SAPO-17, and mixtures thereof.

[0144] As a second method for obtaining olefins from an alcohol-containing raw material, for example, a method using a shape-selective catalyst, such as that described in Japanese Patent No. 3844734, can be used. Examples of shape-selective catalysts include proton-containing pentasil-type catalysts having an alkali content of less than 380 ppm, preferably less than 200 ppm.

[0145] As a third method for obtaining olefins from a raw material containing alcohol, for example, a method described in JP 2014-46273 A can be used, in which a catalyst obtained through a silylation treatment of CHA-type aluminosilicate is used.

[0146] A fourth method for obtaining olefins from an alcohol-containing raw material can be, for example, the method described in Japanese Patent Publication No. 2007 / 083684, which uses a catalyst in which one or more elements selected from the group consisting of nickel, aluminum, manganese, iron, and copper are supported on a regular mesoporous material. Examples of regular mesoporous materials include MCM-41.

[0147] As a fifth method for obtaining olefins from a raw material containing an alcohol, for example, a method described in WO 2012 / 077723 can be used, in which a catalyst made of zirconium oxide having a surface area ratio of zirconium oxide of 50 area % or more is used.

[0148] As a sixth method for obtaining olefins from a raw material containing an alcohol, for example, a method described in JP 2012-136516 A can be used, in which a catalyst for olefin production containing an oxide of at least one element selected from the group consisting of metal elements of groups 2 and 3, 5 to 9, 11 and 12 of the periodic table, titanium, nickel, boron, gallium, thallium, germanium, tin, lead, and bismuth is used.

[0149] As a seventh method for obtaining olefins from a raw material containing an alcohol, for example, a method described in WO 2012 / 077724 using an olefin production catalyst containing an oxide of indium can be used.

[0150] As an eighth method for obtaining olefins from a raw material containing an alcohol, for example, a method described in JP 2013-43794 A can be used, which comprises hydrothermal treatment of a mixture containing (i) a silicon source, (ii) an aluminum source, (iii) a phosphorus source, (iv) a structure-directing agent, and (v) 0.001 to 0.1 mol of an inorganic or organic magnesium salt or manganese salt per 1 mol of the aluminum source, and which uses a silicoaluminophosphate molecular sieve or the like.

[0151] As a ninth method for obtaining olefins from a raw material containing an alcohol, for example, a method described in JP 2010-18556 A can be used, in which a catalyst in which one or more metals selected from Group 4 metals of the periodic table are supported on an aluminosilicate having an MFI structure is used.

[0152] In the tenth method for obtaining olefins from an alcohol-containing raw material, when the alcohol dehydration reaction is carried out, a solvent or gas inert to the catalyst and the alcohol can be added to the reaction system to carry out the dehydration reaction in a diluted state. The alcohol dehydration method may be any of a batch method, a semi-batch method, or a continuous flow method. Furthermore, any of the liquid phase, gas phase, and gas-liquid mixed phase forms may be used. Various methods such as a fixed bed, a fluidized bed, a suspension bed, and a tray-type fixed bed may be used as the catalyst packing method, and any of these methods may be used.

[0153] The catalyst may be used in combination with a known catalyst or binder that can be normally used in dehydration reactions. When the catalyst is used with a binder, they may be kneaded and extruded to form a molded body with increased mechanical strength. Examples of catalysts or binders that can normally be used in dehydration reactions include silica, alumina, clay, titania, zirconia, zinc oxide, ceria, lanthana, graphite, and ethyl cellulose.

[0154] The temperature during the alcohol dehydration reaction is preferably 450° C. or lower, more preferably 400° C. or lower, even more preferably 300° C. or lower, and particularly preferably 200° C. or lower. There are no particular restrictions on the lower limit of the temperature as long as it is equal to or higher than the temperature at which the dehydration reaction is carried out, but from the viewpoint of enhancing the activity of the obtained catalyst, it is preferably 160° C. or higher, or may be 180° C. or higher. The temperature of the catalyst layer can be adjusted as appropriate by changing the temperature of the apparatus used for the dehydration treatment, for example.

[0155] If the temperature of the dehydration reaction is within the above range, the dehydration reaction can be carried out at a relatively low temperature, thereby reducing the energy required for the reaction. Furthermore, if the catalytic activity decreases, the activity of the dehydration catalyst may be restored by regeneration using a known method.

[0156] The reaction pressure during the dehydration reaction is not particularly limited, but is preferably 0 to 100,000 KPa (gauge pressure), more preferably 0 to 5,000 KPa (gauge pressure), and even more preferably 0 to 4,000 KPa (gauge pressure).

[0157] Furthermore, although the dehydration reaction can be carried out without pressurization, the unsaturated hydrocarbons having 2 to 8 carbon atoms obtained by the dehydration reaction are in a gaseous state at room temperature and pressure if they have a low number of carbon atoms, and therefore must be liquefied in order to be purified by distillation, etc. Therefore, if the unsaturated hydrocarbons having 2 to 8 carbon atoms are in a gaseous state, they must be liquefied by cooling, pressurization, etc., which makes the production of unsaturated hydrocarbons having 2 to 8 carbon atoms complicated.

[0158] The alcohol in the alcohol-containing raw material described above may be purified, or the alcohol obtained in the step of obtaining alcohol may be used as is. Alternatively, it may be a mixture of alcohols obtained in the step of obtaining a plurality of alcohols. The alcohol in the alcohol-containing raw material may contain water and / or other oxygen-containing compounds, or may be alcohol to which water and / or other oxygen-containing compounds have been intentionally added.

[0159] The reaction product containing unsaturated hydrocarbons having 2 to 8 carbon atoms is separated and purified into a plurality of products with different boiling points by purification. The purification may be installed within the process for producing unsaturated hydrocarbons having 2 to 8 carbon atoms according to the second embodiment, or may be shared within an industrial complex that brings together different technologies. When a naphtha cracker and an ethane cracker are adjacent to each other, the reaction product may be introduced into the distillation columns of the naphtha cracker and the ethane cracker, and separated and purified.

[0160] [Third embodiment of method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms] A method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms according to a third embodiment includes the steps of: (1) separating a plastic mixture (A) containing 50 mass% or more of polyolefin plastics from waste plastics; and (B) a residue; (2) decomposing the plastic mixture (A) to obtain a reaction product containing unsaturated hydrocarbons having 2 to 8 carbon atoms; (3) washing and purifying the reaction product to separate the unsaturated hydrocarbons having 2 to 8 carbon atoms; (12) heating the residue (B) to obtain a mixed gas containing carbon monoxide, carbon dioxide, and hydrogen; and (13) separating the mixed gas from the plastic mixture (A) to obtain a mixture containing carbon monoxide, carbon dioxide, and hydrogen. and at least one gas selected from the group consisting of carbon monoxide, carbon dioxide, and hydrogen, or by removing a portion of at least one gas selected from the group consisting of carbon monoxide, carbon dioxide, and hydrogen from the mixed gas to obtain an adjusted gas in which the ratio by volume of hydrogen to the total volume of carbon monoxide and carbon dioxide is 1.5 to 4.0; a step (14) of reacting the carbon monoxide, carbon dioxide, and hydrogen contained in the adjusted gas to obtain an alcohol; and a step (15) of obtaining an unsaturated hydrocarbon having 2 to 8 carbon atoms using the alcohol as a raw material.

[0161] Steps (1) to (3) and steps (12) to (15) of the third embodiment are the same as steps (1) to (3) of the first embodiment and steps (12) to (15) of the second embodiment. The unsaturated hydrocarbon having 2 to 8 carbon atoms obtained by steps (3) and (15) is, as described above, an olefin having 2 to 5 carbon atoms such as ethylene, propylene, butene, or pentene; a diene having 4 or 5 carbon atoms such as butadiene or pentadiene; or an aromatic hydrocarbon having 6 to 8 carbon atoms such as benzene, toluene, or xylene, and is preferably an olefin having 2 to 4 carbon atoms.

[0162] In the third embodiment of the method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms, the reaction product obtained in step (2) preferably further contains paraffin. One method for increasing the paraffin content is to perform the thermal cracking reaction by setting the temperature conditions of the thermal cracking apparatus in the thermal cracking step to, for example, 450 to 750°C, i.e., a high-severity thermal cracking reaction. Furthermore, when step (2) includes a catalytic cracking step, it is also preferable to select a catalyst with high acidity from catalysts such as unbonded (unsupported) zeolite catalysts and zeolite catalysts combined with a binder or carrier. Examples of binders include silica, alumina, silica-alumina, silica-titania, silica-thoria, silica-magnesia, silica-zironia, silica-beryllia, and ternary compositions of silica and other refractory oxides. Examples of binders or matrix materials include clays such as montmorillonite, kaolin, bentonite, halloysite, dickite, nacrite, and anaxite.

[0163] The reaction product containing unsaturated hydrocarbons having 2 to 8 carbon atoms is separated and purified into a plurality of products with different boiling points by purification. The purification may be installed within the process for producing unsaturated hydrocarbons having 2 to 8 carbon atoms according to the third embodiment, or may be shared within an industrial complex that brings together different technologies. When a naphtha cracker and an ethane cracker are adjacent to each other, the reaction product may be introduced into the distillation columns of the naphtha cracker and the ethane cracker, and separated and purified.

[0164] [Fourth Embodiment of Method for Producing Unsaturated Hydrocarbons Having 2 to 8 Carbon Aces] A fourth embodiment of a method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms includes a step (21) of reacting carbon dioxide with hydrogen to obtain a reaction mixture containing an alcohol, carbon dioxide, and carbon monoxide, and a step (22) of obtaining unsaturated hydrocarbons having 2 to 8 carbon atoms from the alcohol and / or carbon monoxide contained in the reaction mixture.

[0165] In step (21), carbon dioxide and hydrogen are reacted to obtain a reaction mixture containing an alcohol, carbon dioxide, and carbon monoxide. The hydrogen and carbon dioxide used in step (21) are not particularly limited, and those obtained by known methods can be used.

[0166] The hydrogen that can be used may be obtained by known methods, such as hydrogen generated by a steam reforming reaction, hydrogen generated by an electrolytic reaction, hydrogen obtained by photolysis of water, hydrogen obtained by decomposition of methane, hydrogen obtained by gasifying coal, or hydrogen obtained by decomposition of ammonia.

[0167] Hydrogen may be produced using a hydrogen production system, which may include, for example, a pyrolysis reactor, a solids separator, and a gas purifier.

[0168] A hydrocarbon cracking reactor is a device that cracks hydrocarbon-containing gases to produce hydrogen and solid carbon. Examples of hydrocarbons that can be cracked include methane, ethane, butane, hexane, ethylene, propylene, and acetylene, with methane being preferred.

[0169] One example is the decomposition of methane. Examples of methane-containing raw gases that can be used include natural gas, biogas (methane) obtained by anaerobic fermentation of biomass, and methane-containing off-gas produced as a by-product in hydrocarbon thermal decomposition processes such as naphtha crackers or ethane crackers (thermal cracking).

[0170] Methane is decomposed into hydrogen gas and solid carbon according to equation (10): CH ４ →C+2H ２ (10)

[0171] As the methane decomposition reactor, known reactors such as a tubular reactor, a fixed bed reactor, a fluidized bed reactor, a bubbling fluidized bed reactor, a circulating fluidized bed reactor, a moving bed reactor, a circulating moving bed reactor, etc. Furthermore, as the decomposition method used in the methane decomposition reactor, known methods such as a non-catalytic thermal decomposition method, a decomposition method using a solid catalyst, or a decomposition method using a liquid catalyst such as molten salt or molten metal can be used.

[0172] The solid catalyst is not particularly limited as long as it is capable of decomposing hydrocarbons to produce hydrogen and carbon as by-products, but may include metals of any number from various UPAC groups of the periodic table, such as Group 10 (e.g., nickel), Group 8 (e.g., iron or ruthenium), Group 9 (e.g., cobalt), or Group 6 (e.g., chromium or molybdenum). Other metals that may be present include Group 7 metals (e.g., manganese) or Group 5 metals (e.g., cobalt). The metals listed above are merely exemplary, and other metals from these groups may also be included. Furthermore, a mixture of one or more of these catalysts may be used as the catalyst, or may be supported on a catalyst carrier.

[0173] Because the decomposition reaction of hydrocarbons including methane is an endothermic reaction, the decomposition reaction apparatus is equipped with a heating device that supplies reaction heat. Known heating devices that can be used for decomposition include a heating furnace, a heat exchanger that uses steam or molten salt as a heat medium, a microwave heating device, a plasma heating device, an induction heating device, and a resistance heating device. Furthermore, by using renewable energy as the energy required in the hydrogen production process, the method for producing hydrogen can reduce carbon dioxide emissions.

[0174] The solid separator is a device that separates a solid-gas mixture containing hydrogen, unreacted hydrocarbons, and / or solid carbon discharged from the cracking reactor into solid and gas components. Any separator that can separate solids and gases can be used as the solid separator. For example, known separation means such as a cyclone, a bag filter, a ceramic filter, or a sieve can be used.

[0175] The separated solid carbon is in the form of carbon black, graphite, carbon nanotubes, etc. The solid carbon can be used for applications such as battery materials, raw materials for chemicals, soil conditioners, and building materials.

[0176] The gas purification device is a solid separation device for separating hydrogen from a gas containing hydrogen from which solids have been removed and unreacted hydrocarbons, and any known gas separation device such as a PSA (Pressure Swing Adsorption) device, a cryogenic separation device, or a membrane separation device can be used.

[0177] At least a portion of the gas components containing hydrogen and unreacted hydrocarbons separated by the solid separator can be separated into hydrogen and gas components containing unreacted hydrocarbons by a gas purification device.

[0178] The hydrogen separated by the gas purification unit can be used as a feedstock for other chemical products and as fuel. The gas components, including unreacted hydrocarbons, separated from the hydrogen by the gas purification unit can be re-supplied to the cracking reactor as feedstock, thereby improving the conversion rate of hydrocarbons.

[0179] Examples of carbon dioxide include carbon dioxide recovered from the atmosphere, carbon dioxide recovered from various carbon dioxide-emitting plants, incinerators, etc. Examples of carbon dioxide recovered from various carbon dioxide-emitting plants include carbon dioxide recovered from the flue gas of a steam reformer by chemical absorption, membrane separation, or pressure swing adsorption (PSA), carbon dioxide obtained in the carbon dioxide gas recovery process of an ammonia plant, carbon dioxide recovered from blast furnace gas or coke oven gas by-products in steelworks by chemical absorption, membrane separation, or pressure swing adsorption (PSA), carbon dioxide recovered from the exhaust gas from fuel combustion in a thermal power plant by chemical absorption, membrane separation, or pressure swing adsorption (PSA), and carbon dioxide recovered from a waste incineration facility by the above-mentioned methods and obtained in the carbon dioxide gas recovery process of an ammonia plant. Note that when the carbon dioxide-containing gas contains impurities such as chlorine compounds, carbon dioxide from which the impurities have been removed in advance is used.

[0180] In step (21), carbon dioxide and hydrogen are reacted to obtain a reaction mixture containing an alcohol, carbon dioxide, and carbon monoxide. The alcohol contained in the reaction mixture refers to any compound in which one or more hydrogen atoms of a hydrocarbon are substituted with a hydroxyl group (—OH). The alcohol may be linear, branched, or cyclic, but linear or branched saturated aliphatic alcohols are preferred. The alcohol is also preferably a monohydric alcohol having one hydroxyl group. Alcohols having 1 to 5 carbon atoms are preferred, and alcohols having 1 to 4 carbon atoms are more preferred. Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, and 2-methyl-2-propanol.

[0181] The raw materials in step (21) are hydrogen and carbon dioxide. Therefore, step (21) is almost the same as step (14) in the second embodiment, except that when carbon dioxide alone is used as the raw material, the reaction product contains more water than when carbon monoxide is also included, and the equilibrium conversion is lower. Since the catalyst is easily deactivated when the reaction product contains a large amount of water, it is necessary to use a catalyst with high water resistance. To address the problem of low equilibrium conversion, it is preferable to actively remove the alcohol and water produced in the reaction. Therefore, it is preferable that the reactor has a condensation surface that condenses the high-boiling components, including the alcohol and water produced, within the reactor. As a result, a reaction mixture containing alcohol, carbon dioxide, and carbon monoxide can be obtained.

[0182] Step (22) is a step of obtaining unsaturated hydrocarbons having 2 to 8 carbon atoms from the alcohol and / or carbon monoxide contained in the reaction mixture. The unsaturated hydrocarbons having 2 to 8 carbon atoms obtained in step (22) are, as described above, olefins having 2 to 5 carbon atoms such as ethylene, propylene, butene, and pentene, dienes having 4 or 5 carbon atoms such as butadiene and pentadiene, and aromatic hydrocarbons having 6 to 8 carbon atoms such as benzene, toluene, and xylene, and are preferably olefins having 2 to 4 carbon atoms.

[0183] The method for producing an unsaturated hydrocarbon having 2 to 8 carbon atoms from an alcohol and / or carbon monoxide is not particularly limited, and any known method may be used.

[0184] The temperature in the step of producing unsaturated hydrocarbons having 2 to 8 carbon atoms from alcohols and / or carbon monoxide is preferably 200 to 400° C., more preferably 250 to 350° C. The pressure in the step of producing unsaturated hydrocarbons having 2 to 8 carbon atoms from alcohols and / or carbon monoxide is preferably normal pressure to 10 MPa, more preferably 0.1 to 10 MPa, and particularly preferably 0.3 to 5 MPa.

[0185] Examples of methods for producing unsaturated hydrocarbons having 2 to 8 carbon atoms from alcohol and / or carbon monoxide include the method described in JP 2014-55126 A, which uses a catalyst containing iron or cobalt; the method described in Republished Patent Publication No. 2014 / 024774, which uses a catalyst containing iron, cobalt, and nickel or ruthenium; and the method described in JP 2022-30433 A, which uses a catalyst having a core-shell structure with a solid containing at least iron and manganese as the core and a solid containing zeolite containing at least silicon and a Group 13 element as the shell. Also suitable are the catalysts described in "Carbon Circulation (Carbon Recycling) Technology 2021 from the Perspective of Catalysts" (CMC Research, published April 20, 2021), pp. 210-214.

[0186] The reaction product containing unsaturated hydrocarbons having 2 to 8 carbon atoms is separated and purified into a plurality of products with different boiling points by purification. The purification may be installed within the process of the method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms according to the fourth embodiment, or may be shared within an industrial complex that brings together different technologies. When a naphtha cracker and an ethane cracker are adjacent to each other, the reaction product may be introduced into the distillation columns of the naphtha cracker and the ethane cracker, and separated and purified.

[0187] [Fifth Embodiment of Method for Producing Unsaturated Hydrocarbons Having 2 to 8 Carbon Atoms] A method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms according to the fifth embodiment is a combination of the method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms according to any one of the first to third embodiments and the method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms according to the fourth embodiment.

[0188] One aspect of the fifth embodiment includes a step (1) of separating from waste plastics a plastic mixture (A) containing 50% by mass or more of polyolefin-based plastics and a residue (B); a step (2) of decomposing the plastic mixture (A) to obtain a reaction product containing unsaturated hydrocarbons having 2 to 8 carbon atoms; a step (3) of washing and purifying the reaction product to separate the unsaturated hydrocarbons having 2 to 8 carbon atoms; a step (21) of reacting carbon dioxide with hydrogen to obtain a reaction mixture containing alcohol, carbon dioxide, and carbon monoxide; and a step (22) of obtaining unsaturated hydrocarbons having 2 to 8 carbon atoms from the alcohol and / or carbon monoxide contained in the reaction mixture.

