Method for producing unsaturated hydrocarbon having 2-8 carbon atoms, method for producing mixture of unsaturated hydrocarbon having 2-8 carbon atoms, method for producing olefin polymer, method for producing compound, method for producing polymer, olefin polymer, and polymer

Abstract

A method for producing a C2-8 unsaturated hydrocarbon according to the present invention comprises: a step (1) in which a plastic mixture (A) having a polyolefin plastic content of 50 mass% or more and a residue (B) are sorted from waste plastics; a step (2) in which the plastic mixture (A) is decomposed to obtain a reaction product containing an unsaturated hydrocarbon having 2-8 carbon atoms; and a step (3) in which the reaction product is washed and purified, thereby separating an unsaturated hydrocarbon having 2-8 carbon atoms.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the priority of Japanese Patent Application No. 2022-106346, which is incorporated by reference into the description of the present application specification. Technical Field

[0003] 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 olefin polymers, a method for producing compounds, a method for producing polymers, olefin polymers and polymers. Background Art

[0004] Plastics are produced in large quantities because they are simple, durable, and relatively cheap, but most of them are disposable and discarded as garbage, so environmental pollution caused by microplastics after plastics are micronized has become a problem.

[0005] In addition, from the perspective of resource recovery, the regeneration and reuse of plastics are also important. Therefore, in order to recycle waste plastic resources, treatments such as reuse, material recycling, and chemical recycling are carried out. In particular, chemical recycling can chemically decompose plastics and regenerate them into petrochemical raw materials, so there is the possibility of breaking through the limitations of performance degradation caused by recycling. For example, in non-patent document 1, a catalytic cracking method for converting polyolefins into lower olefins using a catalyst is disclosed as one of the chemical recycling technologies.

[0006] Prior art literature

[0007] Non-patent literature

[0008] Non-patent literature 1: Monthly Fine Chemicals, Vol. 46 (Issue 12), pp. 44-50 (2017) Summary of the invention

[0009] Problems to be solved by the invention

[0010] In recent years, as the development of chemical recycling technology has become popular, there is a demand for more efficient technology for obtaining compounds such as petrochemical raw materials. In particular, products made from unsaturated hydrocarbons having 2 to 8 carbon atoms are involved in many aspects, so it is desired to efficiently obtain unsaturated hydrocarbons having 2 to 8 carbon atoms.

[0011] The present invention has been made in view of such circumstances, and its object is to provide a method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms that can effectively obtain compounds such as petrochemical raw materials 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 olefin polymers, a method for producing compounds and a method for producing polymers, an olefin polymer obtained by the above-mentioned method for producing olefin polymers, and a polymer obtained by the above-mentioned method for producing polymers.

[0012] Means used to solve problems

[0013] The method for producing an unsaturated hydrocarbon having 2 to 8 carbon atoms according to the first aspect of the present invention comprises the following steps:

[0014] Step (1), wherein a plastic mixture (A) and a residue (B) are separated from waste plastics, wherein the content of polyolefin plastic in the plastic mixture (A) is 50% by mass or more;

[0015] Step (2), wherein the plastic mixture (A) is decomposed to obtain a reaction product containing an unsaturated hydrocarbon having 2 to 8 carbon atoms; and

[0016] Step (3) in which the reaction product is washed and purified to separate unsaturated hydrocarbons having 2 to 8 carbon atoms.

[0017] The method for producing an unsaturated hydrocarbon having 2 to 8 carbon atoms according to the second aspect of the present invention comprises the following steps:

[0018] Step (1), wherein a plastic mixture (A) and a residue (B) are separated from waste plastics, wherein the content of polyolefin plastic in the plastic mixture (A) is 50% by mass or more;

[0019] Step (12), wherein the residue (B) is heated to obtain a mixed gas containing carbon monoxide, carbon dioxide and hydrogen;

[0020] Step (13), wherein the mixed gas is mixed with at least one gas selected from the group consisting of carbon monoxide, carbon dioxide and hydrogen, or a portion of at least one gas selected from the group consisting of carbon monoxide, carbon dioxide and hydrogen is removed from the mixed gas, thereby obtaining a regulated gas in which the volume amount of hydrogen is 1.5 to 4.0 relative to the total volume amount of carbon monoxide and carbon dioxide;

[0021] step (14), in which carbon monoxide, carbon dioxide and hydrogen contained in the regulating gas are reacted to obtain alcohol; and

[0022] Step (15) in which an unsaturated hydrocarbon having 2 to 8 carbon atoms is obtained using an alcohol as a raw material.