[0189] Another aspect of the fifth embodiment includes a step (1) of separating a plastic mixture (A) containing 50% by mass or more of polyolefin-based plastics from waste plastics and a residue (B); a step (12) of heating the residue (B) to obtain a mixed gas containing carbon monoxide, carbon dioxide, and hydrogen; and a step (13) of mixing the mixed gas with at least one gas selected from the group consisting of carbon monoxide, carbon dioxide, and hydrogen, or removing a portion of at least one gas selected from the group consisting of carbon monoxide, carbon dioxide, and hydrogen from the mixed gas to obtain carbon monoxide and The process includes a step (13) of obtaining an adjusted gas in which the ratio of the volume of hydrogen to the total volume of carbon dioxide and carbon monoxide is 1.5 to 4.0; a step (14) of reacting the carbon monoxide, carbon dioxide, and hydrogen contained in the adjusted gas to obtain an alcohol; a step (15) of obtaining an unsaturated hydrocarbon having 2 to 8 carbon atoms using the alcohol as a raw material; a step (21) of reacting carbon dioxide and hydrogen to obtain a reaction mixture containing the alcohol, carbon dioxide, and carbon monoxide; and a step (22) of obtaining an unsaturated hydrocarbon having 2 to 8 carbon atoms from the alcohol and / or carbon monoxide contained in the reaction mixture.

[0190] Another aspect of the fifth embodiment is a process (1) for separating a plastic mixture (A) containing 50% by mass or more of polyolefin-based plastics from waste plastics and a residue (B); a process (2) for decomposing the plastic mixture (A) to obtain a reaction product containing unsaturated hydrocarbons having 2 to 8 carbon atoms; a process (3) for washing and purifying the reaction product to separate the unsaturated hydrocarbons having 2 to 8 carbon atoms; a process (12) for heating the residue (B) to obtain a mixed gas containing carbon monoxide, carbon dioxide, and hydrogen; and a process (13) for mixing the mixed gas with at least one gas selected from the group consisting of carbon monoxide, carbon dioxide, and hydrogen, or for separating carbon monoxide from the mixed gas. the step (13) of removing a portion of at least one gas selected from the group consisting of carbon dioxide and hydrogen to obtain an adjusted gas in which the ratio by volume of hydrogen to the total volume of carbon monoxide and carbon dioxide is 1.5 to 4.0; the step (14) of reacting the carbon monoxide, carbon dioxide, and hydrogen contained in the adjusted gas to obtain an alcohol; the step (15) of obtaining an unsaturated hydrocarbon having 2 to 8 carbon atoms using the alcohol as a raw material; the step (21) of reacting carbon dioxide with hydrogen to obtain a reaction mixture containing the alcohol, carbon dioxide, and carbon monoxide; and the step (22) of obtaining an unsaturated hydrocarbon having 2 to 8 carbon atoms from the alcohol and / or carbon monoxide contained in the reaction mixture.

[0191] Steps (1) to (3), steps (12) to (15), steps (21) and (22) in the fifth embodiment are similar to steps (1) to (3) in the first embodiment, steps (12) to (15) in the second embodiment and steps (21) and (22) in the fourth embodiment, respectively.

[0192] The reaction product containing unsaturated hydrocarbons having 2 to 8 carbon atoms is separated and purified into a plurality of products with different boiling points by purification. The purification may be installed within the process of the method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms according to the fifth embodiment, or may be shared within an industrial complex that brings together different technologies. When a naphtha cracker and an ethane cracker are adjacent to each other, the reaction product may be introduced into the distillation columns of the naphtha cracker and the ethane cracker, and separated and purified.

[0193] [Sixth Embodiment of the Method for Producing Unsaturated Hydrocarbons Having 2 to 8 Carbon Atoms] A method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms according to the sixth embodiment is a combination of the method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms according to any one of the first to fourth embodiments and a method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms, the method including a step (31) of dehydrating at least one alcohol selected from the group consisting of ethanol, propanol, and butanol to obtain unsaturated hydrocarbons having 2 to 8 carbon atoms.

[0194] One aspect of the sixth embodiment includes a step (1) of separating from waste plastics a plastic mixture (A) containing 50% by mass or more of polyolefin-based plastics and a residue (B); a step (2) of decomposing the plastic mixture (A) to obtain a reaction product containing unsaturated hydrocarbons having 2 to 8 carbon atoms; a step (3) of washing and purifying the reaction product to separate the unsaturated hydrocarbons having 2 to 8 carbon atoms; and a step (31) of dehydrating at least one alcohol selected from the group consisting of ethanol, propanol, and butanol to obtain unsaturated hydrocarbons having 2 to 8 carbon atoms.

[0195] Another aspect of the sixth embodiment includes the steps of: (1) separating a plastic mixture (A) containing 50% or more by mass of polyolefin plastics from waste plastics; (12) heating the residue (B) to obtain a mixed gas containing carbon monoxide, carbon dioxide, and hydrogen; (13) mixing the mixed gas with at least one gas selected from the group consisting of carbon monoxide, carbon dioxide, and hydrogen, or removing a portion of at least one gas selected from the group consisting of carbon monoxide, carbon dioxide, and hydrogen from the mixed gas to obtain an adjusted gas in which the volume ratio of hydrogen to the total volume of carbon monoxide and carbon dioxide is 1.5 to 4.0; (14) reacting the carbon monoxide, carbon dioxide, and hydrogen contained in the adjusted gas to obtain an alcohol; (15) obtaining unsaturated hydrocarbons having 2 to 8 carbon atoms using the alcohol as a raw material; and (31) dehydrating at least one alcohol selected from the group consisting of ethanol, propanol, and butanol to obtain unsaturated hydrocarbons having 2 to 8 carbon atoms.

[0196] Another aspect of the sixth embodiment includes a step (1) of separating a plastic mixture (A) containing 50% by mass or more of polyolefin-based plastics from waste plastics and a residue (B); a step (2) of decomposing the plastic mixture (A) to obtain a reaction product containing unsaturated hydrocarbons having 2 to 8 carbon atoms; a step (3) of washing and purifying the reaction product to separate the unsaturated hydrocarbons having 2 to 8 carbon atoms; a step (12) of heating the residue (B) to obtain a mixed gas containing carbon monoxide, carbon dioxide, and hydrogen; and a step (13) of mixing the mixed gas with at least one gas selected from the group consisting of carbon monoxide, carbon dioxide, and hydrogen, or Alternatively, the method includes a step (13) of removing a portion of at least one gas selected from the group consisting of carbon monoxide, carbon dioxide, and hydrogen from the mixed gas to obtain an adjusted gas in which the ratio by volume of hydrogen to the total volume of carbon monoxide and carbon dioxide is 1.5 to 4.0; a step (14) of reacting the carbon monoxide, carbon dioxide, and hydrogen contained in the adjusted gas to obtain an alcohol; a step (15) of obtaining unsaturated hydrocarbons having 2 to 8 carbon atoms using the alcohol as a raw material; and a step (31) of dehydrating at least one alcohol selected from the group consisting of ethanol, propanol, and butanol to obtain unsaturated hydrocarbons having 2 to 8 carbon atoms.

[0197] Another aspect of the sixth embodiment includes a step (21) of reacting carbon dioxide with hydrogen to obtain a reaction mixture containing an alcohol, carbon dioxide, and carbon monoxide, a step (22) of obtaining an unsaturated hydrocarbon having 2 to 8 carbon atoms from the alcohol and / or carbon monoxide contained in the reaction mixture, and a step (31) of dehydrating at least one alcohol selected from the group consisting of ethanol, propanol, and butanol to obtain an unsaturated hydrocarbon having 2 to 8 carbon atoms.

[0198] Steps (1) to (3), steps (12) to (15), steps (21) and (22) in the sixth embodiment are similar to steps (1) to (3) in the first embodiment, steps (12) to (15) in the second embodiment, and steps (21) and (22) in the fourth embodiment.

[0199] Step (31) is a step of dehydrating an alcohol to obtain an unsaturated hydrocarbon having 2 to 8 carbon atoms. The alcohol used in step (31) is ethanol, propanol, or butanol.

[0200] The ethanol, propanol, and butanol used in step (31) may be produced by a chemical method from a synthesis gas using a metal catalyst, or may be produced by a fermentation method.

[0201] The metal catalyst may be a hydrogenation active metal or a combination of a hydrogenation active metal and a co-active metal. The hydrogenation active metal may be any metal that has been known to be capable of synthesizing ethanol from a mixed gas, and examples thereof include alkali metals such as lithium and sodium, elements belonging to Group 7 of the periodic table such as manganese and rhenium, elements belonging to Group 8 of the periodic table such as ruthenium, elements belonging to Group 9 of the periodic table such as cobalt and rhodium, and elements belonging to Group 10 of the periodic table such as nickel and palladium.

[0202] These hydrogenation active metals may be used alone or in combination of two or more. As the hydrogenation active metal, from the viewpoint of further improving the carbon monoxide conversion rate and the ethanol selectivity, for example, a combination of rhodium, manganese, and lithium, a combination of ruthenium, rhenium, and sodium, or a combination of rhodium or ruthenium with an alkali metal and another hydrogenation active metal is preferred.

[0203] Examples of the promoter active metal include titanium, magnesium, vanadium, etc. By supporting a promoter active metal in addition to a hydrogenation active metal, it is possible to further increase the carbon monoxide conversion rate, ethanol selectivity, etc.

[0204] Furthermore, the catalyst used in step (14) is also a catalyst suitable for this reaction.

[0205] In the production of alcohol by fermentation, the culture is typically carried out in a bioreactor. The term "bioreactor" includes fermentation devices comprising one or more vessels, columns, piping configurations, etc., such as continuous stirred tank reactors (CSTRs), immobilized cell reactors (ICRs), trickle-bed reactors (TBRs), bubble columns, gas-lift fermentors, static mixers, other vessels or other devices suitable for gas-liquid contact, etc. In one embodiment, the bioreactor may include a first growth reactor and a second fermentation reactor. An alcohol feedstock is provided to one or both of these reactors.

[0206] The bioreactor may be of any shape, such as a stirring type, airlift type, bubble column type, loop type, open bond type, photobio type, etc. The bioreactor is preferably a known loop type reactor having a main tank section and a reflux section.

[0207] The raw materials used in the fermentation method can include agricultural crops such as sugarcane, sugar beet, corn, wheat, rice, sweet potato, potato, etc., as well as non-edible lignocellulosic raw materials, but lignocellulosic raw materials are preferred. Lignocellulosic raw materials contain cellulose and hemicellulose (hereinafter sometimes referred to as celluloses), and alcohol can be obtained by decomposing the celluloses into sugars such as glucose and xylose using saccharifying enzymes and fermenting the resulting sugars.

[0208] Examples of lignocellulosic raw materials include wood, rice straw, wheat straw, bagasse, bamboo, corn (stalks, leaves, cobs, etc.), pulp, and waste products derived from these materials (e.g., waste paper, etc.). One type of lignocellulosic raw material may be used alone, or two or more types may be used in combination.

[0209] Examples of pulp include wood pulp obtained from conifers, broad-leaved trees, forest residues, construction waste, etc., non-wood pulp such as cotton linter or cotton lint, hemp, straw, bagasse, etc., waste paper pulp made from waste paper, deinked pulp, etc. Preferred pulp production methods are chemical pulp production methods such as alkali extraction and alkali cooking, which remove lignin to a high extent, and among pulps produced by chemical pulp production methods, papermaking pulp is preferred in terms of ease of availability. Examples of papermaking pulp include hardwood kraft pulp (e.g., bleached kraft pulp (LBKP), unbleached kraft pulp (LUKP), and oxygen-bleached kraft pulp (LOKP)), softwood kraft pulp (e.g., bleached kraft pulp (NBKP), unbleached kraft pulp (NUKP), and oxygen-bleached kraft pulp (NOKP)), chemical pulps such as sulfite pulp (SP) and soda pulp (AP), and semi-chemical pulps such as semi-chemical pulp (SCP) and chemi-groundwood pulp (CGP). Hardwood kraft pulp, softwood kraft pulp, sulfite pulp (SP), and semi-chemical pulp (SCP) are preferred, and hardwood bleached kraft pulp (LBKP) and softwood oxygen-bleached kraft pulp (NOKP) are more preferred.

[0210] Among lignocellulose-based raw materials other than pulp, woody lignocellulose-based raw materials include chips or bark of trees for papermaking, forest residues, thinning materials, etc., sprouts generated from stumps of woody plants, sawdust or sawdust generated from sawmills, etc., pruned branches and leaves of street trees, construction waste, etc. Examples of woody lignocellulose-based raw materials that can be used include plants of the genus Eucalyptus, willow (Salix), poplar, acacia, and cedar (Cryptomeria). Among these, plants of the genus Eucalyptus, acacia, and willow are preferred because they can be easily harvested in large quantities as raw materials. Examples of herbaceous lignocellulosic raw materials include agricultural waste such as kenaf, rice straw, wheat straw, corn cobs, and bagasse, residues and waste from industrial crops such as oil crops and rubber (e.g., EFB: Empty Fruit Bunch), and herbaceous energy crops such as Erianthus, Miscanthus, and Napier grass.

[0211] The lignocellulosic raw material other than pulp may be biomass. Examples of biomass include wood-derived paper, waste paper, pulp sludge, sludge, sewage sludge, and food waste. These biomasses can be used alone or in combination. The biomass may be a dry solid, a wet solid, or a slurry.

[0212] The lignocellulosic raw materials used in the fermentation method may also be pretreated. Examples of pretreatment include coarse crushing, explosion, and hydrolysis. In the coarse crushing process, the lignocellulosic raw materials are coarsely crushed using a crusher or grinder. At this time, it is preferable to crush the lignocellulosic raw materials into small pieces with an average diameter of 10 to 100 mm or less. The coarsely crushed lignocellulosic raw materials are then digested using an aqueous solution of a metal hydroxide such as sodium hydroxide. This cooking process removes a portion of the lignin contained in the bagasse, improving the reactivity of the cellulose and hemicellulose with enzymes. The biomass after the cooking process is neutralized using an acid.

[0213] The explosion treatment involves saccharifying the hemicellulose components of lignocellulosic feedstock and partially removing lignin. The lignocellulosic feedstock treated in the explosion equipment contains a C5 saccharification solution derived from hemicellulose, a lignin solution, and a solid residue. When the C5 saccharification solution is fermented into hemicellulose sugars separately from the C6 saccharification solution, the explosion treatment product is subjected to solid-liquid separation using a filter press or the like to separate the explosion treatment solution and the solid residue. The solid residue can be further washed with water to recover the sugars contained in the solid residue. When C5 sugar fermentation and C6 sugar fermentation are performed simultaneously, solid-liquid separation is optional. The explosion treatment conditions are, for example, 200 to 240°C, 1.5 to 4 MPa, and 1 to 15 min, preferably 225 to 230°C, 2.5 to 3 MPa, and 1 to 5 min.

[0214] The solid residue obtained by the explosion treatment is washed with water to remove sugars and dissolved lignin, and then immersed in an ethanol solution having an ethanol concentration of 30% or more, preferably 50% or more, at room temperature for 0.5 to 48 hours, preferably 1 to 24 hours, to dissolve and remove the lignin coating the cellulose. After immersion in ethanol, the solid residue is subjected to a removal treatment of ethanol mechanically or by heating or heating under reduced pressure. When a high-concentration ethanol solution is used, the solid residue may be first washed with water and then subjected to the removal of ethanol.

[0215] Hemicellulose contained in lignocellulosic raw materials is hydrolyzed using high-temperature, high-pressure water or by hemicellulose hydrolase enzymes such as hemicellulase. When hydrolyzing using high-temperature, high-pressure water, hemicellulose can be decomposed into sugars (mainly C5 monosaccharides) at temperatures between 140°C and 180°C. In the case of biomass with a high hemicellulose content, treatment at high temperatures can over-decompose the C5 monosaccharides into organic acids, etc., so it is preferable to perform the decomposition treatment under relatively mild conditions. When hydrolyzing hemicellulose using high-temperature, high-pressure water, it is also preferable to add an acid such as phosphoric acid or hydrochloric acid as a catalyst. When hydrolyzing hemicellulose using a hemicellulose hydrolase enzyme, commercially available enzymes or microorganisms that produce hemicellulase may be used.

[0216] The carbon source for the fermentation reaction in the fermentation method is a gaseous substrate containing carbon monoxide. The gaseous substrate may be a by-product of an industrial process, a carbon monoxide-containing waste gas obtained from automobile exhaust, or the like. Industrial processes include ferrous metal product manufacturing, e.g., steel mills, non-ferrous product manufacturing, petroleum refining processes, coal gasification, power generation, carbon black production, ammonia production, methanol production, coke production, and the like. The gaseous substrate may be captured from the industrial process before being released into the atmosphere using any convenient method. Depending on the composition of the gaseous substrate, it may also be desirable to treat it to remove any unwanted impurities, such as dust particles, before introducing it into the fermentation. For example, the gaseous substrate may be filtered or washed using known methods.

[0217] The gaseous substrate may also be sourced from biomass gasification. The gasification process involves the partial combustion of biomass under a limited supply of air or oxygen. The resulting gas typically contains primarily carbon monoxide and hydrogen, with minimal amounts of carbon dioxide, methane, ethylene, and ethane. For example, biomass by-products obtained during the extraction and processing of food products, such as sugar from sugarcane or starch from corn or grains, or non-food biomass waste produced by forestry, can be gasified to produce the gaseous substrate.

[0218] The gaseous substrate contains carbon monoxide, e.g., at least 20-100%, 43-95%, 60-90%, or 70-90% by volume. In one embodiment, the gaseous substrate contains 25%, 30%, 35%, 40%, 45%, or 50% by volume of carbon monoxide. Gaseous substrates having lower concentrations of carbon monoxide, e.g., 6% by volume, may also be suitable, particularly when hydrogen and carbon dioxide are also present.

[0219] Industrial flue gases containing carbon dioxide and hydrogen may also be used as the gaseous substrate. Examples of industrial flue gases include flue gases from hydrogen production plants. The flue gases from hydrogen production plants contain 50-60% carbon dioxide, 20-30% hydrogen, 5-15% carbon monoxide, and 5-15% methane. Also, flue gases from ammonia production are rich in carbon dioxide and hydrogen. Furthermore, industrial flue gases include gases produced from the processing of any carbonaceous raw materials, such as petroleum, coal, and biomass.

[0220] Processes for the production of ethanol and other alcohols from gaseous substrates are known. Exemplary processes include those described in, for example, WO 2007 / 117157, WO 2008 / 115080, U.S. Pat. No. 6,340,581, U.S. Pat. No. 6,136,577, U.S. Pat. No. 5,593,886, U.S. Pat. No. 5,807,722, and U.S. Pat. No. 5,821,111, each of which is incorporated herein by reference.

[0221] The gaseous substrate may be derived from waste materials. The waste materials may be industrial waste materials such as industrial solid waste, or municipal waste materials such as municipal solid waste (MSW), including combustible materials such as plastic waste, food waste, discarded tires, biomass waste, food waste, building materials, wood, wood chips, fibers, and paper. Municipal solid waste (MSW) is preferred.

[0222] The gaseous substrate is preferably a synthesis gas containing carbon monoxide and hydrogen. An example in which the waste-derived gas is synthesis gas will be described in detail below. Synthesis gas can be obtained by performing a raw material gas production step in which raw material gas is produced by gasifying waste, and then performing a synthesis gas purification step in which specific substances such as various pollutants, soot particles, impurities, and undesirable amounts of compounds are removed or reduced from the produced raw material gas.

[0223] In the raw material gas generation step, the waste may be gasified using, for example, a gasification furnace. A gasification furnace is a furnace that combusts (incompletely combusts) a carbon source. Examples of gasification furnaces include shaft furnaces, kiln furnaces, fluidized bed furnaces, gasification reforming furnaces, and plasma gasification furnaces. The temperature at which the waste is gasified into the raw material gas is not particularly limited, but is usually 100 to 2500°C, and preferably 200 to 2100°C.

[0224] The raw material gas obtained by gasifying waste preferably contains carbon monoxide and hydrogen, but may further contain carbon dioxide, oxygen, and nitrogen. The raw material gas may also contain components such as soot, tar, nitrogen compounds, sulfur compounds, phosphorus compounds, and organic compounds. The raw material gas typically contains 0.1 to 80% by volume of carbon monoxide and 0.1 to 80% by volume of hydrogen. The raw material gas may also preferably contain 0.1 to 70% by volume of carbon dioxide.

[0225] The raw material gas may be produced by subjecting waste to a heat treatment (commonly known as gasification) in which the waste is combusted (incompletely combusted), i.e., by partially oxidizing the waste, as a gas containing carbon monoxide in an amount of, but not limited to, 0.1% by volume or more, preferably 10% by volume or more, and more preferably 20% by volume or more.

[0226] The feed gas is preferably converted into a synthesis gas by removing or reducing certain substances such as various pollutants, dust particles, impurities, and undesirable amounts of compounds.

[0227] In the synthesis gas purification step, the raw material gas may be purified by processing using one or more of a water separation device such as a gas chiller, a low-temperature separation (cryogenic) separation device, a particulate separation device that separates particulates such as soot using various filters such as a cyclone or a bag filter, a water-soluble impurity separation device such as a scrubber, a desulfurization device (sulfide separation device), a membrane separation device, a deoxygenation device, a pressure swing adsorption (PSA) separation device, a temperature swing adsorption (TSA) separation device, a pressure temperature swing adsorption (PTSA) separation device, a separation device using activated carbon, and a separation device using a deoxygenation catalyst, specifically a copper catalyst or a palladium catalyst, to obtain a synthesis gas.

[0228] When alcohol is obtained by fermentation, it is preferable to reduce the carbon dioxide gas concentration in the raw material gas. For example, it is preferable to use a pressure swing adsorption type separation device filled with a regenerated adsorbent containing zeolite to adsorb the carbon dioxide gas in the synthesis gas onto the regenerated adsorbent, thereby reducing the carbon dioxide gas concentration in the synthesis gas.

[0229] The resulting synthesis gas contains at least carbon monoxide and hydrogen, and may further contain carbon dioxide and nitrogen. The concentration of carbon monoxide in the synthesis gas is 20 to 80% by volume, preferably 25 to 50% by volume, and more preferably 30 to 45% by volume, based on the total concentration of carbon monoxide, carbon dioxide, hydrogen, and nitrogen in the synthesis gas.

[0230] The hydrogen concentration in the synthesis gas is usually 10 to 80% by volume, preferably 30 to 55% by volume, and more preferably 30 to 50% by volume, based on the total concentration of carbon monoxide, carbon dioxide, hydrogen, and nitrogen in the synthesis gas.

[0231] The carbon dioxide concentration in the synthesis gas is not particularly limited, but is usually 0.1 to 40% by volume, and preferably 0.3 to 30% by volume, based on the total concentration of carbon monoxide, carbon dioxide, hydrogen, and nitrogen in the synthesis gas. It is particularly preferable to lower the carbon dioxide concentration when ethanol is produced by microbial fermentation, and from this perspective, the carbon dioxide concentration is more preferably 0.5 to 25% by volume.

[0232] The nitrogen concentration in the synthesis gas is 40% by volume or less, preferably 1 to 20% by volume, and more preferably 5 to 15% by volume, based on the total concentration of carbon monoxide, carbon dioxide, hydrogen, and nitrogen in the synthesis gas.

[0233] The concentrations of carbon monoxide, carbon dioxide, hydrogen, and nitrogen in the synthesis gas can be kept within a predetermined range by appropriately changing combustion conditions such as the type of waste, the gasification temperature in the raw material gas generation process, the oxygen concentration of the supply gas during gasification, etc. For example, if you want to change the carbon monoxide or hydrogen concentration, you can change the waste to one with a high ratio of hydrocarbons (carbon and hydrogen), such as waste plastics, and if you want to decrease the nitrogen concentration, you can supply a gas with a high oxygen concentration in the raw material gas generation process.

[0234] Furthermore, the concentrations of carbon monoxide, carbon dioxide, hydrogen, and nitrogen in at least one of the feed gas and the synthesis gas may be adjusted as appropriate. The concentration adjustment may be achieved by adding at least one of these components to the feed gas or the synthesis gas. The amount of addition is, for example, less than 50% by volume, preferably less than 30% by volume, and more preferably less than 10% by volume, based on the total amount of the feed gas or the synthesis gas.

[0235] The alcohol produced by fermentation varies depending on the microorganism. Below we will explain ethanol, propanol, and butanol.

[0236] The production of ethanol by fermentation will be described. Examples of microorganisms that produce ethanol by fermentation include yeast and bacteria. The yeast is preferably capable of fermenting sugars (hexoses and pentoses). Specific examples of yeast include yeasts of the genus Saccharomyces such as Saccharomyces cerevisiae, yeasts of the genus Pichia such as Pichia stipitis, yeasts of the genus Candida such as Candida shihatae, yeasts of the genus Pachysolen such as Pachysolen tannophilus, and yeasts of the genus Issatchenkia such as Issatchenkia orientalis. The yeast is preferably a yeast belonging to the genus Saccharomyces or Isachenkia, more preferably Saccharomyces cerevisiae or Isachenkia orientalis. Genetically modified yeast produced using genetic engineering techniques can also be used. As the genetically modified yeast, any yeast capable of simultaneously fermenting hexose and pentose can be used without any particular limitation.

[0237] Some anaerobic microorganisms are cultured in a liquid medium. For example, a liquid medium and gas-utilizing bacteria may be supplied and housed in a bioreactor, and then synthetic gas may be supplied into the bioreactor while stirring the liquid medium. This allows the gas-utilizing bacteria to be cultured in the liquid medium, and ethanol can be produced from the synthetic gas by the fermentation process.

[0238] In the bioreactor, the temperature of the medium (culture temperature) may be any temperature, but is preferably 30 to 45°C, more preferably 33 to 42°C, and even more preferably 36.5 to 37.5°C. The culture time is preferably 1 hour or more in continuous culture, more preferably 7 days or more, particularly preferably 30 days or more, and most preferably 60 days or more. There is no particular upper limit, but from the viewpoint of periodic maintenance of equipment, it is preferably 720 days or less, more preferably 365 days or less. The culture time means the time from adding the seed bacteria to the culture tank to discharging the entire amount of the culture medium in the culture tank.

[0239] Some anaerobic bacteria are known to ferment carbon dioxide and hydrogen to alcohols, including ethanol, and acetic acid. Acetogens have the ability to convert gaseous substrates to acetate, ethanol, and other fermentation products via the Wood-Ljungdahl pathway. Examples of such bacteria include strains of Acetobacterium woodii, a bacterium of the genus Acetobacterium (Demler, M., Wester-Botz, "Reaction Engineering Analysis of Hydrogenotrophic Production of Acetic Acid by Acetobacterium woodii", Biotechnology and Bioengineering, Vol. 108, No. 2, February 2011). Acetobacterium woodii has been shown to produce acetate by fermenting gaseous substrates containing carbon dioxide and hydrogen. Buschhorn et al. demonstrated the ability of A. woodii to produce ethanol in glucose fermentation with phosphate limitation.

[0240] Additionally, some anaerobic bacteria are known to ferment carbon monoxide into ethanol. Such bacteria are preferably those having a metabolic pathway for acetyl-CoA. Examples of such bacteria include Clostridium autoethanogenum, Clostridium ljungdahlii, Clostridium aceticum, Clostridium carboxydivorans, Moorella thermoacetica, and Acetobacterium woodii, all of which belong to the genus Clostridium. Among these, Clostridium autoethanogenum is preferred.

[0241] Fermentation is desirably carried out under appropriate conditions for fermentation to occur. Reaction conditions to be considered include pressure, temperature, gas flow rate, liquid flow rate, fermentation broth pH, ​​fermentation broth redox potential, agitation rate (if using a continuous stirred tank reactor), inoculum level, maximum gas substrate concentration to ensure carbon dioxide in the liquid phase is not limiting, and maximum product concentration to avoid product inhibition. Suitable conditions are described in WO 2002 / 08438, WO 2007 / 117157, and WO 2008 / 115080.

[0242] Optimal fermentation conditions depend in part on the particular microorganism used. However, it is generally preferred that the fermentation be carried out at pressures higher than ambient pressure. Operating at increased pressure allows for a large increase in the rate of carbon dioxide transfer from the gas phase to the liquid phase, which can be taken up by the microorganism as a carbon source for the production of ethanol. On the other hand, this means that the retention time (defined as the liquid volume in the bioreactor divided by the input gas flow rate) can be reduced if the bioreactor is maintained at a pressure higher than atmospheric pressure.

[0243] It is also preferred that the rate of introduction of the carbon dioxide and hydrogen-containing gaseous substrate be such that the concentration of carbon dioxide and hydrogen in the liquid phase does not become limiting, as carbon dioxide and hydrogen-limited conditions can result in ethanol production being consumed by the culture.

[0244] The temperature of the fermentation broth in the bioreactor is not particularly limited as long as it is within the optimum temperature range for fermentation, but is preferably 20 to 40°C, more preferably 30 to 40°C. The optimum temperature for the fastest bacterial growth and the highest acetate production rate can be determined by operating the bioreactor at various different temperatures. The bioreactor is initially operated at 30°C, and the temperature is increased to several different temperatures. The optimum temperature for the fastest bacterial growth is at least 32°C, or at least 33°C, or at least 34°C, or at least 35°C, or at least 36°C.

[0245] The pH of the fermentation liquid in the bioreactor is not particularly limited, but is preferably maintained in the range of 3 to 10, more preferably 4 to 8.

[0246] Fermentation is carried out in the bioreactor, and a fermentation broth containing ethanol is obtained. The ethanol-containing fermentation broth is then subjected to a separation step. In the separation step, for example, the ethanol-containing fermentation broth is heated to 23 to 500°C under conditions of 0.01 to 1000 kPa (absolute pressure) to separate it into a liquid or solid component containing microorganisms and a gaseous component containing ethanol. By carrying out such a separation step, foaming does not occur in the distillation apparatus during the distillation operation for ethanol separation and purification, which will be described later, and therefore the distillation operation can be carried out continuously. Furthermore, ethanol separation and purification can be carried out efficiently during the separation and purification, which will be described later.

[0247] In the separation step, from the viewpoint of efficiently separating the ethanol-containing culture solution into a liquid or solid component containing microorganisms, their carcasses, proteins derived from microorganisms, etc., and a gaseous component containing ethanol, the ethanol-containing culture solution is heated preferably under conditions of 10 to 200 kPa, more preferably under conditions of 50 to 150 kPa, and even more preferably at atmospheric pressure, at a temperature of preferably 50 to 200°C, more preferably at a temperature of 80 to 180°C, and even more preferably at a temperature of 100 to 150°C.

[0248] The gaseous component containing ethanol obtained in the separation step may be liquefied by condensation to produce an ethanol-containing liquid (liquefaction step). The device used in the liquefaction step is not particularly limited, but a heat exchanger, particularly a condenser, is preferably used. Examples of condensers include water-cooled, air-cooled, and evaporative types, with water-cooled types being preferred. The condenser may be a single-stage or multi-stage type.

[0249] In addition, in the separation step, instead of separating into a liquid or solid component containing microorganisms and a gaseous component containing ethanol, the solid component containing microorganisms and the liquid component containing ethanol may be separated using a solid-liquid separation device such as a solid-liquid separation filter device.

[0250] After the separation step, a purification step may be carried out to further purify the ethanol-containing liquid. Furthermore, when the ethanol-containing liquid obtained by microbial fermentation has already had components such as microorganisms removed, the purification step may be carried out without going through the above-mentioned separation step.

[0251] The purification step is a step of separating an ethanol-containing liquid into a distillate with an increased ethanol concentration and a bottoms liquid with a decreased ethanol concentration. Examples of equipment used in the purification step include a distillation apparatus, a treatment apparatus including a pervaporation membrane, a treatment apparatus including a zeolite membrane, a treatment apparatus for removing low-boiling substances with a boiling point lower than that of ethanol, a treatment apparatus for removing high-boiling substances with a boiling point higher than that of ethanol, and a treatment apparatus including an ion exchange membrane. These apparatuses may be used alone or in combination of two or more. A distillation apparatus or membrane separation can be suitably used as a unit operation, with a distillation apparatus being more preferred. Furthermore, a zeolite membrane can be suitably used for membrane separation.

[0252] When a distillation apparatus is used, heated distillation is performed. In heated distillation, the desired ethanol can be obtained as a distillate with high purity. The temperature inside the distillation apparatus during ethanol distillation is not particularly limited, but is preferably 110°C or less, and more preferably about 70 to 105°C. By setting the temperature inside the distillation apparatus within the above range, separation of ethanol from other components, i.e., distillation of ethanol, can be performed more reliably.

[0253] In thermal distillation, the ethanol-containing liquid may be introduced into a distillation apparatus equipped with a heater using steam at 100 ° C or higher, and the temperature of the bottom of the distillation column may be raised to 90 ° C or higher within 30 minutes, and then the ethanol-containing liquid may be introduced from the middle of the distillation column. In addition, in thermal distillation using a distillation apparatus, it is preferable to perform the distillation process with a temperature difference between the bottom, middle, and top of the column within ± 15 ° C. A temperature difference of ± 15 ° C or less makes it easier to obtain high-purity ethanol. The distillation temperature difference is preferably ± 13 ° C, more preferably ± 11 ° C. With these distillation temperature differences, separation from other components, i.e., purification by distillation of ethanol can be more reliably performed.

[0254] The pressure inside the distillation apparatus during ethanol distillation may be normal pressure, but is preferably less than atmospheric pressure, more preferably about 60 to 95 kPa (absolute pressure). By setting the pressure inside the distillation apparatus within this range, it is possible to improve the ethanol separation efficiency and, in turn, the ethanol yield.

[0255] The ethanol obtained in the purification step can be further concentrated by distillation or using various separation membranes, such as a zeolite membrane, to produce high-purity ethanol. Alternatively, the ethanol-containing liquid may be transferred to a bioreactor after ethanol removal.

[0256] The ethanol obtained through the purification step is used as a raw material for obtaining an ethylene-containing product in the production of ethylene, which will be described later. The "ethanol" used as a raw material in the present invention is pure ethanol (chemical formula: CH ３ CH ２ The term "raw material ethanol" does not refer to raw material ethanol (ethanol represented by OH), but rather a composition containing impurities, also known as "raw material ethanol." Impurities are contained in raw material ethanol produced through the above-mentioned processes, and many of these are compounds derived from waste.

[0257] The purification step may be omitted. That is, after ethanol production, it is not necessary to perform both the above purification step and the purification step (31') described below, and only the purification step (31') may be performed. In this case, the ethanol-containing liquid serves as raw material ethanol, and the purification step (31') is preferably performed using a distillation apparatus or membrane separation, with thermal distillation using a distillation apparatus being particularly preferred. Of course, when the purification step (31'') described below is performed, both the purification step and the purification step (31') may be omitted. However, it is preferable to perform the purification step, and it is more preferable to perform the purification step (31') in addition.

[0258] The raw material ethanol has an ethanol purity (i.e., ethanol content) of, for example, 85% by volume or more. When the ethanol purity is equal to or higher than the lower limit, the polymerization reaction using ethylene as a raw material proceeds smoothly by undergoing at least one of the purification steps (31') and (31''), and the quality of the polymer obtained from ethylene is improved. The ethanol purity of the raw material ethanol is preferably 90% by volume or more, more preferably 95% by volume or more, and even more preferably 99.5% by volume or more. The raw material ethanol may have an ethanol purity of less than 100% by volume. A commercially available product may be used as the raw material ethanol, as long as it contains ethanol derived from waste.

[0259] Next, the production of propanol by fermentation will be described. In the microbial fermentation of propanol, for example, any recombinant microorganism capable of producing propanol may be used. The propanol-producing ability of the recombinant microorganism may be obtained by modifying (e.g., enhancing) the propanol production pathway originally possessed by the microorganism, or by introducing a new propanol production pathway into the microorganism. Such modification and introduction can be carried out by genetic recombination. Specifically, DNA such as genes for enzymes involved in the propanol production pathway and transcriptional regulatory factors can be modified or introduced using known means such as plasmids.

[0260] A suitable example of a recombinant microorganism is Escherichia coli equipped with a propanol production system for producing propanol. Examples include the propanol-producing Escherichia coli described in International Publication Nos. 2009 / 008377, 2011 / 034031, 2011 / 111638, and 2012 / 020833. Since Escherichia coli does not inherently have a propanol production system, the propanol-producing Escherichia coli is Escherichia coli that has been introduced or modified by genetic recombination to possess propanol production ability. Such a propanol production system may be any system that allows the target Escherichia coli to produce propanol. It is also sufficient that at least a portion of the propanol production system has been introduced or modified by genetic recombination. Introduction or modification by genetic recombination can be performed using known methods, such as homologous recombination into the genome or introduction via a plasmid.

[0261] The propanol-producing E. coli is preferably E. coli in which the activity of an enzyme involved in propanol production has been enhanced. The term "by genetic recombination" encompasses any alteration in the base sequence caused by the insertion of a foreign base sequence that differs from the base sequence of the native gene, or by substitution or deletion of a portion of the gene, or a combination thereof, and may also include alterations caused by, for example, mutation.

[0262] It is preferable that the propanol-producing Escherichia coli has four enzyme activities, namely, acetoacetate decarboxylase activity, propanol dehydrogenase activity, CoA transferase activity, and thiolase activity, which are imparted extracellularly or whose expression is enhanced intracellularly, or both.

[0263] Here, thiolase is a general term for enzymes classified as enzyme number 2.3.1.9 in accordance with the report of the Commission on Enzymes of the International Union of Biochemistry (IUB), which catalyze the reaction of producing acetoacetyl-CoA from acetyl-CoA. Acetoacetate decarboxylase is a general term for enzymes classified as enzyme number 4.1.1.4 in accordance with the report of the Commission on Enzymes of the International Union of Biochemistry (IUB), which catalyze the reaction of producing acetone from acetoacetate.

[0264] Isopropanol dehydrogenase is classified as enzyme number 1.1.1.80 in accordance with the report of the International Union of Biochemistry (IUB) Commission on Enzymes, and is a general term for enzymes that catalyze the reaction of producing isopropanol from acetone. CoA transferase is classified as enzyme number 2.8.3.8 in accordance with the report of the International Union of Biochemistry (IUB) Commission on Enzymes, and is a general term for enzymes that catalyze the reaction of producing acetoacetate from acetoacetyl-CoA.