[0023] The method for producing an unsaturated hydrocarbon having 2 to 8 carbon atoms of the third formula of the present invention comprises the following steps:

[0024] Step (1), wherein a plastic mixture (A) and a residue (B) are separated from waste plastics, wherein the content of polyolefin plastic in the plastic mixture (A) is 50% by mass or more;

[0025] Step (2), wherein the plastic mixture (A) is decomposed to obtain a reaction product containing an unsaturated hydrocarbon having 2 to 8 carbon atoms;

[0026] Step (3), wherein the reaction product is washed and purified to separate unsaturated hydrocarbons having 2 to 8 carbon atoms;

[0027] Step (12), wherein the residue (B) is heated to obtain a mixed gas containing carbon monoxide, carbon dioxide and hydrogen;

[0028] Step (13), wherein the mixed gas is mixed with at least one gas selected from the group consisting of carbon monoxide, carbon dioxide and hydrogen, or a portion of at least one gas selected from the group consisting of carbon monoxide, carbon dioxide and hydrogen is removed from the mixed gas, thereby obtaining a regulated gas in which the volume amount of hydrogen is 1.5 to 4.0 relative to the total volume amount of carbon monoxide and carbon dioxide;

[0029] step (14), in which carbon monoxide, carbon dioxide and hydrogen contained in the regulating gas are reacted to obtain alcohol; and

[0030] Step (15) in which an unsaturated hydrocarbon having 2 to 8 carbon atoms is obtained using an alcohol as a raw material.

[0031] The method for producing an unsaturated hydrocarbon having 2 to 8 carbon atoms according to the fourth aspect of the present invention comprises the following steps:

[0032] step (21), wherein carbon dioxide is reacted with hydrogen to obtain a reaction mixture containing alcohol, carbon dioxide and carbon monoxide; and

[0033] Step (22) in which an unsaturated hydrocarbon having 2 to 8 carbon atoms is obtained from the alcohol and / or carbon monoxide contained in the reaction mixture.

[0034] The fifth aspect of the present invention includes the method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms of any one of the first to third aspects and the method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms of the fourth aspect.

[0035] A sixth aspect of the present invention is a method for producing an unsaturated hydrocarbon having 2 to 8 carbon atoms, comprising:

[0036] The method for producing an unsaturated hydrocarbon having 2 to 8 carbon atoms according to any one of the first to fourth aspects; and

[0037] A method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms, comprising the step (31), wherein in the step (31), at least one alcohol selected from the group consisting of ethanol, propanol and butanol is subjected to a dehydration reaction to obtain unsaturated hydrocarbons having 2 to 8 carbon atoms.

[0038] A seventh aspect of the present invention is a method for producing an unsaturated hydrocarbon having 2 to 8 carbon atoms, comprising:

[0039] A fifth aspect of the method for producing an unsaturated hydrocarbon having 2 to 8 carbon atoms; and

[0040] A method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms, comprising the step (31), wherein in the step (31), at least one alcohol selected from the group consisting of ethanol, propanol and butanol is subjected to a dehydration reaction to obtain unsaturated hydrocarbons having 2 to 8 carbon atoms.

[0041] The method for producing a mixture of unsaturated hydrocarbons having 2 to 8 carbon atoms of the present invention comprises a step (41), wherein unsaturated hydrocarbons having 2 to 8 carbon atoms obtained by the method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms using any one of the first to seventh modes are brought into contact with unsaturated hydrocarbons having 2 to 8 carbon atoms derived from fossil resources to obtain a mixture.

[0042] The method for producing an olefin polymer of the present invention comprises a step of polymerizing a monomer, wherein the monomer comprises an unsaturated hydrocarbon having 2 to 8 carbon atoms obtained by the method for producing an unsaturated hydrocarbon having 2 to 8 carbon atoms of any one of the first to seventh modes, 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.

[0043] The method for producing a compound of the present invention comprises the following steps, wherein an unsaturated hydrocarbon having 2 to 8 carbon atoms obtained by the method for producing an unsaturated hydrocarbon having 2 to 8 carbon atoms of any one of the first to seventh embodiments 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 as a raw material is used to synthesize at least one compound selected from the group consisting of methyl methacrylate, propylene oxide, ethylene oxide, ethylene glycol, phenol, acetone and isopropanol.

[0044] The method for producing a polymer of the present invention comprises a step of polymerizing a monomer, wherein the monomer is produced by using as a raw material an unsaturated hydrocarbon having 2 to 8 carbon atoms obtained by a method for producing an unsaturated hydrocarbon having 2 to 8 carbon atoms in any one of the first to seventh modes 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 as described above, and the monomer comprises at least one compound selected from the group consisting of methyl methacrylate, propylene oxide, ethylene oxide and ethylene glycol.

[0045] The olefin polymer of the present invention is obtained by the above-mentioned method for producing an olefin polymer, and the plant-derived carbon concentration of the olefin polymer is 0.1 pMC to 99.9 pMC.

[0046] The polymer of the present invention is obtained by the above-mentioned method for producing a polymer, and the plant-derived carbon concentration of the polymer is 0.1 pMC to 99.9 pMC.

[0047] Effects of the Invention

[0048] According to the present invention, there can be provided a novel and effective method for producing unsaturated hydrocarbons with 2 to 8 carbon atoms, which can effectively obtain unsaturated hydrocarbons with 2 to 8 carbon atoms from waste plastics, a method for producing a mixture of unsaturated hydrocarbons with 2 to 8 carbon atoms using the production method, a method for producing olefin polymers, a method for producing compounds and a method for producing polymers, an olefin polymer obtained by the above-mentioned method for producing olefin polymers, and a polymer obtained by the above-mentioned method for producing polymers. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Figure 1 This is a diagram showing an example of a process for producing an ethylene derivative using ethylene produced in the present invention as a starting material.