[0265] Examples of propanol-producing E. coli equipped with a propanol production system include the pIPA / B strain or pIaaa / B strain described in WO 2009 / 008377. Examples of such E. coli include strains in which, among the enzymes involved in isopropanol production, CoA transferase activity and thiolase activity are enhanced by enhancing the expression of the respective genes on the E. coli genome, and isopropanol dehydrogenase activity and acetoacetate decarboxylase activity are enhanced by enhancing the expression of the respective genes using a plasmid (sometimes referred to as pIa / B::atoDAB strain).

[0266] A recombinant E. coli strain with more effective improved propanol productivity may be used, such as a strain containing an inactivated GntR activity, an inactivated glucose-6-phosphate isomerase (Pgi) activity, an inactivated phosphogluconate dehydrogenase (Gnd) activity, and an enhanced glucose-6-phosphate-1-dehydrogenase (Zwf) activity. The combination of these factors or enzymes can improve propanol productivity compared to other combinations of factors or enzymes.

[0267] Glucose-6-phosphate isomerase (Pgi) is a general term for enzymes that are classified as enzyme number 5.3.1.9 in accordance with the Enzyme Commission Report of the International Union of Biochemistry (IUB), and that catalyze the reaction of producing D-fructose-6-phosphate from D-glucose-6-phosphate.

[0268] Glucose-6-phosphate-1-dehydrogenase (Zwf) is a general term for enzymes that are classified as enzyme number 1.1.1.49 in accordance with the Enzyme Commission Report of the International Union of Biochemistry (IUB), and that catalyze the reaction of producing D-glucono-1,5-lactone-6-phosphate from D-glucose-6-phosphate.

[0269] As the glucose-6-phosphate-1-dehydrogenase (Zwf) gene, DNA having the nucleotide sequence of a gene encoding thiolase obtained from each of the above-mentioned source organisms or a synthetic DNA sequence synthesized based on the known nucleotide sequence can be used.

[0270] Phosphogluconate dehydrogenase (Gnd) is a general term for enzymes that are classified as enzyme number 1.1.1.44 in accordance with the report of the Enzyme Commission of the International Union of Biochemistry (IUB), and that catalyze the reaction of 6-phospho-D-gluconate to produce D-ribulose-5-phosphate and carbon dioxide.

[0271] Examples of propanol-producing E. coli include strains obtained by inactivating the GntR activity of the pIPA / B strain, pIaaa / B strain, or pIa / B::atoDAB strain; strains obtained by inactivating the GntR activity and glucose-6-phosphate isomerase (Pgi) activity of the pIa / B::atoDAB strain and enhancing the glucose-6-phosphate-1-dehydrogenase (Zwf) activity; and strains obtained by inactivating the GntR activity, glucose-6-phosphate isomerase (Pgi) activity, and phosphogluconate dehydrogenase (Gnd) activity of the pIa / B::atoDAB strain and enhancing the glucose-6-phosphate-1-dehydrogenase (Zwf) activity.

[0272] Fermentation is carried out in a bioreactor using the above-mentioned microorganisms to obtain a fermentation broth containing propanol, which is then subjected to the same separation and purification steps as those described above for the production of ethanol by fermentation.

[0273] In addition to the above, propanol obtained by hydrogenating acetone obtained by microbial fermentation as described in JP 2021-185862 A can also be used as a suitable propanol.

[0274] Next, production of butanol by fermentation will be described. There are no particular limitations on the microorganisms that can produce butanol by fermentation. Some anaerobic bacteria are known to be capable of fermenting carbon monoxide to produce n-butanol, alcohols including butanol, and acetic acid. Examples of such bacteria include bacteria of the genus Clostridium, including Clostridium rujungudalii, Clostridium carboxydivorans (Liou et al., International Journal of Systematic and Evolutionary Microbiology 33: pp. 2085-2091), Clostridium ragsdalei (WO 2008 / 028055), and Clostridium autoethanogenum (Abrini et al., Archives of Microbiology 161: pp. 345-351); Moorella sp. HUC22-1 (Sakai et al., Biotechnology Letters 29: pp. 2085-2091); Moorella bacteria, including bacteria of the genus Moorella (Svetlichny, V.A., Sokolova, T.G. et al. (1991), Systematic and Applied Microbiology 14:254-260), Moorella thermoacetica, Moorella thermoautotrophica, Ruminococcus productus, Acetobacterium woodii, Eubacterium limosum, Butyrivacterium methylotrophicum, Oxobacter phenidii, Methanosarcina barkeri, Methanosarcina acetivorans, and Desulfotomaculum kuznetsovii (Simpa et al. Critical Reviews in Biotechnology, 2006 Vol. 26, pp. 41-65).

[0275] Additionally, Clostridium gender bacteria, such as Clostridium acetobutylicum species, directly produce 1-butanol by fermenting sugars (including starch and cellulose). The use of these bacteria in the production of 1-butanol based on sugar fermentation is known as the Weizmann process. Other well-known 1-butanol production pathways are disclosed in U.S. Patent Nos. 4,539,293 and 5,753,474. In the processes disclosed in those patent documents, sugars are first used to produce butyric acid, which is then converted to 1-butanol.

[0276] Another known method is acetone-butanol-ethanol (ABE) fermentation, which uses bacterial fermentation to produce acetone, n-butanol, and ethanol from starch. The industrial development of ABE fermentation began in 1916, when Chaim Weizmann described the isolation of Clostridium acetobutylicum in U.S. Patent No. 1,315,585A. This method produces a mixture containing acetone, n-butanol, and ethanol in a ratio of approximately 3:6:1. The raw material and the strain of microorganism used directly affect the composition of the mixture removed from the fermenter. For example, Cobalt Technologies, Inc., in U.S. Patent Application No. US2010330633A1, claims that the yield of butanol using fermentation raw materials and Clostridium saccharubutylium reaches 80%. In addition, Lanzatech New Zealand, Inc., in U.S. Patent No. US8119844B2, claims that a yield of 63% can be achieved by using glycerol and Clostridium pasteurinum. To optimize ABE fermentation, various methods have been developed to recover products from the reaction mixture, including distillation, pervaporation, membrane separation, adsorption, and reverse osmosis.

[0277] Fermentation is carried out in a bioreactor using the above-mentioned microorganisms to obtain a fermentation broth containing butanol, which is then subjected to the same separation and purification steps as those described above for the production of ethanol by fermentation.

[0278] Step (31) is a step of dehydrating an alcohol to obtain an unsaturated hydrocarbon having 2 to 8 carbon atoms. In one embodiment, ethanol is dehydrated to obtain ethylene. In another embodiment, propanol is dehydrated to obtain propylene. In yet another embodiment, butanol is dehydrated to obtain butene. In yet another embodiment, two or more of ethanol, propanol, and butanol are dehydrated to obtain ethylene, propylene, and butene.

[0279] Hereinafter, step (31) will be described by taking as examples a method for obtaining ethylene by dehydrating ethanol as one embodiment and a method for obtaining propylene by dehydrating propanol as another embodiment.

[0280] One embodiment of step (31) is a step of obtaining ethylene by dehydrating ethanol. The ethanol is converted into ethylene in an ethylene production step, thereby obtaining an ethylene-containing product. Specifically, the ethanol is brought into contact with a catalyst to be converted into ethylene. The ethanol is converted into ethylene by a dehydration reaction.

[0281] When carrying out the dehydration reaction of ethanol, a solvent or gas inert to the catalyst and alcohol can be added to the reaction system to carry out the dehydration reaction in a diluted state. The method for dehydrating ethanol may be any of a batch system, semi-batch system, or continuous flow system. Furthermore, any of the liquid phase, gas phase, and gas-liquid mixed phase systems may be used. Various methods such as a fixed bed, fluidized bed, suspension bed, and tray fixed bed may be used as the catalyst packing method, and any of these methods may be used.

[0282] The catalyst used is not limited as long as it can convert ethanol to ethylene. Examples of the catalyst include zeolite, modified zeolites such as P-modified zeolite, silica-alumina, alumina, silicated, titanated, zirconated, or fluorinated alumina, and acid catalysts such as silicoaluminophosphate (hereinafter, these may be collectively referred to as "zeolite or alumina-based catalysts"). Other examples include heteropolyacid-supported catalysts.

[0283] The zeolite is advantageously one containing at least one 10-membered ring in its structure, and has a microporous material consisting of silicon, aluminum, oxygen, and optionally boron, and examples thereof include MFI (ZSM-5, silicalite-1, boralite C, TS-1), MEL (ZSM-11, silicalite-2, boralite D, TS-2, SSZ-46), FER (ferrierite, FU-9, ZSM-35), MTT (ZSM-23), MWW (MCM-22, PSH-3, ITQ-1, MCM-49), TON (ZSM-22, Theta-1, NU-10), EUO (ZSM-50, EU-1), MFS (ZSM-57), ZSM-48, etc.

[0284] The zeolite is preferably a zeolite having a Si / Al ratio of 10 or more. The zeolite having a Si / Al ratio of 10 or more preferably has a Si / Al ratio of 100 or more. Also, it preferably contains at least one selected from MFI and MEL.

[0285] The zeolite is also preferably a dealuminated zeolite, from which about 10% by weight of aluminum is advantageously removed, and this dealumination is advantageously carried out by steam treatment, followed, if necessary, by leaching.

[0286] The zeolite and the dealuminated zeolite are advantageously essentially in the H form, and may contain, as a secondary component (component of about 50% or less), at least one metal compensating ion selected from the group consisting of Na, Mg, Ca, La, Ni, Ce, Zn, and Co.

[0287] The zeolite is mixed with a binder, preferably an inorganic binder, and formed into a desired shape, such as pellets. The binder is selected to be durable under the temperatures and other conditions used in the dehydration process of the present invention. The binder may be clay, silica, metal silicates, metal oxides (e.g., ZrO ２ ) or a gel comprising a mixture of silica and a metal oxide.

[0288] The P-modified zeolite is a phosphorus-modified zeolite. In the ethylene production process, a preferred embodiment uses the P-modified zeolite. The phosphorus-modified zeolite can be produced, for example, based on a microporous zeolite having an initial Si / Al ratio of 4 to 500, specifically, MFI, MOR, MEL, clinoptilolite, FER, MWW, TON, EUO, MFS, ZSM-48, or the like. The initial Si / Al ratio is preferably 100 or less, more preferably 4 to 30. The P-modified zeolite produced by this method can also be obtained based on an inexpensive zeolite having a low Si / Al ratio (30 or less).

[0289] Furthermore, the P-modified zeolite can also be further modified with at least one metal selected from Mg, Ca, La, Ni, Ce, Zn, Co, Ag, Fe, and Cu.

[0290] The phosphorus atom content in the P-modified zeolite is at least 0.05% by mass, preferably 0.3 to 7% by mass, and advantageously at least 10% by mass of aluminum has been extracted and removed from the zeolite by leaching, relative to the starting zeolite.

[0291] The catalyst using P-modified zeolite may be the P-modified zeolite itself or may be a blended P-modified zeolite in which the P-modified zeolite is combined with other materials, which can improve the hardness or catalytic activity of the catalyst.

[0292] Materials that can be mixed with the P-modified zeolite include various inert or catalytically active materials, or various binder materials. These include kaolin, other clay-like compositions, various forms of rare earth metals, phosphates, alumina or alumina sol, titania, zirconia, quartz, silica or silica sol, and mixtures thereof. These components are effective in increasing the compressive strength of the catalyst and catalyst formulations. The catalyst can be formed into pellets, spheres, extruded into other shapes, or spray-dried particles. The amount of P-modified zeolite in the final catalyst product is 10 to 90% by weight of the total catalyst, preferably 20 to 70% by weight of the total catalyst.

[0293] A suitable example of a P-modified zeolite is a silicoaluminophosphate, more preferably a silicoaluminophosphate of the AEL group, a representative example of which is SAPO-11. SAPO-11 is based on ALPO-11, and the Al / P ratio is essentially 1 atom / atom. By adding a silicon precursor during synthesis, silicon is inserted into the ALPO framework, creating acid sites on the surface of the micropores of the 10-membered ring zeolite. The silicon content is 0.1 to 10 atomic % (Al + P + Si = 100).

[0294] A preferred embodiment is to use alumina (particularly γ-alumina) as a catalyst in the ethylene production step. It is also preferred to use alumina that has been silicated, zirconated, titanated, or fluorinated. Alumina generally has a wide range of acid strength distribution and Lewis-type and Bronsted-type acid sites. Activated alumina is preferably used as the alumina.

[0295] It is also preferable to deposit silicon, zirconium, titanium, fluorite, etc. on the surface of alumina to improve the selectivity of the catalyst. That is, the selectivity of the catalyst may be improved by silicating, zirconating, or titanating. To prepare such a catalyst, a suitable commercially available alumina, preferably one having a surface area of ​​10 to 500 m, is used. ２It is preferable to use eta- or gamma-alumina having an alkali content of 0.5% or less per 10000 kJ / g. It is also preferable to prepare the alumina by adding silicon, zirconium, titanium, etc. in a total amount of 0.05 to 10 mass%. These metals may be added during the production of the alumina, or may be added to the alumina after production, or may be added in the form of a precursor. Fluorinated alumina itself is known and can be produced according to conventional techniques.

[0296] In the ethylene production step, a preferred embodiment is one in which a heteropolyacid-supported catalyst is used as the catalyst. The heteropolyacid-supported catalyst comprises a heteropolyacid supported on a suitable catalyst support. The term "heteropolyacid" refers to a heteropolyacid compound in the form of a free acid or a heteropolyacid salt such as an alkali metal salt, an alkaline earth metal salt, an ammonium salt, a salt of a bulky cation, and / or a metal salt (in these cases, the salt may be either a complete salt or a partial salt).

[0297] The anion of a heteropolyacid typically comprises 12 to 18 oxygen-bonded polyvalent metal atoms, known as peripheral atoms, symmetrically surrounding one or more central atoms. The peripheral atoms are suitably selected from molybdenum, tungsten, vanadium, niobium, tantalum, and combinations thereof. The central atom is preferably silicon or phosphorus. The central atom may also include any one selected from atoms of Groups I to VIII of the Periodic Table of the Elements, such as copper, beryllium, zinc, cobalt, nickel, boron, aluminum, gallium, iron, cerium, arsenic, antimony, bismuth, chromium, rhodium, silicon, germanium, tin, titanium, zirconium, vanadium, sulfur, tellurium, manganese nickel, platinum, thorium, hafnium, tellurium, and iodine. Suitable heteropolyacids include Keggin, Wells-Dawson and Anderson-Evans-Perloff heteropolyacids.

[0298] The heteropolyacid component of the heteropolyacid supported catalyst is preferably heteropolytungstic acid, which is a heteropolyacid in which the peripheral atoms are tungsten atoms. Preferred heteropolytungstic acids are any based on the Keggin or Wells-Dawson structure.

[0299] An example of a heteropolytungstic acid is 18-phosphotungstic acid (H ６ [P ２ W １８ O ６２ ]・xH ２ O), 12-phosphotungstic acid (H ３ [P.W. １２ O ４０ ]・xH ２ O), 12-silicotungstic acid (H ４ [SiW １２ O ４０ ]・xH ２ O), cesium hydrogen silicotungstate (Cs ３ H[SiW １２ O ４０ ]・xH ２ O), monopotassium phosphotungstate (KH5[P ２ W １８ O ６２ ]・xH ２ O), 12-monosodium silicotungstate (NaK ３ [SiW １２ O ４０ ]・xH ２ O), and potassium phosphotungstate (K ６ [P ２ W １８ O ６２ ]・xH ２ Mixtures of two or more different heteropolytungstic acids and salts can also be used.

[0300] More preferably, the heteropolyacid component of the heteropolyacid supported catalyst is silicotungstic acid, phosphotungstic acid, and mixtures thereof, such as 12-silicotungstic acid (H ４ [SiW １２ O ４０ ]・xH ２ O), 12-phosphotungstic acid (H３ [P.W. １２ O ４０ ]・xH ２ O), and mixtures thereof. More preferably, the heteropolyacid is tungstosilicic acid, and most preferably, the heteropolyacid is 12-tungstosilicic acid.

[0301] The molecular weight of the heteropolyacid is preferably more than 700 and less than 8500, more preferably more than 2800 and less than 6000. Such heteropolyacids also include dimerized complexes thereof.

[0302] The catalyst support used in the heteropolyacid supported catalyst may be any suitable catalyst support known in the art. Suitable sources of catalyst support include mordenite (e.g., montmorillonite), clay, bentonite, diatomaceous earth, titania, activated carbon, alumina, silica, silica-alumina, silica-titania cogel, silica-zirconia cogel, carbon-coated alumina, zeolite, zinc oxide, and flame-pyrolyzed oxides. Silica gel supports and SiCl ４ Silica-based catalyst supports such as those prepared by flame hydrolysis of are preferred.

[0303] The shape of the catalyst support is not particularly limited, and may be, for example, in powder form, granular form, pelletized form, spherical form, or extruded form.

[0304] Although not particularly limited, ethanol is preferably converted to ethylene in a gas phase by contacting the catalyst. Furthermore, ethanol may be further mixed with water, and optional components other than ethanol and water may be mixed as appropriate. Either or both of water and optional components may be contacted with the catalyst in the form of a gas together with the raw material ethanol.

[0305] The catalyst may be filled, for example, in a reaction vessel, and ethanol or ethanol and at least one selected from water and other optional components may be supplied as a gas to the reaction vessel filled with the catalyst to carry out a gas-phase dehydration reaction, thereby discharging an ethylene-containing product in the gas phase from the reaction vessel. When ethanol remains in the gas discharged from the reaction vessel, the ethanol-containing component may be separated from the ethylene-containing product, and the ethanol-containing component may be supplied again to the reaction vessel.

[0306] In the case of a zeolite or alumina catalyst, the temperature of the reaction vessel is, for example, 280 to 600° C., preferably 300 to 550° C., and more preferably 330 to 530° C. The pressure (absolute pressure) of the reaction vessel is, for example, 0.05 to 3 MPa, preferably 0.05 to 2.5 MPa, and more preferably 0.12 to 2 MPa.

[0307] In the case of a heteropolyacid-supported catalyst, the temperature of the reaction vessel is, for example, 170° C. or higher, preferably in the range of 180 to 270° C., more preferably in the range of 190 to 260° C., and even more preferably in the range of 200 to 250° C. The pressure is preferably in the range of 0.1 to 4.5 MPa, more preferably in the range of 1.0 to 3.5 MPa, and even more preferably in the range of 1.0 to 2.8 MPa.

[0308] In the case of a heteropolyacid-supported catalyst, the heteropolyacid-supported catalyst may be heated to a temperature of 220°C or higher before contacting with ethanol and maintained at that temperature for a sufficient period of time to remove bound water from the heteropolyacid component of the heteropolyacid-supported catalyst.

[0309] In the step (31), a step (31') of purifying ethanol may be carried out before the ethylene production step, and a step (31'') of purifying the ethylene-containing product may be carried out after the ethylene production step.

[0310] When step (31") is performed, the ethylene-containing product purified in step (31") is referred to as "ethylene" produced by the production method according to the sixth embodiment, and when step (31") is omitted, the ethylene-containing product obtained in the ethylene production step is referred to as "ethylene" produced by the sixth embodiment. The "ethylene" produced by the sixth embodiment may consist of ethylene alone, or may be a composition containing impurities that are inevitably mixed in even after synthesis or purification.

[0311] In the step (31'), it is preferable to remove at least one organic compound selected from the group consisting of aliphatic unsaturated hydrocarbons having 3 to 14 carbon atoms, aliphatic saturated hydrocarbons having 3 to 14 carbon atoms, alcohols having 3 to 10 carbon atoms, and ethers having 3 to 10 carbon atoms from ethanol.

[0312] When the raw material is derived from waste, the waste contains various components. Therefore, the raw material ethanol produced from the waste contains various organic compounds. Furthermore, among the organic compounds, organic compounds with the above-mentioned number of carbon atoms often remain in the ethanol obtained through various processes. If such organic compounds remain in the ethanol, they may inhibit the dehydration reaction in the ethylene production process and the subsequent polymerization reaction using ethylene, or may reduce the quality of the polymer obtained from ethylene. Therefore, removing hydrocarbons, alcohols, and ethers with specific numbers of carbon atoms in step (31′) allows the ethylene polymerization reaction to proceed smoothly and also tends to improve the quality of the resulting polymer.

[0313] On the other hand, in the step (31"), it is preferable to remove at least one selected from specific organic compounds consisting of aliphatic unsaturated hydrocarbons having 3 to 14 carbon atoms, aliphatic saturated hydrocarbons having 3 to 14 carbon atoms, alcohols having 3 to 10 carbon atoms, and ethers having 3 to 10 carbon atoms, carbon monoxide, carbon dioxide, and oxygen from the produced ethylene-containing product.

[0314] The term "removal" in steps (31') and (31'') includes not only a mode in which the target substance is completely removed from the ethanol or ethylene-containing product, but also a mode in which the content of the target substance is reduced.

[0315] In the step (31″), as described in the explanation of the step (31′), removal of hydrocarbons, alcohols, and ethers having a specific number of carbon atoms allows the polymerization reaction of ethylene to proceed favorably and also tends to improve the quality of the obtained polymer.

[0316] Carbon monoxide, carbon dioxide and oxygen can inhibit the polymerization reaction of ethylene.

[0317] The ethylene produced by the production method according to the sixth embodiment preferably has a carbon monoxide content of 100 ppm by volume or less due to the removal of carbon monoxide. The carbon monoxide content is more preferably 10 ppm by volume or less, and even more preferably 1 ppm by volume or less. Furthermore, the ethylene produced by the present invention may not contain any carbon monoxide at all, and therefore the lower limit of the carbon monoxide content is 0% by volume.

[0318] The ethylene produced by the production method according to the sixth embodiment preferably has a carbon dioxide content of 1% by volume or less by removing carbon dioxide. The carbon dioxide content is more preferably 0.5% by volume or less, and even more preferably 0.1% by volume or less. Furthermore, the ethylene produced by the present invention may not contain any carbon dioxide at all, and therefore the lower limit of the carbon dioxide content is 0% by volume.

[0319] The ethylene produced by the production method according to the sixth embodiment preferably has an oxygen content of 1% by volume or less by removing oxygen. The oxygen content is more preferably 0.5% by volume or less, and even more preferably 0.1% by volume or less. Furthermore, the ethylene produced by the present invention may not contain any oxygen at all, and therefore the lower limit of the oxygen content is 0% by volume.

[0320] The aliphatic unsaturated hydrocarbons having 3 to 14 carbon atoms may be removed in step (31'), step (31"), or both. If the aliphatic unsaturated hydrocarbons having 3 to 14 carbon atoms are contained in ethylene, when a polymerization reaction is carried out using the ethylene, the aliphatic unsaturated hydrocarbons having 3 to 14 carbon atoms will become branched chains in the polymer. Therefore, by removing the aliphatic unsaturated hydrocarbons having 3 to 14 carbon atoms, the number of branched chains can be reduced. Therefore, removal of the aliphatic unsaturated hydrocarbons having 3 to 14 carbon atoms is particularly suitable when it is desired to reduce the number of branched chains in the polymer, such as when producing high-density polyethylene (HDPE) from ethylene, as will be described later.

[0321] In the ethylene produced by the production method according to the sixth embodiment, the content of aliphatic unsaturated hydrocarbons having 3 to 14 carbon atoms is preferably 1% by volume or less by removing the aliphatic unsaturated hydrocarbons having 3 to 14 carbon atoms. The content of aliphatic unsaturated hydrocarbons having 3 to 14 carbon atoms is more preferably 0.5% by volume or less, and even more preferably 0.1% by volume or less. Furthermore, the ethylene produced by the present invention may not contain any aliphatic unsaturated hydrocarbons having 3 to 14 carbon atoms at all, and therefore the lower limit of the content of aliphatic unsaturated hydrocarbons having 3 to 14 carbon atoms is 0% by volume.

[0322] Furthermore, the aliphatic saturated hydrocarbons having 3 to 14 carbon atoms may be removed in step (31'), step (31"), or both, and it is preferable that the aliphatic saturated hydrocarbons having 3 to 14 carbon atoms removed in either step include aliphatic saturated hydrocarbons having 6 to 14 carbon atoms. The aliphatic saturated hydrocarbons having 6 to 14 carbon atoms may be linear or may have at least one of a branched structure and a cyclic structure. A specific example of the aliphatic saturated hydrocarbons having 6 to 14 carbon atoms is preferably at least one selected from n-hexane, n-heptane, n-octane, n-decane, n-dodecane, and n-tetradecane.

[0323] These aliphatic saturated hydrocarbons with a relatively large number of carbon atoms (6 to 14 carbon atoms) may be contained in relatively large amounts in raw material ethanol derived from waste.

[0324] In the ethylene produced by the production method according to the sixth embodiment, the content of aliphatic saturated hydrocarbons having 6 to 14 carbon atoms is preferably 0.3% by volume or less, more preferably 0.2% by volume or less, and even more preferably 0.1% by volume or less, due to the removal of the aliphatic saturated hydrocarbons having 6 to 14 carbon atoms. Furthermore, the ethylene produced by the present invention may not contain any aliphatic saturated hydrocarbons having 6 to 14 carbon atoms at all, and therefore the lower limit of the content of aliphatic saturated hydrocarbons having 6 to 14 carbon atoms is 0% by volume.

[0325] The alcohol having 3 to 10 carbon atoms may be removed in step (31'), step (31"), or both. The alcohol having 3 to 10 carbon atoms removed in either step includes, for example, at least one selected from 1-propanol, 2-propanol, 1-butanol, 2-butanol, and tert-butanol. These alcohols may be contained in relatively large amounts in the raw material ethanol derived from waste.

[0326] In the ethylene produced by the production method according to the sixth embodiment, the content of alcohols having 3 to 10 carbon atoms is preferably 0.3% by volume or less by removing the alcohols having 3 to 10 carbon atoms. The content of alcohols having 3 to 10 carbon atoms is more preferably 0.1% by volume or less, and even more preferably 0.05% by volume or less. Furthermore, the ethylene produced by the present invention may not contain any alcohols having 3 to 10 carbon atoms at all, and therefore the lower limit of the content of alcohols having 3 to 10 carbon atoms is 0% by volume.

[0327] The ethers having 3 to 10 carbon atoms may be removed in step (31'), step (31"), or both of these. The ethers having 3 to 10 carbon atoms removed in either step include, for example, at least one selected from diethyl ether and dibutyl ether. These ethers are contained in relatively large amounts in the raw material ethanol derived from waste, and these ethers may be removed in step (31'), step (31"), or both of these.

[0328] In the ethylene produced by the production method according to the sixth embodiment, the content of ethers having 3 to 10 carbon atoms is preferably 0.3% by volume or less due to the removal of ethers having 3 to 10 carbon atoms. The content of ethers having 3 to 10 carbon atoms is more preferably 0.1% by volume or less, and even more preferably 0.05% by volume or less. Furthermore, the ethylene produced by the present invention may not contain any ethers having 3 to 10 carbon atoms at all, and therefore the lower limit of the content of ethers having 3 to 10 carbon atoms is 0% by volume.

[0329] In the ethylene production step, water is produced by a dehydration reaction, and therefore, it is preferable to remove at least water in the step (31''). In addition, unreacted ethanol generally remains in the ethylene-containing product produced in the ethylene production step, and therefore, it is preferable to remove the unreacted ethanol as well. Removal of water and ethanol allows the polymerization reaction using ethylene, which will be described later, to proceed favorably, and also tends to improve the quality of the obtained polymer.

[0330] The ethylene produced by the production method according to the sixth embodiment preferably has a water content of 0.3 vol% or less by removing water in step (31''). By adjusting the water content to 0.3 vol% or less, the polymerization reaction using ethylene can be easily carried out favorably, and the quality of the obtained polymer can be easily improved. From this viewpoint, the water content is more preferably 0.1 vol% or less, and even more preferably 0.05 vol% or less. Furthermore, the ethylene produced by the present invention may not contain any water at all, and therefore the lower limit of the water content is 0 vol%.

[0331] The ethylene produced by the production method according to the sixth embodiment preferably has an ethanol content of 0.3 vol% or less by removing ethanol in step (31''). By adjusting the ethanol content to 0.3 vol% or less, the polymerization reaction using ethylene can be easily carried out favorably, and the quality of the obtained polymer can be easily improved. From this viewpoint, the ethanol content is more preferably 0.1 vol% or less, and even more preferably 0.05 vol% or less. Furthermore, the ethylene produced by the present invention may not contain any ethanol at all, and therefore the lower limit of the ethanol content is 0 vol%.

[0332] The ethylene produced by the production method according to the sixth embodiment is generally in a gaseous state, and the ethylene gas is analyzed for each inorganic gas (oxygen, carbon monoxide, carbon dioxide, etc.) and organic gas using GC-TCD and GC-FID, whereby the volume percentage of each of the components can be measured.

[0333] Examples of the purification method in each of steps (31') and (31'') include a water separation device consisting of a gas chiller or the like, a separation device using an adsorbent such as activated carbon, a pressure swing adsorption separation device (PSA), a temperature swing adsorption separation device (TSA), a pressure temperature swing adsorption separation device (PTSA), a low-temperature separation device (cryogenic method), a water-soluble impurity separation device such as a scrubber, a desulfurization device (sulfide separation device), a membrane separation device, a distillation device, a separation device with chromatography, a solution absorption device, and the like.

[0334] Various types of low-temperature separation methods can be used, including, for example, a method using a condenser. The solution absorption device is a device equipped with an absorbing solution that selectively absorbs specific gas components by contacting the gas, and an alkaline solution such as an amine solution can be used as the absorbing solution. For example, if an alkaline solution is used in step (31'), carbon dioxide and the like in the gasified raw material ethanol can be absorbed.

[0335] In step (31'), as described above, it is preferable to remove any of the aliphatic unsaturated hydrocarbons having 3 to 14 carbon atoms, the aliphatic saturated hydrocarbons having 3 to 14 carbon atoms, the alcohols having 3 to 10 carbon atoms, and the ethers having 3 to 10 carbon atoms. Among these, it is more preferable to remove those with a relatively large number of carbon atoms, and it is particularly preferable to remove the aliphatic unsaturated hydrocarbons having 6 to 14 carbon atoms. Due to the difference in molecular weight between the organic compounds with a large number of carbon atoms and ethanol, the organic compounds with a large number of carbon atoms can be easily removed in step (31'), and removing them also makes it easier to proceed with the reaction in the ethylene production step more appropriately.

[0336] In step (31'), the method for removing the aliphatic unsaturated hydrocarbons having 6 to 14 carbon atoms is not particularly limited, but it is preferable to remove them using a separation device having chromatography. As the chromatography, it is preferable to use reverse phase chromatography or the like. Furthermore, they may also be removed using a distillation device, activated carbon adsorption, or the like.

[0337] In step (31"), it is preferable to remove either water produced in the ethylene production step or unreacted ethanol, and it is preferable to remove both of them. Furthermore, as described above, it is preferable to remove at least one selected from specific organic compounds, carbon monoxide, carbon dioxide, and oxygen in step (31"), and it is more preferable that the specific organic compound removed is a low-molecular-weight organic compound having a relatively low molecular weight (for example, having 3 to 5 carbon atoms). That is, it is more preferable that aliphatic saturated hydrocarbons having 6 to 14 carbon atoms are removed in step (31'), and that at least specific low-molecular-weight organic compounds having a relatively low molecular weight are removed in step (31") in addition to water and unreacted ethanol, and it is also preferable that carbon monoxide, carbon dioxide, and oxygen are removed in step (31") in addition to these.

[0338] More preferably, the specific organic compound removed in step (31'') specifically includes at least one selected from alcohols having 3 to 10 carbon atoms, such as 2-propanol, and ethers having 3 to 10 carbon atoms, such as diethyl ether.

[0339] By using a specific separation device, low-molecular-weight organic compounds can be efficiently removed from ethylene together with unreacted ethanol, carbon monoxide, carbon dioxide, oxygen, etc. Furthermore, diethyl ether can be a raw material for producing ethylene together with ethanol in the ethylene production step. Therefore, it is preferable to remove a larger proportion of diethyl ether in step (31") than in step (31'). The "proportion" refers to the proportion relative to ethanol in step (31') and the proportion relative to the ethylene-containing product in step (31").

[0340] In the step (31"), although not particularly limited, purification is preferably performed using a separation apparatus of a low-temperature separation type. Specifically, there is a method of solidifying ethylene using a condenser using a refrigerant (chiller) cooled to a temperature below the melting point of ethylene (-170°C or lower at atmospheric pressure), and separating the ethylene.

[0341] In this case, substances such as water, carbon dioxide, ethanol, and other organic compounds having a melting point higher than that of ethylene may be removed by using one or more upstream condensers in which the refrigerant temperature is higher than that of the condenser. The upstream condensers may be, for example, a combination of a first condenser in which the refrigerant temperature is relatively high (e.g., 0 to 25°C at atmospheric pressure) and a second condenser in which the refrigerant temperature is lower than that of the first condenser (e.g., -50 to -90°C at atmospheric pressure). The condenser may have any form, and the gaseous ethylene-containing product may be brought into contact with a metal tube or the like through which a refrigerant passes, or the refrigerant and the ethylene-containing product may be brought into direct contact with each other.

[0342] Another embodiment of step (31) is a step of obtaining propylene by dehydrating propanol. Propanol is converted to propylene in a propylene production step, thereby obtaining a propylene-containing product. Specifically, propanol is brought into contact with a catalyst to be converted to propylene. Propanol is converted to propylene by a dehydration reaction.

[0343] When carrying out the dehydration reaction of propanol, a solvent or gas inert to the catalyst and propanol may be added to the reaction system to carry out the dehydration reaction in a diluted state. The method for the dehydration reaction of propanol may be any of a batch system, a semi-batch system, or a continuous flow system. The system may be in any of a liquid phase, a gas phase, or a gas-liquid mixed phase. As a method for packing the catalyst, various systems may be adopted, such as a fixed bed, a fluidized bed, a suspension bed, or a tray fixed bed, and any of these systems may be used.

[0344] The catalyst used is not limited as long as it can convert propanol to propylene, and examples thereof include acid catalysts such as zeolite, silica alumina, and alumina. The acid catalyst may be used alone or in combination with a catalyst or molding agent (binder) typically used in dehydration reactions. When the acid catalyst is used with a molding agent, it may be used in the form of a molded product obtained by kneading and extruding the mixture to increase mechanical strength. The shape of the molded product may be granular, cylindrical, ring-shaped, or the like, and is not particularly limited. Methods for molding the catalyst include, but are not limited to, tableting, compression molding, and extrusion molding. Examples of catalysts or molding agents typically used in dehydration reactions include silica, alumina, clay, titania, zirconia, zinc oxide, ceria, lanthana, graphite, and ethyl cellulose.

[0345] Regarding the combination of catalysts to be packed, the dehydration catalyst may be packed solely with the acid catalyst, or may contain a catalyst that is usually used for dehydration reactions. For example, since the water content increases near the reactor outlet as the reaction proceeds, it is also useful to use a catalyst in the latter half of the reactor. If the catalytic activity decreases over a certain period of time, the activity of the dehydration catalyst can be restored by regeneration using a known method.

[0346] To maintain propylene production, a merry-go-round system may be used in which two or three reactors are arranged in parallel and one reactor is regenerated while the other two reactors are reacting. Furthermore, when there are three reactors, the other two reactors may be connected in series to reduce fluctuations in production. Furthermore, when a fluidized bed flow reactor or a moving bed reactor is used, a constant activity can be maintained by continuously or intermittently withdrawing part or all of the catalyst from the reactor and replenishing the corresponding amount.

[0347] The temperature of the catalyst layer is preferably 450° C. or lower, more preferably 400° C. or lower, even more preferably 300° C. or lower, and particularly preferably 200° C. or lower. There are no particular restrictions on the lower limit of the temperature as long as it is equal to or higher than the temperature at which the dehydration reaction is carried out, but from the viewpoint of enhancing the activity of the obtained catalyst, it is preferably 160° C. or higher, or may be 180° C. or higher. The temperature of the catalyst layer can be adjusted as appropriate by, for example, changing the temperature of the apparatus used for the dehydration reaction.

[0348] If the temperature of the catalyst layer is within the above range, the dehydration reaction can be carried out at a relatively low temperature, thereby reducing the energy required for the reaction.

[0349] The reaction pressure during the dehydration reaction is not particularly limited, but is preferably 0 to 100 MPa (gauge pressure), more preferably 0 to 5 MPa (gauge pressure), and even more preferably 0 to 4 MPa (gauge pressure).

[0350] Although the dehydration reaction can be carried out without applying pressure, the propylene obtained by the dehydration reaction is in a gaseous state at room temperature and pressure, and therefore must be liquefied in order to be purified by distillation, etc. Therefore, if propylene is in a gaseous state, it must be liquefied by cooling, pressurizing, etc., which makes the production of propylene complicated.

[0351] Propanol flow rate during the dehydration reaction process (mol h) －１ The ratio of the catalyst weight (g) to the catalyst weight (W / F) is not particularly limited, but is preferably 0.01 to 10,000 g h mol －１ is preferred, and more preferably 0.1 to 5000 g·h·mol －１ and even more preferably 1 to 200 g h mol －１ is.

[0352] In order to quickly discharge the propylene produced in the dehydration reaction from the reaction system, an inert gaseous substance may be mixed into the dehydration reaction. Examples of the gaseous substance include nitrogen, helium, argon, methane, ethane, propane, and butane. The gaseous substance may be in a liquid state before the dehydration reaction of propanol, as long as it becomes gaseous during the dehydration reaction. Examples of such gaseous substances include aliphatic hydrocarbons such as pentane, hexane, heptane, and cyclopentane, and aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and cumene. When a gaseous substance is used, the amount of the gaseous substance is preferably in the range of 0.05 to 10 moles per mole of propylene.

[0353] Furthermore, when the catalytic activity decreases, the dehydration catalyst may be regenerated by a known method to restore its activity. To maintain the propylene production volume, two or more reactors may be arranged in parallel, and a switching system may be used in which one reactor undergoes catalytic activity restoration while another reactor performs the dehydration reaction. Furthermore, when there are three or more reactors, two or more reactors in which catalytic activity restoration is not performed may be connected in series to reduce fluctuations in production volume. Furthermore, when the reactor system is a fluidized-bed flow reaction system or a moving-bed reaction system, a constant catalytic activity can be maintained by continuously or intermittently withdrawing part or all of the catalyst from the reactor and replenishing an amount of catalyst equivalent to the amount withdrawn. After the dehydration reaction step, for example, the product propylene may be extracted in a gas-liquid separation step, followed by a purification step such as distillation.