[0050] Figure 2 This is a diagram showing an example of a process for producing a propylene derivative using propylene produced in the present invention as a starting material.

[0051] Figure 3 This is a diagram showing an example of a process for producing a derivative using the unsaturated hydrocarbon having 4 carbon atoms produced in the present invention as a starting material.

[0052] Figure 4 This is a diagram showing an example of a process for producing a derivative using the unsaturated hydrocarbon having 5 carbon atoms produced in the present invention as a starting material.

[0053] Figure 5 This is a diagram showing an example of a process for producing a derivative using benzene, toluene, and xylene produced in the present invention as starting materials.

[0054] Figure 6 This is a diagram showing an example of the invention of claim 1.

[0055] Figure 7 This is a diagram showing an example of the invention of claim 2.

[0056] Figure 8 This is a diagram showing an example of the invention according to claim 3.

[0057] Fig. 9 This is a diagram showing an example of the invention according to claim 5.

[0058] Fig.10 This is a diagram showing an example of the invention according to claim 6.

[0059] Fig.11 This is a diagram showing an example of the invention according to claim 7.

[0060] Fig.12 This is a diagram showing an example of the invention according to claim 8. DETAILED DESCRIPTION

[0061] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments.

[0062] [First Embodiment of the Method for Producing Unsaturated Hydrocarbons Having 2 to 8 Carbon Atoms]

[0063] The first embodiment of the method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms comprises the following steps: step (1), wherein a plastic mixture (A) and a residue (B) are separated from waste plastics, wherein the content of polyolefin plastic in the plastic mixture (A) is 50% by mass or more; step (2), wherein the plastic mixture (A) is decomposed to obtain a reaction product containing unsaturated hydrocarbons having 2 to 8 carbon atoms; and step (3), wherein the reaction product is cleaned and purified to separate the unsaturated hydrocarbons having 2 to 8 carbon atoms.

[0064] Step (1) is a step of separating a plastic mixture (A) and a residue (B) from waste plastics. The waste plastics separated in step (1) mainly include two types: general waste plastics and industrial waste plastics. General waste plastics are plastic waste mainly discharged from households, such as used plastic bottles, food trays, plastic bags, seasoning bottles, hangers, etc. On the other hand, industrial waste plastics are waste materials and packaging materials discharged from the manufacturing, processing and circulation of plastic products; plastic bags and food containers discharged from offices are plastic waste mainly discharged from factories, stores and other business premises.

[0065] 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 generally contain foreign matter such as paper, glass, stone, wood, and metal as undesirable components other than plastics.

[0066] Step (1) is a step of treating waste plastics to separate into a plastic mixture (A) with an increased polyolefin content suitable for decomposition reaction and a residue (B) which is a component other than the plastic mixture (A) that is not desired in the decomposition reaction. Step (1) may use a plurality of devices that perform different treatments. Such devices may include, for example, one or more of a sorting device, a crushing device, a cleaning device, a dehydrating device, and a drying device, as disclosed in Japanese Patent Application Publication No. 2022-2833 and Japanese Patent Application Publication No. 2017-170653.

[0067] The sorting device is a device for sorting polyolefin plastics from waste plastics by means of magnetic separation, optical separation, specific gravity separation, swing sorting machine, centrifugal separator, etc.

[0068] For example, in a swing-type sorting machine, waste plastics can be separated into heavy objects (solid plastics), small-diameter objects (metal sheets, wood chips, etc.) and light objects (film-type plastics), and film-type plastics and pallet-type plastics mainly composed of polyolefins as light objects can be sorted out, and solid plastics such as plastic bottles, metals, etc. as heavy objects and small-diameter objects can be removed, and the removal rate of foreign matter can be further improved by performing air separation, magnetic separation, specific gravity separation, etc.

[0069] In addition, in the centrifuge, as a type of plastic material, polyvinyl chloride, polyvinylidene chloride, etc., which are chlorine-containing plastics that generate chlorine gas when burned, are separated from polypropylene with high precision. More specifically, the centrifuge is a device that separates light-weight plastics from heavy-weight plastics by rotating a container into which water and waste plastics are placed, for example, to perform centrifugal separation, thereby using water as a medium, and can effectively separate PP with a specific gravity of about 0.9 and chlorine-containing plastics with a specific gravity of about 1.1 to about 1.4.

[0070] The crushing device is a device for crushing plastic. The cleaning device is a device for cleaning the sorted and crushed plastic. The dehydrating device and the drying device are devices for dehydrating and drying the cleaned plastic.

[0071] Through step (1), a plastic mixture (A) with an increased content of polyolefin plastics can be obtained. The plastic mixture (A) contains polyolefins suitable for decomposition reactions. The content of polyolefin plastics is 50% by mass or more relative to the total mass of the plastic mixture (A). Examples of polyolefin 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, and preferably polyethylene, polypropylene and ethylene-propylene copolymer. It should be noted that the polyolefin plastics contained in the plastic mixture (A) may be a mixture of two or more of these polyolefin plastics.