[0354] The purification equipment may be installed within the process of the production method according to the sixth embodiment, or may be shared within an industrial complex that brings together different technologies. When a naphtha cracker and an ethane cracker are adjacent to each other, the reaction product may be introduced into the distillation columns of the naphtha cracker and the ethane cracker to be separated and purified.

[0355] [Seventh Embodiment of Method for Producing Unsaturated Hydrocarbons Having 2 to 8 Carbon Atoms] A method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms according to the seventh embodiment is a combination of the method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms according to the fifth embodiment and a method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms, the method including a step (31) of dehydrating at least one alcohol selected from the group consisting of ethanol, propanol, and butanol to obtain unsaturated hydrocarbons having 2 to 8 carbon atoms.

[0356] The step (31) in the method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms according to the seventh embodiment is the same as the step (31) in the sixth embodiment described above.

[0357] [Method for Producing a Mixture of Unsaturated Hydrocarbons Having 2 to 8 Carbon Atoms] The method for producing a mixture of unsaturated hydrocarbons having 2 to 8 carbon atoms includes a step (41) of contacting the unsaturated hydrocarbons having 2 to 8 carbon atoms obtained by the method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms according to any of the first to seventh embodiments described above with unsaturated hydrocarbons having 2 to 8 carbon atoms derived from a fossil resource to obtain a mixture.

[0358] Step (41) is a step of contacting and mixing the unsaturated hydrocarbons having 2 to 8 carbon atoms produced by the present invention with unsaturated hydrocarbons having 2 to 8 carbon atoms derived from a fossil resource to obtain a mixture of unsaturated hydrocarbons having 2 to 8 carbon atoms.

[0359] In step (41), the ratio of the contact mass of the fossil resource-derived unsaturated hydrocarbons having 2 to 8 carbon atoms to the contact mass of the unsaturated hydrocarbons having 2 to 8 carbon atoms produced by the method for producing a mixture of unsaturated hydrocarbons having 2 to 8 carbon atoms of the present invention (contact mass of the fossil resource-derived unsaturated hydrocarbons having 2 to 8 carbon atoms / contact mass of the unsaturated hydrocarbons having 2 to 8 carbon atoms) is preferably 0.001 to 10,000, more preferably 0.01 to 10,000.

[0360] The unsaturated hydrocarbon compounds having 2 to 8 carbon atoms produced by the present invention can be used in a variety of applications. Furthermore, various derivatives may be produced using these compounds as starting materials. An example of the flow of derivative production is shown in Figures 1 to 5. These derivatives can be produced by known methods. Note that Figures 1 to 5 show only one component used in the synthesis reaction.

[0361] Furthermore, in producing these derivatives, in addition to the compounds produced in the present invention, compounds produced using fossil resources such as petroleum, coal, and natural gas as raw materials (fossil resource-derived compounds) may be used, compounds produced using plants such as sugarcane and corn as raw materials (biomass-derived compounds) may be used, or both fossil resource-derived compounds and biomass-derived compounds may be used.

[0362] Derivatives described below include polymers using olefin as a monomer (olefin polymers), polymers using butadiene as a monomer (butadiene polymers), polymers using methyl methacrylate as a monomer (methyl methacrylate polymers), polymers using methyl methacrylate and propylene oxide as monomers (propylene oxide polymers), polymers using propylene oxide and ethylene oxide as monomers (ethylene oxide polymers), polymers using ethylene oxide and ethylene glycol as monomers (ethylene glycol polymers), ethylene glycol, phenol, acetone, and isopropyl alcohol.

[0363] [Method for producing olefin-based polymer] The method for producing an olefin-based polymer includes a step of polymerizing a monomer containing an unsaturated hydrocarbon having 2 to 8 carbon atoms obtained by the method for producing an unsaturated hydrocarbon having 2 to 8 carbon atoms according to any one of the first to seventh embodiments described above, or a mixture of unsaturated hydrocarbons having 2 to 8 carbon atoms obtained by the method for producing a mixture of unsaturated hydrocarbons having 2 to 8 carbon atoms described above.

[0364] The unsaturated hydrocarbon having 2 to 8 carbon atoms and the mixture of unsaturated hydrocarbons having 2 to 8 carbon atoms produced by the present invention are subjected to a polymerization step for producing an olefin polymer. In the polymerization step, a polymer is obtained by polymerizing a monomer containing an unsaturated hydrocarbon having 2 to 8 carbon atoms.

[0365] In the production of olefin polymers, in addition to the unsaturated hydrocarbons having 2 to 8 carbon atoms and the mixture of unsaturated hydrocarbons having 2 to 8 carbon atoms produced by the present invention, olefins produced using fossil resources such as petroleum, coal, and natural gas as raw materials (fossil resource-derived olefins) may be used, olefins produced using plants such as sugarcane and corn as raw materials (biomass-derived olefins) may be used, or both fossil resource-derived olefins and biomass-derived olefins may be used. Examples of polymers produced by the method for producing olefin polymers include ethylene polymers, propylene polymers, and butadiene polymers, and the following description will be given taking ethylene polymers, propylene polymers, and butadiene polymers as examples.

[0366] [Olefin-Based Polymer] <Ethylene-Based Polymer> By polymerizing the ethylene-containing monomer produced by the present invention, it is possible to produce ethylene-based polymers such as high-density polyethylene, low-density polyethylene, linear low-density polyethylene, very low-density polyethylene, long-chain branched polyethylene, etc. The polymer may be a homopolyethylene obtained by polymerizing ethylene alone, or a copolymer obtained by polymerizing ethylene and a monomer other than ethylene.

[0367] Examples of monomers copolymerizable with ethylene include olefins having 3 to 20 carbon atoms such as propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene, and 4-methyl-1-hexene; cyclic olefins such as norbornene; alkenyl aromatic hydrocarbyls such as styrene; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate; vinyl ester compounds such as vinyl acetate; polyene compounds such as 5-ethylidene-2-norbornene and dicyclopentadiene; vinyl fluoride, vinyl chloride, vinyl bromide, tetrafluoroethylene, diethyl maleate, and diethyl fumarate. These may be used alone or in combination of two or more.

[0368] As the ethylene, in addition to the ethylene produced by the present invention, ethylene derived from a fossil resource, ethylene derived from biomass, or both ethylene derived from a fossil resource and ethylene derived from biomass may be used.

[0369] Furthermore, as the monomer other than ethylene, a monomer produced by the present invention (e.g., propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1-heptene) may be used, a fossil resource-derived monomer (e.g., propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1-heptene) may be used, or a biomass-derived monomer (e.g., propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1-heptene) may be used, or two or more of these may be used in combination, such as a monomer produced by the present invention / fossil resource-derived monomer, a monomer produced by the present invention / biomass-derived monomer, a fossil resource-derived monomer / biomass-derived monomer, or a monomer produced by the present invention / fossil resource-derived monomer / biomass-derived monomer.

[0370] Specific examples of the polymer include ethylene homopolymer, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-butene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, and ethylene-propylene-5-ethylidene-2-norbornene copolymer.

[0371] The content of ethylene units in the ethylene polymer is usually 50% by mass or more, and preferably 70% by mass or more, based on 100% by mass of the ethylene polymer. １３ It is measured by C-NMR method.

[0372] The density of the ethylene polymer depends on the content of ethylene units, but is usually 870 to 965 kg / m ３ is.

[0373] The melt mass flow rate (MFR) of the ethylene polymer is usually 0.01 to 1000 g / 10 min, preferably 0.05 to 100 g / 10 min, as measured at a temperature of 190°C and a load of 2.16 kg, as specified in JIS K7210-1-2014.

[0374] The molecular weight distribution (mass average molecular weight (Mw) / number average molecular weight (Mn)) of the ethylene polymer is usually 2-15, and preferably 3-10.

[0375] When the ethylene polymer is a long-chain branched polyethylene, the branching index (gc') is usually 0.3 to 0.8. The gc' is measured by the method described in JP 2012-214780 A.

[0376] Examples of methods for producing ethylene polymers include a method of polymerizing ethylene alone or ethylene and a monomer other than ethylene in the presence of a radical polymerization initiator (high-pressure radical polymerization method).

[0377] The radical polymerization initiator may be an oxygen-based initiator such as an organic peroxide, a peroxyester, a dialkyl peroxide, or a combination thereof. Examples of the radical polymerization initiator include t-butyl peroxypivalate, di-t-butyl peroxide (DTBP), t-butyl peroxyacetate (TBPO), t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyneodecanoate (PND), t-butyl peroxyoctoate, and combinations of any two or more thereof. In the high-pressure radical polymerization method, the polymerization pressure is usually 50 to 400 MPa, and the polymerization temperature is usually 100 to 350°C.

[0378] Examples of a method for producing an ethylene polymer include a method of polymerizing ethylene alone or ethylene and a monomer other than ethylene in the presence of a polymerization catalyst such as a Ziegler-Natta catalyst, a metallocene catalyst, a Phillips catalyst, or a standard catalyst.

[0379] The Ziegler-Natta catalyst may be, for example, a triethylaluminum-titanium tetrachloride solid composite. The Ziegler-Natta catalyst may be, for example, a titanium trichloride composition obtained by reducing titanium tetrachloride with an organoaluminum compound and further treating it with various electron donors and electron acceptors, combined with an organoaluminum compound and an aromatic carboxylic acid ester, or a supported catalyst may be prepared by contacting magnesium halide with titanium tetrachloride and various electron donors.

[0380] Examples of metallocene catalysts include compounds such as bis(cyclopentadienyl) metal complexes having a structure in which a transition metal is sandwiched between π-electron unsaturated compounds. More specifically, examples include compounds in which one or more cyclopentadienyl rings or analogs thereof are present as ligands on a tetravalent transition metal such as titanium, zirconium, nickel, palladium, hafnium, or platinum.

[0381] The Ziegler-Natta catalyst and the metallocene catalyst may each be used in combination with a specific cocatalyst (promoter), such as methylaluminoxane (MAO) or a boron-based compound.

[0382] The Phillips catalyst is a catalyst system containing a chromium compound such as chromium oxide, and specific examples thereof include catalysts in which a chromium compound such as chromium trioxide or a chromate ester is supported on a solid oxide such as silica, alumina, silica-alumina, or silica-titania.

[0383] Furthermore, the standard catalyst is a known catalyst using molybdenum oxide, such as gamma-alumina molybdenum oxide, etc. Furthermore, as a polymerization catalyst for producing long-chain branched polyethylene, the polymerization catalysts described in JP-A-2004-292772, JP-A-2012-214780, JP-A-2015-189973, and JP-A-2017-20019 can be used.

[0384] Examples of the polymerization method include solvent polymerization or slurry polymerization using a solvent such as an aliphatic hydrocarbyl such as butane, pentane, hexane, heptane, or octane; an aromatic hydrocarbyl such as benzene or toluene; or a halogenated hydrocarbyl such as methylene dichloride; and gas-phase polymerization in which polymerization is carried out in a gaseous monomer. Also usable are methods that combine these, such as a method in which polymerization is carried out by solution polymerization followed by gas-phase polymerization, or a method in which polymerization is carried out by slurry polymerization followed by gas-phase polymerization.

[0385] The polymerization pressure is usually normal pressure to 5 MPa. The polymerization temperature can be in the range of 0 to 220°C. It is preferably 20°C or higher, more preferably 40°C or higher, and even more preferably 50°C or higher. The polymerization temperature is preferably 130°C or lower, more preferably 100°C or lower. The polymerization time is generally determined appropriately depending on the type of target polymer and the reaction apparatus, but is generally 1 minute to 20 hours. A chain transfer agent such as hydrogen can also be added to adjust the molecular weight of the ethylene polymer.

[0386] In addition, either a continuous polymerization method or a batch polymerization method is possible. Furthermore, either a single-stage polymerization method or a multi-stage polymerization method may be used. When polymerization is carried out by a multi-stage polymerization method, the multiple polymerization reactors may be connected in series or in parallel, or both polymerization reactors connected in series and polymerization reactors connected in parallel may be used.

[0387] The ethylene polymer may be blended with various known resins, rubbers, and additives. The resins and rubbers may be olefin polymers (fossil resource-derived polyolefins) such as ethylene polymers (fossil resource-derived polyethylene) and propylene polymers (fossil resource-derived polypropylene) produced using fossil resource-derived olefins as raw materials, or olefin polymers (biomass-derived polyolefins) such as ethylene polymers (biomass-derived polyethylene) and propylene polymers (biomass-derived polypropylene) produced from biomass olefins. Furthermore, olefin polymers (recycled polyolefins) such as recycled ethylene polymers (recycled polyethylene) and propylene polymers (recycled polypropylene) may also be used. Furthermore, two or more of these may be combined.

[0388] The additives may be one or more of known additives such as antioxidants (phenolic, phosphorus-based, sulfur-based), UV absorbers, light stabilizers, lubricants, antistatic agents, antifogging agents, antiblocking agents, mold release agents, processing aids, inorganic pigments, organic pigments, content dispersants, dyes, crosslinking agents, foaming agents, organic peroxides, neutralizing agents, adsorbents, weathering stabilizers, heat stabilizers, copper inhibitors, nucleating agents, plasticizers, inorganic or organic fillers, flame retardants, antibacterial agents, and light diffusers. Examples of these known additives include compounds described in "Handbook of Rubber and Plastic Compounding Chemicals" (Rubber Digest Co., Ltd., published April 27, 2001) and "Plastics Data Book" (co-edited by Asahi Kasei Amidas Co., Ltd. and the "Plastics" editorial department, published by Kogyo Chosakai Co., Ltd., December 1, 1999).

[0389] Examples of organic fillers include carbon fiber, carbon black, carbon nanotubes, cellulose nanofiber, wood flour, etc. Examples of inorganic fillers include silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloons, aluminum hydroxide, magnesium hydroxide, dolomite, calcium sulfate, potassium titanate, barium sulfate, talc, clay, mica, glass flakes, glass beads, glass fiber, aluminum silicate, calcium silicate, montmorillonite, bentonite, molybdenum sulfide, graphite, calcium carbonate, metal powder (aluminum, copper, iron, lead, etc.), silica stone, etc.

[0390] The ethylene polymer can be molded into various molded articles (films, sheets, containers (bottles, trays, etc.), etc.) by known molding methods such as injection molding, extrusion molding, blow molding, compression molding, vacuum molding, calendar molding, foam molding, etc. Examples of film molding methods include extrusion lamination molding, T-die film molding, and inflation molding (air cooling, water cooling, multistage cooling, high-speed processing).

[0391] The molded article using an ethylene-based polymer may be a single-layer molded article containing an ethylene-based polymer, or may be a multi-layer molded article having a layer other than the layer containing an ethylene-based polymer. Examples of the layer other than the layer containing an ethylene-based polymer include vinyl polymers such as polyvinyl chloride, polyvinylidene chloride, polystyrene, polyacrylate, and polyacrylonitrile; polyamide polymers such as nylon 6, nylon 66, nylon 10, nylon 11, nylon 12, nylon 610, and polymetaxylylene adipamide; polyester polymers such as polyethylene terephthalate, polyethylene terephthalate / isophthalate, and polybutylene terephthalate; polyvinyl alcohol; ethylene-vinyl alcohol copolymers; polycarbonate polymers; paper; and barrier films (aluminum foil, vapor-deposited film, coating film, etc.).

[0392] The molded article can be used in a variety of known applications, including, for example, various packaging films for food packaging and the like, wrap films, standard bags, heavy-duty bags, sugar bags, liquid paper containers, laminated raw materials, special-shaped liquid packaging bags (standing pouches and the like), infusion bags, bag-in-boxes, clean films used in packaging semiconductor materials, pharmaceuticals, and the like, protective films, blow bottles, squeeze bottles, caps, labels, tubes, pipes, gasoline tanks, agricultural materials, daily commodities, and fibers.

[0393] <Propylene-Based Polymer> By polymerizing the propylene-containing monomer produced in the present invention, propylene-based polymers such as homopolypropylene, random polypropylene, and block polypropylene (heterophalous polypropylene) can be produced.

[0394] Examples of monomers copolymerizable with propylene include olefins having 2 to 20 carbon atoms, such as ethylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene, and 4-methyl-1-hexene; cyclic olefins, such as norbornene; alkenyl aromatic hydrocarbyls, such as styrene; unsaturated carboxylic acids, such as acrylic acid and methacrylic acid; unsaturated carboxylic acid esters, such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate; vinyl ester compounds, such as vinyl acetate; polyene compounds, such as 5-ethylidene-2-norbornene and dicyclopentadiene; vinyl fluoride, vinyl chloride, vinyl bromide, tetrafluoroethylene, diethyl maleate, and diethyl fumarate.

[0395] In addition to the propylene produced by the present invention, fossil resource-derived propylene may be used as the propylene, biomass-derived propylene may be used, or both fossil resource-derived propylene and biomass-derived propylene may be used. Furthermore, as a monomer other than propylene, a monomer produced by the present invention (e.g., ethylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1-heptene) may be used, a fossil resource-derived monomer (e.g., ethylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1-heptene) may be used, or a biomass-derived monomer (e.g., ethylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1-heptene) may be used, or two or more of these may be used in combination, such as a monomer produced by the present invention / fossil resource-derived monomer, a monomer produced by the present invention / biomass-derived monomer, a fossil resource-derived monomer / biomass-derived monomer, or a monomer produced by the present invention / fossil resource-derived monomer / biomass-derived monomer.

[0396] Specific polymers include propylene homopolymer, propylene-ethylene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-ethylene-1-butene copolymer, propylene-ethylene-1-hexene copolymer, propylene-ethylene-1-butene-1-hexene copolymer, etc. Furthermore, these copolymers may be random polypropylenes or block polypropylenes (heterophalous polypropylenes).

[0397] The propylene unit content of the propylene polymer is usually 50% by mass or more, preferably 70% by mass or more, based on 100% by mass of the propylene polymer. １３ It is measured by C-NMR method.

[0398] The melt mass flow rate (MFR) of the propylene polymer is usually 0.01 to 1000 g / 10 min, preferably 0.05 to 100 g / 10 min, as measured at a temperature of 230°C and a load of 2.16 kg, as specified in JIS K7210-1-2014.

[0399] The molecular weight distribution (mass average molecular weight (Mw) / number average molecular weight (Mn)) of the propylene polymer is usually 2-15, and preferably 3-10.

[0400] When the propylene-based polymer is a homopolypropylene, the isotactic pentad fraction of the homopolypropylene is preferably 0.9 to 0.999, and more preferably 0.95 to 0.998. The isotactic pentad fraction is measured by the method described in Macromolecules, Vol. 6, p. 925 (published in 1973). The isotactic pentad fraction refers to the isotactic fraction of consecutive pentad units in a polymer chain. １３ In the measurement by C-NMR spectrum, １３ The isotactic pentad fraction is the intensity fraction of the mmmm peak among all absorption peaks in the methyl carbon region of the C-NMR spectrum. The peak assignments in the NMR spectrum are based on the description in Macromolecules, Vol. 8, p. 687 (published in 1975).

[0401] When the propylene-based polymer is a random polypropylene obtained by random copolymerization of propylene and an olefin, the content of propylene units in the random polypropylene is preferably 90 to 99.9% by mass, more preferably 92 to 99% by mass, and the content of olefin units is preferably 0.1 to 10% by mass, more preferably 1 to 8% by mass, based on 100% by mass of the random polypropylene. １３ It is measured by C-NMR method.