[0072] In the plastic mixture (A) having an increased content of polyolefin plastics, the total content of polyvinyl chloride (PVC) and polyvinylidene chloride (PVDC) is preferably 1% by mass or less, the content of polyamide is preferably 4% by mass or less, and the content of polyethylene terephthalate (PET) is preferably 5% by mass or less.

[0073] The residue (B) separated by step (1) is the remaining waste plastics other than the plastic mixture (A). Examples of the residue (B) include: polyolefins with a lot of dirt, films obtained by laminating polyolefins and non-polyolefins, non-polyolefin resins, paper, glass, wood, stone, metal, etc. Examples of non-polyolefin resins include: 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. The content of polyolefin plastics in the residue (B) is less than the content of polyolefin plastics in the plastic mixture (A).

[0074] 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 pyrolysis step in which the decomposition is performed by heating. In another embodiment, a catalytic cracking step is included in which the reaction is performed while in contact with a catalyst in addition to heating. In yet another embodiment, a pyrolysis step and a catalytic cracking step are included. In addition, the product obtained in the pyrolysis step and / or the catalytic cracking step may be decomposed again in another pyrolysis step to obtain a reaction product containing unsaturated hydrocarbons having 2 to 8 carbon atoms. In addition, when decomposition is performed by combining multiple decomposition steps, the reaction product obtained in the first decomposition step may be directly supplied to the subsequent decomposition step, or at least a portion of the reaction product may be purified and supplied to the subsequent decomposition step.

[0075] First, an embodiment in which the decomposition of the plastic mixture (A) in the step (2) includes a pyrolysis step will be described below.

[0076] The pyrolysis step decomposes the plastic mixture (A) by heating. In the pyrolysis step, a pyrolysis device can be used, or a cracking device using naphtha or ethane as a raw material can be used. In the pyrolysis step, the plastic mixture (A) is decomposed to obtain a reaction product containing unsaturated hydrocarbons having a carbon number of 2 to 8. By decomposing the plastic mixture (A), unsaturated hydrocarbons having a carbon number of 2 to 8 can be directly obtained, and / or saturated hydrocarbons and hydrocarbon components having a carbon number of 9 or more can also be obtained. In addition, a mixture of the two can also be obtained.

[0077] As the pyrolysis device, for example, one or more heated extruders, heated rotary furnaces, heated container-type reactors, fixed bed reactors, bubbling fluidized bed reactors, internal circulating fluidized bed reactors, circulating fluidized bed reactors, devices that cause plastic to flow down along the inner wall of a heated container to decompose, microwave heating devices, etc. can be used. In addition, as a heat source in the pyrolysis step, the pyrolysis residue produced in the pyrolysis device, and the hydrocarbon gas and / or liquid hydrocarbon obtained by washing and purification in the step (3) described later can be burned and used. Alternatively, electricity, microwaves, or electricity or microwaves can be used in combination with the above-mentioned combustion. In the pyrolysis step, there can be a combustion device for burning the pyrolysis residue produced in the pyrolysis reaction. In addition, a heat transfer surface or a heat transfer medium can be used to supply the necessary heat from the combustion device to the pyrolysis device.

[0078] The conditions of the pyrolysis device in the pyrolysis process can be carried out at low severity or high severity. The low severity pyrolysis reaction can be carried out at a temperature of 250°C to 450°C, for example, and sometimes produces pyrolysis oil rich in monoolefins and diolefins and a considerable amount of aromatic compounds, and the reaction products may contain chloride compounds. The high severity pyrolysis reaction is, for example, a reaction carried out at a temperature of 450°C to 750°C, which can produce pyrolysis oil rich in aromatic compounds. The liquid product of the high severity pyrolysis reaction sometimes contains chloride compounds. The residence time of the reaction product in the pyrolysis process is 0.1 seconds to 100 seconds.

[0079] The pyrolysis device may have a supply device for supplying the plastic mixture (A) sorted in step (1). The supply device may include, for example, a rotary feeder, a screw feeder, a flat plate feeder, etc. as a quantitative supply device, and may include a double damper, a lock hopper, etc. for sealing the device and the supply device. In addition, the shape of the plastic mixture (A) to be pyrolyzed is not particularly limited, and may be, for example, any of a fluffy shape, a compression-molded granular shape, a granular shape formed by semi-melting, full melting, etc.

[0080] The pyrolysis apparatus used in the pyrolysis step may include a devolatilization extruder. The devolatilization extruder introduces a purge gas during the pyrolysis step to remove gaseous chlorides from the resulting reaction product. A devolatilization extruder that can be used for pyrolysis and treatment of mixed plastics is described in more detail in U.S. Provisional Patent Application No. 62 / 369,379 filed on August 1, 2016.

[0081] The reaction product containing unsaturated hydrocarbons having 2 to 8 carbon atoms after decomposition in the pyrolysis step can be separated into a gas product and a liquid product. In this case, the gas product contains at least a portion of the gas phase of the reaction product, and the liquid product contains at least a portion of the liquid phase of the reaction product. At this time, the pyrolysis device may have a device for separating the gas product and the liquid product. As a device for separating the gas product and the liquid product, for example, there can be listed: a vapor-liquid separator, an oil-gas separator, a gas-liquid separator, a degassing device, a deliquidating device, a scrubber, a collector, a flash tank, a compressor suction tank, a gravity separation device, a centrifuge, a filter blade separator, a demister pad, a liquid-gas coalescer, a distillation tower, or a device obtained by combining them.

[0082] In one embodiment, the pyrolysis device may be a condenser that operates under the conditions that a portion of the reaction product is condensed to produce a hydrocarbon liquid (e.g., a liquid product) and hydrocarbon gases remain in a gas phase (e.g., a gas product). The gas product of the reaction product may be cooled by a cooler or the like, and separated into, for example, a heavy oil equivalent, a light oil equivalent, a kerosene equivalent, etc. according to different boiling points and recovered.

[0083] The reaction product obtained in the pyrolysis step can be hydrogenated. The hydrogenation is performed by hydrogenating the liquid product in the reaction product. By hydrogenating the liquid product, hydrocarbon products and gas products having 1 to 4 carbon atoms can be generated. The hydrogenation is performed, for example, in a hydrocracker, a catalytic cracker, a fluid catalytic cracker, a hydrotreating unit, or a hydrotreating reactor obtained by combining them. By hydrogenating the reaction product obtained by the pyrolysis step, long-chain molecules having a large number of carbon atoms are hydrogenolyzed and dechlorinated. In the hydrogenation, the liquid product, hydrogen, or a combination thereof are added stepwise to an upflow, downflow, radial flow, or a hydrotreating catalyst in combination thereof and brought into contact.

[0084] The hydroprocessing reactor for hydrogenation comprises a hydroprocessing catalyst, which can process gas phase, liquid phase, gas-liquid phase, gas-liquid solid phase or slurry phase. The hydroprocessing reactor can comprise one or more beds of a hydroprocessing catalyst of a fixed bed, a fluidized bed, a moving bed, an ebullated bed, a slurry bed or a combination thereof. The hydroprocessing reactor can operate in adiabatic, isothermal, non-adiabatic, non-isothermal or a combination thereof. In one embodiment, the hydroprocessing reactor can comprise one or more containers. In addition, the hydroprocessing reactor can make it easy to react arbitrarily with the composition of the liquid product of hydrogen or in the presence of hydrogen.

[0085] A reaction based on hydrogenation is a reaction in which hydrogen atoms are added to double bonds of unsaturated molecules (e.g., olefins, aromatic compounds), resulting in the formation of saturated molecules (e.g., paraffins, isoparaffins, cycloparaffins). In addition, a reaction based on hydrogenation can cut the bonds of organic compounds, resulting in the cracking of hydrocarbon molecules into smaller hydrocarbon molecules having a carbon number of 2 or more, or resulting in subsequent reaction and / or substitution of heteroatoms with hydrogen. Examples of reactions that may occur in hydrogenation include: hydrogenation of olefins, removal of heteroatoms from heteroatom-containing hydrocarbons (e.g., dechlorination), hydrocracking of large paraffins or isoparaffins into smaller hydrocarbon molecules, hydrocracking of aromatic hydrocarbons into smaller cyclic or non-cyclic hydrocarbons, conversion of one or more aromatic compounds into one or more cycloparaffins, isomerization of one or more normal paraffins into one or more isoparaffins, selective ring opening of one or more cycloparaffins into one or more isoparaffins, or combinations thereof, but are not limited thereto.

[0086] In one embodiment, a liquid product is brought into contact with a hydrotreating catalyst in the presence of hydrogen to obtain a gas product having a carbon number of 1 to 4 and a liquid hydrocarbon having a carbon number of 5 or more. Here, the advantages of dechlorination using a hydrotreating catalyst include: no chlorine adsorbent is required, and an effective amount of Na2CO3 that acts as a dechlorinating agent does not need to be added.

[0087] Hydrotreating catalyst can be any catalyst (such as commercially available hydrotreating catalyst) for the hydrogenation of olefins and aromatic hydrocarbons. As hydrotreating catalyst, for example, can be listed: alumina loaded cobalt and molybdenum catalyst (Co-Mo catalyst), alumina loaded nickel and molybdenum catalyst (Ni-Mo catalyst), alumina loaded tungsten and molybdenum catalyst (W-Mo catalyst), alumina loaded cobalt oxide and molybdenum oxide, alumina loaded nickel oxide and molybdenum oxide, alumina loaded tungsten oxide and molybdenum oxide, alumina loaded cobalt sulfide and molybdenum sulfide, alumina loaded nickel sulfide and molybdenum sulfide, alumina loaded tungsten sulfide and molybdenum sulfide, zeolite containing one or more metals or their combination. In addition, as other catalysts suitable for use as hydrotreating catalyst, can also be listed: alumina loaded platinum and palladium catalyst (Pt-Pd catalyst) suitable for slurry treatment, nickel sulfide suitable for slurry treatment, molybdenum sulfide suitable for slurry treatment or their combination etc. As zeolite, can be listed: ZSM-5, ZSM-11, Y, high silica Y, USY or their combination etc. Each of the one or more metals of the zeolite may 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.