[0402] The melting point of random polypropylene is usually 100 to 160°C, and preferably 115 to 155°C. A melting point within this range provides excellent transparency and sealability. The melting point is measured using a differential scanning calorimeter in accordance with JIS-K7121.

[0403] When the propylene-based polymer is a block polypropylene, the block polypropylene is preferably a propylene-ethylene block copolymer containing a polymer component (a) consisting of a propylene homopolymer or a propylene-ethylene random copolymer containing 95 to 100% by mass of propylene units and 0 to 5% by mass of ethylene units (where the total amount of propylene units and ethylene units is 100% by mass), and a propylene-ethylene random copolymer component (b) containing 20 to 80% by mass of propylene units and 20 to 80% by mass of ethylene units.

[0404] The intrinsic viscosity [η] of the polymer component (a) contained in the propylene-ethylene block copolymer is preferably 0.8 to 3 dL / g. The intrinsic viscosity [η] of the propylene-ethylene random copolymer component (b) contained in the propylene-ethylene block copolymer is preferably 1 to 10 dL / g. The intrinsic viscosity is measured in a tetralin solution at a temperature of 135°C.

[0405] The content of polymer component (a) contained in the propylene-ethylene block copolymer is preferably 55 to 95% by mass, more preferably 65 to 90% by mass. The content of propylene-ethylene random copolymer component (b) contained in the propylene-ethylene block copolymer is preferably 5 to 45% by mass, more preferably 10 to 35% by mass. However, the total amount of polymer component (a) and propylene-ethylene random copolymer component (b) contained in the propylene-ethylene block copolymer is taken as 100% by mass.

[0406] Examples of methods for producing propylene-based polymers include a method of polymerizing a propylene-containing monomer using a stereoregular olefin polymerization catalyst. Examples of the polymerization catalyst include known stereoregular olefin polymerization catalysts, such as those described in "New Edition Polypropylene Handbook" (edited by Nero Pasquini, published by Nikkan Kogyo Shimbun, September 28, 2012). Examples include Ziegler-Natta catalysts, metallocene catalysts, and catalyst systems combining these. Examples of polymerization methods include bulk polymerization, solution polymerization, slurry polymerization, gas-phase polymerization, and polymerization methods combining these polymerization methods. These methods can be either continuous or batch polymerization. Furthermore, the method for producing propylene-based polymers may be a single-stage polymerization method or a multi-stage polymerization method. When performing polymerization using a multi-stage polymerization method, multiple polymerization reactors may be connected in series or in parallel, or both series-connected and parallel-connected polymerization reactors may be used. The process described in "New Edition Polypropylene Handbook" (published by Nikkan Kogyo Shimbun, 2012) can be used. The method for producing the propylene polymer is preferably a continuous gas phase polymerization method. Polymerization conditions such as polymerization temperature, polymerization pressure, monomer concentration, catalyst input amount, and polymerization time can be appropriately determined depending on the composition, structure, etc. of the target propylene polymer.

[0407] The propylene-based polymer may be blended with various known resins, rubbers, and additives. Examples of the resins and rubbers include the polymers exemplified as the resins and rubbers that may be blended with the ethylene-based polymer. Other examples include ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-propylene-5-ethylidene-2-norbornene copolymer, styrene-butadiene-styrene block copolymer, hydrogenated styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, and hydrogenated styrene-isoprene-styrene block copolymer.

[0408] Examples of the additives include those exemplified as additives that may be blended into the ethylene-based polymer, and also include additives and blends described in "New Edition Polypropylene Handbook" (edited by Nello Pasquini, published by Nikkan Kogyo Shimbun, September 28, 2012).

[0409] The propylene polymer can be molded into various molded articles by known molding methods, including the molding methods exemplified for the ethylene polymer.

[0410] The molded article using a propylene-based polymer may be a single-layer molded article containing a propylene-based polymer, or may be a multi-layer molded article having a layer other than the layer containing a propylene-based polymer. Examples of the layer other than the layer containing a propylene-based polymer include the layers exemplified for the molded article using an ethylene-based polymer.

[0411] The molded articles can be used in a variety of known applications, including automobile parts such as automobile interior and exterior parts, motorcycle parts, food and medical containers, furniture and electrical appliance parts, and civil engineering and building materials. Examples of automobile exterior parts include bumpers, fenders, and wheel covers. Examples of automobile interior parts include instrument panels, door trims, door panels, pillars, side protectors, console boxes, and column covers. Examples of motorcycle parts include cowlings and muffler covers. Examples of food and medical containers include retort pouches, retort containers, microwave heat-resistant containers, frozen food containers, specially shaped liquid packaging bags (e.g., stand-up pouches), plastic wrap, blown bottles, caps, labels, infusion bags, infusion bottles, medical supply containers, and cosmetic containers. Examples of furniture and electrical appliance parts include wallpaper, flooring, decorative sheets, and drain hoses for washing machines. Examples of civil engineering and building materials include waterproof sheets, waterproof sheets, hoses, ducts, and gaskets.

[0412] <Butadiene-Based Polymer> By polymerizing the butadiene-containing monomer produced by the present invention, it is possible to produce a butadiene homopolymer and a copolymer of butadiene and a monomer other than butadiene.

[0413] Examples of butadiene include 1,3-butadiene, 1,2-butadiene, etc. In addition to the butadiene produced by the present invention, butadiene produced using fossil resources such as petroleum, coal, and natural gas as raw materials (fossil resource-derived butadiene) may be used, or butadiene produced using plants such as sugarcane and corn as raw materials (biomass-derived butadiene) may be used, or both fossil resource-derived butadiene and biomass-derived butadiene may be used.

[0414] Examples of monomers copolymerizable with butadiene include aromatic vinyl compounds, non-conjugated dienes, vinyl cyanide compounds, unsaturated carboxylic acids, unsaturated carboxylic acid alkyl esters, and unsaturated carboxylic acid amides.

[0415] Examples of aromatic vinyl compounds include styrene, p-methylstyrene, α-methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, and diphenylethylene. Examples of non-conjugated dienes include dicyclopentadiene, 5-ethylidene-2-norbornene, and 1,5-hexadiene. Examples of cyanide vinyl compounds include acrylonitrile and methacrylonitrile. Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid. Examples of unsaturated carboxylic acid alkyl esters include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid. Examples of the unsaturated carboxylic acid amide include acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N,N-dimethylacrylamide, N,N-dimethylaminopropylacrylamide, and N,N-dimethylaminopropylmethacrylamide.

[0416] Furthermore, these copolymerizable monomers may be the compounds produced by the present invention or those derived therefrom, or may be monomers derived from fossil resources, or may be monomers derived from biomass, or may be a combination of these.

[0417] Specific examples of the polymer include 1,3-butadiene homopolymer, 1,3-butadiene-styrene copolymer, 1,3-butadiene-acrylonitrile copolymer, 1,3-butadiene-methyl methacrylate copolymer, 1,3-butadiene-styrene-acrylonitrile copolymer, 1,3-butadiene-acrylonitrile-acrylic acid copolymer, 1,3-butadiene-styrene-acrylonitrile-methyl methacrylate copolymer, 1,3-butadiene-styrene-acrylonitrile-acrylic acid copolymer, 1,3-butadiene-styrene-acrylonitrile-acrylic acid copolymer, and 1,3-butadiene-styrene-acrylonitrile-methyl methacrylate-acrylic acid copolymer.

[0418] The butadiene unit content of the butadiene polymer is preferably 20% by mass or more, with the butadiene polymer being 100% by mass.

[0419] Among butadiene-based polymers, copolymers of butadiene and other monomers copolymerizable with unsaturated carboxylic acids are suitable for latexes for paper coatings and adhesives. The content of butadiene units in the copolymer is preferably 20 to 80% by mass, the content of unsaturated carboxylic acid units is preferably 0.5 to 15% by mass, and the content of other copolymerizable monomer units is preferably 5 to 79.5% by mass, where the copolymer is taken as 100% by mass.

[0420] The butadiene polymer suitable for the latex preferably has at least two glass transition points between −100 and 50° C., more preferably at least one low glass transition point between −100 and 0° C. and at least one high glass transition point between −5 and 50° C. The glass transition points are measured using a differential scanning calorimeter.

[0421] Examples of methods for producing butadiene-based polymers include emulsion polymerization methods in which butadiene-containing monomers are polymerized using a known radical polymerization initiator. In emulsion polymerization methods, batch polymerization is preferred, but multi-stage polymerization and seed polymerization methods may also be used. Examples of methods for producing butadiene-based polymers include solution polymerization methods in which butadiene-containing monomers are polymerized using an organic alkali metal catalyst or a metallocene catalyst. In solution polymerization, either continuous polymerization or batch polymerization is possible, and either single-stage polymerization or multi-stage polymerization may be used.

[0422] Butadiene-based polymers suitable for latex are useful as binders for particles, powders, or fillers composed of metals, inorganic compounds, ceramics, pigments, phosphors, glass, etc. In particular, they can be suitably used as binders for paper coating compositions and for compositions for forming electrodes of electrochemical devices such as batteries, capacitors, and lithium ion capacitors. In addition, butadiene-based polymers can be used in various rubber applications, such as industrial products such as tires, vibration-proof rubber, belts, hoses, and seismic isolation rubber, and footwear such as men's shoes, women's shoes, and sports shoes.

[0423] [Method for producing compound and method for producing polymer] The method for producing a compound according to this embodiment includes a step of synthesizing at least one compound selected from the group of compounds consisting of methyl methacrylate, propylene oxide, ethylene oxide, ethylene glycol, phenol, acetone, and isopropyl alcohol, using as a raw material the unsaturated hydrocarbon having 2 to 8 carbon atoms obtained by the method for producing an unsaturated hydrocarbon having 2 to 8 carbon atoms according to any of the first to seventh embodiments, or the unsaturated hydrocarbon mixture having 2 to 8 carbon atoms obtained by the method for producing a mixture of unsaturated hydrocarbons having 2 to 8 carbon atoms described above.

[0424] The method for producing a polymer according to this embodiment includes a step of polymerizing a monomer produced using, as a raw material, the unsaturated hydrocarbon having 2 to 8 carbon atoms obtained by the method for producing an unsaturated hydrocarbon having 2 to 8 carbon atoms according to any one of the first to seventh embodiments, or the unsaturated hydrocarbon mixture having 2 to 8 carbon atoms obtained by the method for producing a mixture of unsaturated hydrocarbons having 2 to 8 carbon atoms described above, and the monomer contains at least one compound selected from the group of compounds consisting of methyl methacrylate, propylene oxide, ethylene oxide, and ethylene glycol.

[0425] <Method for Producing Methyl Methacrylate> Methyl methacrylate, a monomer for methyl methacrylate polymers, can be produced by known methods, such as the method described on pages 4 to 14 of "Sumitomo Chemical 2004-II," using the unsaturated hydrocarbon having 2 to 8 carbon atoms produced by the present invention and a mixture of unsaturated hydrocarbons having 2 to 8 carbon atoms as raw materials. For example, methods for producing methyl methacrylate from ethylene include the BASF process and the Alpha process. Methods for producing methyl methacrylate from isobutylene include the direct oxidation method (direct oxidation method), the methacrylonitrile method (MAN method), and the direct oxidation esterification method (direct meth method). This isobutylene may be produced by dehydrogenation of isobutane, from tert-butyl alcohol produced using isobutane, isobutylene, or the like as starting materials, or from methyl tert-butyl ether (MTBE) produced using isobutane, isobutylene, or the like as starting materials. Furthermore, the acetone cyanohydrin (ACH) method is an example of a method for producing methyl methacrylate from acetone. Acetone is produced using propylene, benzene, toluene, etc. as starting materials.

[0426] Among these, the method for producing methyl methacrylate is preferably a method for producing methyl methacrylate using, as a raw material, at least one compound selected from the group consisting of ethylene, propylene, and isobutylene obtained by the production method of the present invention.

[0427] The Alpha Process is a preferred method for producing methyl methacrylate using ethylene as a raw material. The Alpha Process is a method in which ethylene, carbon monoxide, and methanol are reacted to synthesize methyl propionate, and then the methyl propionate is reacted with formaldehyde to produce methyl methacrylate. Examples of catalysts for the reaction of ethylene, carbon monoxide, and methanol include palladium complex catalysts, and examples of catalysts for the reaction of methyl propionate and formaldehyde include Cs / SiO ２ Examples include solid base catalysts.

[0428] A preferred method for producing methyl methacrylate using propylene as a raw material is the acetone cyanohydrin (ACH) method, which uses acetone synthesized using propylene as a raw material. Acetone can be synthesized by a known method using propylene as a raw material. For example, a method can be mentioned in which propylene is reacted with oxygen to directly oxidize propylene. An example of the catalyst is a palladium chloride-copper chloride catalyst. Another example of a method for synthesizing acetone is a method in which propylene is reacted with benzene to synthesize cumene (isopropylbenzene), which is then oxidized to synthesize cumene hydroperoxide, and acetone and phenol are produced by decomposing the cumene hydroperoxide. Examples of the ACH method include a method of reacting acetone with hydrogen cyanide to synthesize acetone cyanohydrin, reacting acetone cyanohydrin with sulfuric acid to synthesize methacrylamide sulfate, and reacting methacrylamide sulfate with methanol to produce methyl methacrylate; and a method of reacting acetone with hydrogen cyanide to synthesize acetone cyanohydrin, hydrating the acetone cyanohydrin to synthesize α-hydroxyisobutyric acid amide, reacting α-hydroxyisobutyric acid amide with methyl formate to synthesize methyl α-hydroxyisobutyrate, and dehydrating the methyl α-hydroxyisobutyrate to produce methyl methacrylate.

[0429] The method for producing methyl methacrylate using isobutylene as a raw material is preferably a direct oxidation method (direct oxidation method). Examples of the direct oxidation method (direct oxidation method) include a method of oxidizing isobutylene with oxygen to synthesize methacrolein, further oxidizing methacrolein with oxygen to synthesize methacrylic acid, and then reacting methacrylic acid with methanol to produce methyl methacrylate; a method of hydrating isobutylene to synthesize tert-butyl alcohol, oxidizing tert-butyl alcohol with oxygen to synthesize methacrolein, further oxidizing methacrolein with oxygen to synthesize methacrylic acid, and then reacting methacrylic acid with methanol to produce methyl methacrylate; and a method of hydrating isobutylene to synthesize tert-butyl alcohol, then dehydrating the tert-butyl alcohol to synthesize isobutylene, then oxidizing isobutylene with oxygen to synthesize methacrolein, further oxidizing methacrolein with oxygen to synthesize methacrylic acid, and then reacting methacrylic acid with methanol to produce methyl methacrylate.

[0430] The catalyst used in the oxidation reaction of isobutylene and tert-butyl alcohol is preferably a catalyst containing molybdenum and bismuth, more preferably a Mo-Bi-Fe-X-A-O catalyst (wherein X represents at least one element selected from the group consisting of cobalt and nickel, and A represents at least one element selected from the group consisting of alkali metals, alkaline earth metals, and thallium). The catalyst used in the oxidation reaction of methacrolein is preferably a catalyst containing molybdenum and phosphorus, more preferably a P-Mo-V-Cu-A-O catalyst (wherein A represents at least one element selected from the group consisting of alkali metals, alkaline earth metals, and thallium). Examples of these catalysts include those described in JP-A-5-23596, WO 2019 / 013116, WO 2020 / 196853, and WO 2021 / 200689.

[0431] Examples of catalysts used in the reaction of methacrylic acid with methanol include acid catalysts such as sulfuric acid and strongly acidic cation exchange resins. Examples of catalysts used in the hydration reaction of isobutylene include acid catalysts such as strongly acidic cation exchange resins and heteropolyacids. Examples of catalysts used in the dehydration reaction of tert-butyl alcohol include acid catalysts such as solid acids such as solid phosphoric acid, activated alumina, and silica-alumina; strong acids such as sulfuric acid; and strongly acidic ion exchange resins containing sulfonic acid groups.

[0432] <Method for producing methyl methacrylate polymer> A method for producing a methyl methacrylate polymer includes a step of polymerizing a monomer containing methyl methacrylate produced using, as a raw material, the unsaturated hydrocarbon having 2 to 8 carbon atoms obtained by the method for producing an unsaturated hydrocarbon having 2 to 8 carbon atoms according to any of the first to seventh embodiments, or the unsaturated hydrocarbon mixture having 2 to 8 carbon atoms obtained by the method for producing an unsaturated hydrocarbon mixture having 2 to 8 carbon atoms described above.

[0433] Examples of methods for producing methyl methacrylate polymers include a method of polymerizing a monomer containing methyl methacrylate using a known radical polymerization initiator. Polymerization methods include suspension polymerization, solution polymerization, bulk polymerization, and the like, with bulk polymerization being preferred. In addition, the method for producing methyl methacrylate polymers can be either a continuous polymerization method or a batch polymerization method, and may be either a single-stage polymerization method or a multi-stage polymerization method. For example, the production methods described in JP 2011-168683 A, JP 2014-108988 A, WO 2017 / 010323 A, and JP 2021-155698 A can be used.

[0434] (Methyl methacrylate polymer) By polymerizing the monomer containing methyl methacrylate obtained by the above production method, it is possible to produce a methyl methacrylate homopolymer and a copolymer of methyl methacrylate and a monomer other than methyl methacrylate.

[0435] As the methyl methacrylate, in addition to the methyl methacrylate obtained by the above-mentioned production method, methyl methacrylate produced using fossil resources such as petroleum, coal, and natural gas as raw materials (fossil resource-derived methyl methacrylate) may be used, methyl methacrylate produced using plants such as sugarcane and corn as raw materials (biomass-derived methyl methacrylate) may be used, or both fossil resource-derived methyl methacrylate and biomass-derived methyl methacrylate may be used.

[0436] Examples of monomers copolymerizable with methyl methacrylate include acrylic esters, unsaturated carboxylic acids, unsaturated carboxylic acid amides, vinyl cyanide compounds, and aromatic vinyl compounds.

[0437] Examples of acrylic acid esters include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, cyclohexyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, and cyclopentadiene acrylate. Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic anhydride, and itaconic anhydride. Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile. Examples of unsaturated carboxylic acid amides include acrylamide and methacrylamide. Examples of aromatic vinyl compounds include styrene and α-methylstyrene.

[0438] Furthermore, these copolymerizable monomers may be the compounds produced by the present invention or those derived therefrom, or may be monomers derived from fossil resources, or may be monomers derived from biomass, or may be a combination of these.

[0439] Specific examples of the polymer include methyl methacrylate homopolymer, methyl methacrylate-methyl acrylate copolymer, methyl methacrylate-ethyl acrylate copolymer, methyl methacrylate-methyl acrylate-butyl acrylate copolymer, methyl methacrylate-butyl acrylate-styrene copolymer, and methyl methacrylate-styrene-maleic anhydride copolymer.

[0440] The content of methyl methacrylate units in the methyl methacrylate polymer is preferably 80% by mass or more, more preferably 90% by mass or more, based on 100% by mass of the methyl methacrylate polymer, as measured by pyrolysis gas chromatography.

[0441] The mass average molecular weight of the methyl methacrylate polymer is preferably 50,000 to 300,000, and the molecular weight distribution (mass average molecular weight (Mw) / number average molecular weight (Mn)) is usually 2-10.