[0088] In addition, the reaction product can 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 with carbon atoms of 6 to 8 in an aromatic compound separation unit. At least a portion of the cracked reaction product and / or at least a portion of the gas product with carbon atoms of 1 to 4 can be introduced into a separation unit to generate unsaturated hydrocarbon gas, saturated hydrocarbon gas, aromatic compounds and heavy components. It should be noted that the unsaturated hydrocarbon gas contains ethylene, propylene, butenes, butadiene or a combination thereof. Saturated hydrocarbon gas contains methane, ethane, propane, butanes, hydrogen or a combination thereof. Aromatic compounds contain aromatic hydrocarbons with carbon atoms of 6 to 8. Moreover, the heavy components contain hydrocarbons with carbon atoms of 5 or more other than aromatic hydrocarbons with carbon atoms of 6 to 8. In one embodiment, the separation unit may include multiple distillation towers.

[0089] Next, an embodiment in which the decomposition of the plastic mixture (A) in the step (2) includes a catalytic cracking step will be described below.

[0090] In the catalytic cracking step, the plastic mixture (A) is heated and further reacted in contact with a catalyst. The catalytic cracking step can use any known suitable reaction vessel. Examples of the material of the reaction vessel include quartz glass, carbon steel, stainless steel, Inconel, Hastelloy, Incoloy, and Monel.

[0091] For the catalyst used in the catalytic cracking process, for example, non-bound (non-loaded) zeolite catalysts, zeolite catalysts combined with a binder or a carrier, etc. can be listed. The binder and the carrier can use any known suitable binder and carrier. As the binder, for example, silica, alumina, silica-alumina, silica-titania, silica-thoria, silica-magnesia, silica-zirconia, silica-beryllium oxide, and ternary compositions of silica and other refractory oxides can be listed. In addition, as the binder or matrix material, for example, clays such as montmorillonite, kaolin, bentonite, halloysite, dickite, perlite and annular clay can be listed.

[0092] As the catalyst used in the catalytic cracking process, it is preferred to use an MFI type zeolite catalyst. The MFI type zeolite catalyst may contain silicon atoms, aluminum atoms, oxygen atoms, and hydrogen atoms as atoms other than sodium atoms. In addition, the MFI type 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 increasing the yield of unsaturated hydrocarbons having 2 to 8 carbon atoms, the MFI type zeolite catalyst preferably contains sodium atoms, silicon atoms, and aluminum atoms.

[0093] From the viewpoint of improving the yield of unsaturated hydrocarbons having 2 to 8 carbon atoms, the ratio of the number of moles of silicon atoms to the number of moles of aluminum atoms (Si / Al ratio) in the MFI zeolite catalyst is preferably 50 or more, more preferably 100 or more.

[0094] The sodium content and Si / Al ratio of the zeolite catalyst can be calculated by analyzing the zeolite catalyst according to the known ICP emission spectrometry method.

[0095] Here, MFI zeolite refers to a crystalline aluminosilicate having an MFI structure in the structure code of IZA (International Zeolite Association). Specific examples of MFI zeolite include: + -ZSM-5, NH4 + -ZSM-5, Na + -ZSM-5, Ca 2+ -ZSM-5. MFI zeolite can be prepared by any known suitable method, and commercially available H + -ZSM-5. The MFI type zeolite can be confirmed by analysis using an X-ray diffraction analysis method.

[0096] The following is a description of a method for producing an MFI zeolite catalyst. The MFI zeolite catalyst can be produced by a method comprising preparing a mixture containing a silicon source, an aluminum source, a template agent, and an alkali metal source and crystallizing the mixture to obtain an MFI zeolite. Here, "template agent" refers to a substance used to impart a pore structure to the zeolite.

[0097] As the silicon source, a known silicon source used in the production of various zeolites can be used, and examples of the silicon source include tetraethyl orthosilicate, colloidal silica, silica gel dry powder, silica hydrogel, sodium silicate, and the like.

[0098] As the aluminum source, a known aluminum source used in the production of various zeolites can be used. Examples of the aluminum source include aluminum nitrate, aluminum chloride, sodium aluminate, aluminum hydroxide, aluminum alkoxide, etc. Among these aluminum sources, aluminum nitrate or sodium aluminate is preferred.

[0099] As the template, a known template 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, triethylenetetramine, etc. Among these templates, tetrapropylammonium salt (tetrapropylammonium hydroxide) is preferred.

[0100] Examples of the alkali metal source include alkali metal hydroxides, alkali metal chlorides, alkali metal bromides, alkali metal sulfides, etc. Examples of the alkali metal include sodium and potassium.

[0101] 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.

[0102] 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.

[0103] The ratio of the molar number of silicon atoms to the molar number of aluminum atoms (Si / Al ratio) in the mixture containing the silicon source, aluminum source, template and alkali metal source is preferably 50 or more, more preferably 100 or more. The above ratio may be 10,000 or less, preferably 2,500 or less.

[0104] In addition, the ratio of the number of moles of each component in the mixture containing the silicon source, the aluminum source, the template, and the alkali metal source to the number of moles of silicon atoms preferably satisfies the following requirements.

[0105] Template: 0.02 or more and 5.0 or less

[0106] Alkali metal source: 0.01 or more and 0.2 or less

[0107] Water: 2 or more and less than 100

[0108] Furthermore, the ratio of the number of moles of each component in the mixture containing the silicon source, the aluminum source, the template, and the alkali metal source to the number of moles of silicon atoms more preferably satisfies the following requirements.

[0109] Template: 0.05 or more and 2.0 or less

[0110] Alkali metal source: 0.04 or more and 0.3 or less

[0111] Water: 5 or more and 50 or less

[0112] 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.

[0113] In the catalytic cracking step, an inert gas such as steam, nitrogen, or carbon dioxide may coexist.

[0114] In the catalytic cracking process, the reaction is carried out while in contact with the catalyst in addition to heating. Therefore, the above-mentioned pyrolysis device can be used in the catalytic cracking process. In this case, the pyrolysis device can contain one or more beds of inert material or pyrolysis catalyst, wherein the inert material or pyrolysis catalyst comprises sand, zeolite, alumina, catalytic cracking catalyst or a combination thereof. The pyrolysis catalyst can transfer heat to the components provided to the pyrolysis process. The pyrolysis device can be operated in an adiabatic, isothermal, non-adiabatic, non-isothermal or a combination thereof.

[0115] The zeolite catalyst used in the catalytic cracking step may be a regenerated catalyst. That is, the first embodiment can be implemented by subjecting 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.

[0116] The catalyst regeneration method is specifically described below. The catalyst regeneration method includes a step of obtaining a regenerated catalyst by calcining the catalyst in an atmosphere containing 1% by volume to 50% by volume of oxygen.

[0117] The step of obtaining the regenerated catalyst is preferably performed in an atmosphere containing oxygen in a range of 1% to 50% by volume, and more preferably performed in an atmosphere containing oxygen in a range of 5% to 30% by volume.

[0118] The step of obtaining the regenerated catalyst can be carried out, for example, in an air atmosphere, a nitrogen atmosphere, an argon atmosphere, a carbon dioxide gas atmosphere, or a gas atmosphere obtained by mixing these gases, while adjusting the oxygen concentration in the atmosphere by any known appropriate method.

[0119] The temperature in the step of obtaining the regenerated catalyst is preferably in the range of 400°C to 700°C, more preferably in the range of 450°C to 600°C.

[0120] The treatment time in the step of obtaining the regenerated catalyst is preferably 30 minutes to 48 hours, more preferably 1 hour to 24 hours.

[0121] When applied to the first embodiment, the regenerated catalyst obtained by the above catalyst regeneration method can be used in the same manner as the "zeolite catalyst" not used in the catalytic cracking step without particularly adjusting conditions such as temperature, treatment time, and atmosphere.

[0122] The following describes a method for performing the decomposition of the plastic mixture (A) in step (2) in multiple stages. In the method for performing step (2) in multiple stages, the product obtained in the pyrolysis step and / or the catalytic cracking step is decomposed again in another pyrolysis step.

[0123] In the case where process (2) is performed in multiple stages, for example, the pyrolysis devices can be connected in series. When two pyrolysis devices are connected, the pyrolysis process can be divided into a first stage implemented in the first pyrolysis device and a second stage implemented in the second pyrolysis device and connected to the downstream fluid of the first stage. As understood by those skilled in the art, the second stage can enhance the pyrolysis of the intermediate pyrolysis product flow flowing from the first stage to the second stage, thereby obtaining a reaction product flowing out of the second stage. In one embodiment, the first stage can perform pyrolysis of the plastic mixture (A), and then the second stage can utilize pyrolysis or catalytic cracking of the plastic mixture (A) to obtain the reaction product flowing out of the second stage. Alternatively, the first stage can perform catalytic cracking of the plastic mixture (A), and then the second stage can utilize pyrolysis or catalytic cracking of the plastic mixture (A) to obtain the reaction product flowing out of the second stage. In another embodiment, the pyrolysis device can include one or more devices configured to convert the plastic mixture (A) into gaseous and liquid products. One or more devices can include the above-mentioned inert substances or pyrolysis catalysts.

[0124] 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 can be performed by known methods. In addition, the purification in step (3) may include the above-mentioned purification by hydrogenation.

[0125] The reaction product containing unsaturated hydrocarbons having 2 to 8 carbon atoms obtained in step (2) is washed in step (3) to remove chlorine-containing compounds, sulfur-containing compounds, nitrogen-containing compounds, etc. Solvent washing, washing with an alkaline solution, absorption removal of ammonia components, and adsorption removal using an adsorbent are performed. In addition, purification is performed to separate and purify a plurality of products having different boiling point differences. Washing and purification can be provided in the process of the method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms of the first embodiment, or can be common in a joint plant that brings together different technologies. When a naphtha cracker and an ethane cracker are adjacent to each other, the reaction product can be introduced into a distillation tower group of the naphtha cracker and the ethane cracker for separation and purification. In addition, in order to increase the yield of unsaturated hydrocarbons having 2 to 8 carbon atoms, a portion of the separated and purified hydrocarbons can be recycled to the catalytic cracking process or the cracker.