[0442] Various known resins, rubbers, and additives may be blended with the methyl methacrylate polymer. The resin and rubber may be a methyl methacrylate polymer (fossil resource-derived polymethyl methacrylate) produced using fossil resource-derived methyl methacrylate as a raw material, or a methyl methacrylate polymer (biomass-derived polymethyl methacrylate) produced using biomass-derived methyl methacrylate as a raw material. Alternatively, a recycled methyl methacrylate polymer (regenerated polymethyl methacrylate) may be used. Furthermore, two or more of these may be combined.

[0443] Examples of the additives include the additives exemplified as additives that may be blended with the ethylene polymer.

[0444] The methyl methacrylate polymer can be molded into various molded articles by known molding methods such as injection molding, extrusion molding, and pressure molding. The obtained molded articles may be further subjected to secondary molding by methods such as pressure molding and vacuum molding.

[0445] The molded article can be used in a variety of known applications, such as optical materials, vehicle parts, lighting materials, construction materials, etc. Examples of vehicle parts for automobiles include rear lamp outer covers, optical members inside rear lamps, inner lenses for headlights (sometimes referred to as projector lenses or PES lenses), meter covers, door mirror housings, pillar covers (sash covers), license garnishes, front grilles, fog garnishes, emblems, etc.

[0446] <Method for Propylene Oxide Production> Propylene oxide can be produced using propylene as a raw material by known methods, for example, the production methods described on pages 4 to 10 of "Sumitomo Chemical 2006-I" and pages 4 to 11 of "Sumitomo Chemical 2019." Examples of such methods include the chlorine method (chlorohydrin method), the cumene method (POC method), the hydrogen peroxide method (HPPO method), the improved hydrogen peroxide method (improved HPPO method), the direct oxidation method, the Halcon method (the ethylbenzene method (propylene oxide / styrene monomer (PO / SM) co-production method), and the isobutane method (propylene oxide / tert-butanol (PO / TBA) co-production method).

[0447] The chlorine process (chlorohydrin process) is a process in which propylene chlorohydrin is synthesized from propylene, chlorine, and water, and then the propylene chlorohydrin is dehydrochlorinated with calcium hydroxide to produce propylene oxide. The hydrogen peroxide process (HPPO process) and improved hydrogen peroxide process (improved HPPO process) are processes in which propylene oxide is produced from propylene and hydrogen peroxide. The cumene process is a process in which cumene is oxidized to synthesize cumene hydroperoxide, propylene is then epoxidized with cumene hydroperoxide to synthesize propylene oxide, and α-cumyl alcohol, a by-product of the epoxidation, is hydrogenated to synthesize cumene.

[0448] <Method for Producing Propylene Oxide Polymer> The method for producing a propylene oxide polymer includes a step of polymerizing a monomer containing propylene oxide produced using propylene obtained by the production method of the present invention as a raw material.

[0449] (Propylene Oxide Polymer) Examples of propylene oxide polymers include polypropylene glycol and copolymers of polypropylene glycol and polyisocyanate. These polymers can be produced by known methods. For example, polypropylene glycol can be produced by homopolymerizing propylene oxide or copolymerizing propylene oxide and ethylene oxide using a polyhydric alcohol (ethylene glycol, dipropylene glycol, glycerin, sorbitol, sucrose, etc.), an amine, a polyamine, etc. as a polymerization initiator. Examples of the catalyst include basic catalysts such as potassium hydroxide. Examples of catalysts for copolymerizing polypropylene glycol and polyisocyanate include amine catalysts (triethylenediamine, bis(2-dimethylaminoethyl)ether, N,N,N',N'-tetramethylhexamethylenediamine, etc.) and metal catalysts (dibutyltin dilaurate, stannous octoate, etc.).

[0450] Examples of polyisocyanates include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymethylene polyphenyl polyisocyanate (polymeric MDI), xylylene diisocyanate (XDI), naphthylene diisocyanate (NDI), paraphenylene diisocyanate (PPDI), tetramethylxylylene diisocyanate (TMXDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), and isophorone diisocyanate (IPDI).

[0451] <Method for Producing Ethylene Oxide> Ethylene oxide can be produced by a known method using the ethylene produced by the present invention as a raw material. For example, it can be produced by a method of catalytic gas phase oxidation of ethylene oxide with a molecular oxygen-containing gas. Examples of the catalyst include a silver catalyst. More specifically, examples of the methods described in JP-A-62-103072, JP-A-2010-36104, JP-A-2014-198680, and WO 2020 / 032279 can be mentioned.

[0452] <Method for Producing Ethylene Oxide Polymer> The method for producing an ethylene oxide polymer includes a step of polymerizing a monomer containing ethylene oxide produced using ethylene obtained by the production method of the present invention as a raw material.

[0453] (Ethylene oxide polymer) Ethylene oxide polymers can be produced by known methods. For example, they can be produced by a method of ring-opening polymerization of ethylene oxide. Examples of catalysts include metal alkoxide catalysts. Examples of methods for producing ethylene oxide polymers include a method of polymerizing ethylene oxide using a polyhydric alcohol (ethylene glycol, glycerin, sorbitol, sucrose, etc.), an amine, a polyamine, etc. as a polymerization initiator. Examples of catalysts include basic catalysts such as potassium hydroxide.

[0454] <Method for Producing Ethylene Glycol> Ethylene glycol can be produced by known methods using the above-mentioned ethylene oxide as a raw material. For example, it can be produced by a method of reacting ethylene oxide with water. This is carried out in the presence or absence of an acid catalyst. Another method for producing ethylene glycol is to react ethylene oxide with carbon dioxide to produce ethylene carbonate, and then react the ethylene carbonate with water. Examples of catalysts that can be used include alkali metal bromides, alkali metal iodides, and quaternary phosphonium halides. More specifically, the methods described in JP-A-54-16416, JP-A-2001-316308, JP-A-2000-128814, and JP-A-2002-201148 can be mentioned.

[0455] <Method for Producing Ethylene Glycol-Based Polymer> The method for producing an ethylene glycol-based polymer includes a step of polymerizing a monomer containing ethylene glycol produced using ethylene obtained by the production method of the present invention as a raw material.

[0456] (Ethylene Glycol-Based Polymer) Examples of ethylene glycol-based polymers include copolymers of ethylene glycol with a dicarboxylic acid or dimethyl dicarboxylate. Examples of dicarboxylic acids include terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid, and examples of dimethyl dicarboxylate include dimethyl terephthalate, dimethyl isophthalate, and dimethyl 2,6-naphthalenedicarboxylate. These polymers can be produced, for example, by directly esterifying a dicarboxylic acid with ethylene glycol or by transesterifying dimethyl dicarboxylate with ethylene glycol to synthesize a bishydroxyethyl compound (e.g., bishydroxyethyl terephthalate, bishydroxyethyl isophthalate, bishydroxyethyl 2,6-naphthalenedicarboxylate), and then polycondensing the bishydroxyethyl compound.

[0457] The direct esterification reaction is usually carried out without a catalyst, and an alkali metal, an amine compound, or the like is used as a diethylene glycol production inhibitor, if necessary. Examples of catalysts for the transesterification reaction include weak acid salts of calcium, manganese, magnesium, zinc, lithium, and the like; titanate esters; and more specifically, calcium acetate, magnesium acetate, lithium acetate, and the like can be used. Examples of catalysts for the polycondensation reaction include antimony compounds such as antimony trioxide, germanium compounds such as germanium dioxide, titanium compounds such as tetra-n-propyl titanate, tetra-i-propyl titanate, and tetra-n-butyl titanate, and aluminum compounds such as aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, and aluminum acetylacetonate.

[0458] <Method for Producing Phenol> Phenol can be produced by a known method using propylene obtained by the production method of the present invention as a raw material. For example, propylene is reacted with benzene to synthesize cumene (isopropylbenzene), and then the cumene is oxidized with an oxygen-containing gas such as a mixed gas containing oxygen and an inert gas or air to synthesize cumene hydroperoxide, and phenol and acetone can be produced by decomposing the cumene hydroperoxide. Here, examples of catalysts for the reaction of propylene and benzene include aluminum chloride catalysts, zeolite catalysts, and phosphoric acid catalysts. The oxidation reaction of cumene is carried out by autoxidation. This oxidation reaction may be carried out without using an additive, or an additive such as an alkali may be used. Examples of such additives include alkali metal compounds such as NaOH and KOH, alkaline earth metal compounds, and Na ２ CO ３ , NaHCO ３ alkali metal carbonates such as ammonia, (NH ４ ) ２ CO ３ , alkali metal ammonium carbonate, etc. Examples of the catalyst for the decomposition reaction of cumene hydroperoxide include acid catalysts such as sulfuric acid.

[0459] <Method for Producing Acetone> Acetone can be produced by known methods using propylene obtained by the production method of the present invention as a raw material. For example, acetone can be produced by a method in which propylene is reacted with oxygen to directly oxidize propylene. An example of the catalyst is a palladium chloride-copper chloride catalyst. Another example of a method for producing acetone is a method similar to the above-mentioned method for producing phenol, in which propylene is reacted with benzene to synthesize cumene (isopropylbenzene), the cumene is then oxidized to synthesize cumene hydroperoxide, and acetone and phenol are produced by decomposing the cumene hydroperoxide.

[0460] <Method for Producing Isopropyl Alcohol> Isopropyl alcohol can be produced by known methods using propylene obtained by the production method of the present invention as a raw material. For example, it can be produced by a method of reacting propylene with water. Examples of catalysts include strongly acidic cation exchange resins; and acid catalysts such as heteropolyacids such as phosphotungstic acid, silicotungstic acid, and silicomolybdic acid. Specific examples include the methods described in JP-A-8-165259, JP-A-8-165260, JP-A-8-291092, and WO 2017 / 217279. Furthermore, examples of methods for producing isopropyl alcohol include, as in the above-mentioned acetone production method, reacting propylene with benzene to synthesize cumene (isopropylbenzene), then oxidizing the cumene to synthesize cumene hydroperoxide, decomposing the cumene hydroperoxide to synthesize acetone and phenol, and then reacting the acetone with hydrogen. Examples of catalysts for the reaction of acetone with hydrogen include hydrogenation catalysts such as copper oxide / chromium oxide catalysts, Raney nickel catalysts, and catalysts of noble metals such as platinum, palladium, and ruthenium. Specific examples include the methods described in JP-A Nos. 2002-121160 and 2002-128716. Preferred are copper oxide / chromium oxide catalysts and Raney nickel catalysts.

[0461] [Plant-derived Carbon Concentration] The production method of the present invention can use a combination of fossil resource-based raw materials (fossil resource-derived raw materials) such as petroleum, coal, and natural gas, and plant-based raw materials (biomass-derived raw materials) such as sugarcane and corn. Therefore, when a biomass-derived raw material is used in the production method of the present invention, the compounds produced by the present invention and derivatives produced using the compounds as starting materials (e.g., the compounds described above and those shown in Figures 1 to 5) contain plant-derived carbon. Furthermore, by applying a mass balance approach to the biomass degree, it is possible to assign a biomass degree to the compounds produced by the present invention and their derivatives as starting materials. Therefore, the production method of the present invention is useful because any product from these compounds and derivatives can be made into a biomass product depending on the biomass degree of the entire compounds and derivatives.

[0462] The plant-derived carbon concentration of the compounds produced according to the present invention and derivatives produced using the compounds as starting materials (e.g., the compounds described above and the compounds shown in Figures 1 to 5) can be varied by adjusting the ratio of the fossil resource-derived raw materials to the biomass-derived raw materials, and is preferably 0.1 to 99.9 pMC(%), more preferably 0.3 to 70 pMC(%). From the viewpoint of reducing the environmental load, the plant-derived carbon concentration is more preferably 0.5 pMC(%) or more, even more preferably 1 pMC(%) or more, and particularly preferably 5 pMC(%) or more. Furthermore, from the viewpoint of cost, the plant-derived carbon concentration is more preferably 60 pMC(%) or less, even more preferably 50 pMC(%) or less, and particularly preferably 40 pMC(%) or less.

[0463] In one embodiment, the plant-derived carbon concentration of an olefin polymer produced using the unsaturated hydrocarbon having 2 to 8 carbon atoms or a mixture of unsaturated hydrocarbons having 2 to 8 carbon atoms produced by the present invention is 0.1 to 99.9 pMC (%).

[0464] In another embodiment, the plant-derived carbon concentration of a polymer produced using the unsaturated hydrocarbon having 2 to 8 carbon atoms or the mixture of unsaturated hydrocarbons having 2 to 8 carbon atoms produced by the present invention is 0.1 to 99.9 pMC (%).

[0465] Plant carbon concentrations are determined by radiocarbon ( １４ C) can be determined by measuring the carbon dioxide in the atmosphere. １４ Because it contains a certain percentage of carbon (105.5 pMC), plants that grow by absorbing carbon dioxide from the atmosphere, such as corn, １４ The carbon content is also known to be about 105.5 pMC. １４ It is also known that almost no carbon atoms are contained in the compound. Therefore, the total carbon atoms contained in the compound and its derivatives are １４ By measuring the proportion of C, the plant-derived carbon concentration of the compounds and derivatives can be calculated. １４ The content of C is [ １４ C], the plant-derived carbon concentration X of the compound and derivative ｂｉｏ can be calculated as follows:

[0466] X ｂｉｏ (%) = [ １４ C] / 105.5×100 Theoretically, if all raw materials for compounds and derivatives are plant-derived, the plant-derived carbon concentration of the compounds and derivatives will be 100%. On the other hand, the plant-derived carbon concentration of compounds and derivatives produced only from raw materials derived from fossil resources will be 0%.

[0467] The plant-derived carbon concentration is determined as pMC (percentage of modern carbon: unit %) by the AMS (Accelerator Mass Spectrometry) method specified in ISO 16620-2:2019.

Claims

1. A step (1) of separating a plastic mixture (A) having a polyolefin plastic content of 50% by mass or more from waste plastic and a residue (B); a step (2) of decomposing the plastic mixture (A) to obtain a reaction product containing unsaturated hydrocarbons having 2 to 8 carbon atoms; and (3) washing and purifying the reaction product to separate unsaturated hydrocarbons having 2 to 8 carbon atoms. A method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms.

2. A step (1) of separating a plastic mixture (A) having a polyolefin plastic content of 50% by mass or more from waste plastic and a residue (B); (12) a step of heating the residue (B) to obtain a mixed gas containing carbon monoxide, carbon dioxide, and hydrogen; a step (13) of mixing the mixed gas with at least one gas selected from the group consisting of carbon monoxide, carbon dioxide, and hydrogen, or removing a portion of at least one gas selected from the group consisting of carbon monoxide, carbon dioxide, and hydrogen from the mixed gas to obtain an adjusted gas in which the ratio of the volume of hydrogen to the total volume of carbon monoxide and carbon dioxide is 1.5 to 4.0; (14) reacting carbon monoxide, carbon dioxide, and hydrogen contained in the conditioning gas to obtain alcohol; and (15) obtaining an unsaturated hydrocarbon having 2 to 8 carbon atoms using an alcohol as a raw material. A method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms.

3. A step (1) of separating a plastic mixture (A) having a polyolefin plastic content of 50% by mass or more from waste plastic and a residue (B); a step (2) of decomposing the plastic mixture (A) to obtain a reaction product containing unsaturated hydrocarbons having 2 to 8 carbon atoms; (3) washing and purifying the reaction product to separate unsaturated hydrocarbons having 2 to 8 carbon atoms; (12) a step of heating the residue (B) to obtain a mixed gas containing carbon monoxide, carbon dioxide, and hydrogen; a step (13) of mixing the mixed gas with at least one gas selected from the group consisting of carbon monoxide, carbon dioxide, and hydrogen, or removing a portion of at least one gas selected from the group consisting of carbon monoxide, carbon dioxide, and hydrogen from the mixed gas to obtain an adjusted gas in which the ratio of the volume of hydrogen to the total volume of carbon monoxide and carbon dioxide is 1.5 to 4.0; (14) reacting carbon monoxide, carbon dioxide, and hydrogen contained in the conditioning gas to obtain alcohol; and (15) obtaining an unsaturated hydrocarbon having 2 to 8 carbon atoms using an alcohol as a raw material. A method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms.

4. The reaction product obtained in the step (2) further contains paraffin. The method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms according to claim 1 or 3.

5. (21) reacting carbon dioxide with hydrogen to obtain a reaction mixture comprising alcohol, carbon dioxide and carbon monoxide; and a step (22) of obtaining an unsaturated hydrocarbon having 2 to 8 carbon atoms from the alcohol and / or carbon monoxide contained in the reaction mixture. A method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms.

6. A method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms according to any one of claims 1 to 3; and a method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms according to claim 5. A method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms.

7. A method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms according to any one of claims 1 to 3 and 5; a method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms, the method comprising a step (31) of dehydrating at least one alcohol selected from the group consisting of ethanol, propanol, and butanol to obtain unsaturated hydrocarbons having 2 to 8 carbon atoms; A method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms.

8. A method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms according to claim 6; and a method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms, the method comprising a step (31) of dehydrating at least one alcohol selected from the group consisting of ethanol, propanol, and butanol to obtain unsaturated hydrocarbons having 2 to 8 carbon atoms. A method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms.

9. The method includes a step (41) of contacting the unsaturated hydrocarbons having 2 to 8 carbon atoms obtained by the method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms according to any one of claims 1 to 3 and 5 with unsaturated hydrocarbons having 2 to 8 carbon atoms derived from a fossil resource to obtain a mixture. A method for producing a mixture of unsaturated hydrocarbons having 2 to 8 carbon atoms.

10. the ratio of the contact mass of the fossil resource-derived unsaturated hydrocarbons having 2 to 8 carbon atoms to the contact mass of the unsaturated hydrocarbons having 2 to 8 carbon atoms is 0.001 to 10,000; The method for producing the unsaturated hydrocarbon mixture having 2 to 8 carbon atoms according to claim 9.

11. The process includes a step of polymerizing a monomer containing an unsaturated hydrocarbon having 2 to 8 carbon atoms obtained by the method for producing an unsaturated hydrocarbon having 2 to 8 carbon atoms according to any one of claims 1 to 3 and 5. A method for producing an olefin polymer.

12. The olefin-based polymer is a butadiene-based polymer. The method for producing an olefin polymer according to claim 11.

13. Using as a raw material the unsaturated hydrocarbon having 2 to 8 carbon atoms obtained by the method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms according to any one of claims 1 to 3 and 5, The method includes a step of synthesizing at least one compound selected from the group consisting of methyl methacrylate, propylene oxide, ethylene oxide, ethylene glycol, phenol, acetone, and isopropyl alcohol, Methods for producing compounds.

14. A method for producing a polymer, comprising a step of polymerizing a monomer produced from the unsaturated hydrocarbon having 2 to 8 carbon atoms obtained by the method for producing an unsaturated hydrocarbon having 2 to 8 carbon atoms according to any one of claims 1 to 3 and 5 as a raw material, the monomer comprising at least one compound selected from the group of compounds consisting of methyl methacrylate, propylene oxide, ethylene oxide and ethylene glycol.

15. The plant-derived carbon concentration is 0.1 to 99.9 pMC; An olefin polymer obtained by the method for producing an olefin polymer according to claim 11.

16. The plant-derived carbon concentration is 0.1 to 99.9 pMC; A polymer obtained by the method for producing a polymer according to claim 14.