[0126] 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, pentene, etc.; diolefins having 4 or 5 carbon atoms such as butadiene and pentadiene; and aromatic hydrocarbons having 6 to 8 carbon atoms such as benzene, toluene, xylene, etc., preferably olefins having 2 to 4 carbon atoms.

[0127] [Second Embodiment of the Method for Producing Unsaturated Hydrocarbons Having 2 to 8 Carbon Atoms]

[0128] The method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms of the second embodiment comprises the following steps: step (1), wherein a plastic mixture (A) and a residue (B) are separated from waste plastics, wherein the content of polyolefin plastic in the plastic mixture (A) is 50% by mass or more; step (12), wherein the residue (B) is heated to obtain a mixed gas containing carbon monoxide, carbon dioxide and hydrogen; step (13), wherein the mixed gas is mixed with at least one gas selected from the group consisting of carbon monoxide, carbon dioxide and hydrogen, or a part of at least one gas selected from the group consisting of carbon monoxide, carbon dioxide and hydrogen is removed from the mixed gas, thereby obtaining a regulating gas in which the volume amount of hydrogen is 1.5 to 4.0 relative to the total volume amount of carbon monoxide and carbon dioxide; step (14), wherein the carbon monoxide, carbon dioxide and hydrogen contained in the regulating gas are reacted to obtain alcohol; and step (15), wherein the unsaturated hydrocarbons having 2 to 8 carbon atoms are obtained using the alcohol as a raw material.

[0129] The process (1) of the second embodiment is the same as the process (1) of the first embodiment described above. In addition, in the second embodiment, the raw material containing the residue (B) sorted out in the process (1) is gasified in the process (12) described later to obtain a mixed gas with carbon monoxide, carbon dioxide and hydrogen as main components. The raw material may contain organic waste that can obtain the gas containing hydrogen and carbon oxide shown below. As the above-mentioned waste, for example, kitchen waste, paper waste, fiber waste, plastic waste, biomass waste, food waste, building materials, wood, wood chips, thinning wood, straw, wheat straw, rice husks, waste oil, rubber tires or mixtures thereof and other wastes can be listed.

[0130] 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 obtaining device. In step (12), the residue (B) is supplied to the mixed gas obtaining device, and the residue (B) reacts in the mixed gas obtaining device. As the mixed gas obtaining device, for example, a fixed bed furnace, a fluidized bed furnace, a bubbling fluidized bed furnace, a circulating fluidized bed furnace, a circulating moving bed furnace and the like can be used.

[0131] The residue (B) supplied to the mixed gas acquisition device may further include waste plastics such as general waste plastics and industrial waste plastics. General waste plastics are, for example, plastic wastes mainly discharged from households, such as used plastic bottles, food trays, plastic bags, seasoning bottles, hangers, etc. On the other hand, industrial waste plastics are waste materials and packaging materials discharged from the manufacturing, processing and circulation of plastic products; plastic bags and food containers discharged from offices are plastic wastes mainly discharged from business premises such as factories and stores.

[0132] In the mixed gas acquisition device, it is assumed that the hydrocarbons react with water vapor or oxygen to cause reactions represented by the following equations (1) to (4), for example.

[0133] C n H 2n +nH2O→nCO+2nH2(1)

[0134] C n H 2n +2nH2O→nCO2+3nH2(2)

[0135] C n H 2n +0.5nO2→nCO+nH2(3)

[0136] C n H 2n +nO2→nCO2+nH2(4)

[0137] It should be noted that, in the above formula (1) and formula (3), carbon monoxide is generated together with hydrogen, but in the second embodiment, the carbon monoxide and water may be used as raw materials to obtain carbon dioxide and hydrogen through the reaction of the following formula (5). In addition, the above carbon monoxide and oxygen may be used as raw materials to obtain the heat energy and carbon dioxide required for step (12) through the reaction of the following formula (6).

[0138] CO+H2O→CO2+H2(5)

[0139] CO+0.5O2→CO2(6)

[0140] In the reactions of the above formulae (1) to (6), 1 to 3 mol of hydrogen gas are obtained per 1 mol of carbon atoms.

[0141] On the other hand, when the residue (B) contains waste containing organic matter derived from nature, for example, a reaction represented by the following formula (7) and / or a reaction represented by the following formula (8) is considered to occur in the mixed gas acquisition device.

[0142] (C6H 12 O6) n →6nCO+6nH2(7)

[0143] (C6H 12 O6) n +6nH2O→6nCO2+12nH2(8)

[0144] It should be noted that in the above formula (7), carbon monoxide is generated together with hydrogen, but the above carbon monoxide and water can also be used as raw materials to obtain carbon dioxide and hydrogen through the reaction of the above formula (5). In the above formulas (7) to (8), 1 to 2 moles of hydrogen are obtained for every 1 mole of carbon atoms.

[0145] The reaction of obtaining carbon monoxide and hydrogen from the above organic matter may require a reaction at a higher temperature than the reaction of obtaining carbon dioxide and hydrogen. In view of the energy cost of heating, the method of obtaining carbon dioxide and hydrogen is expected to be more advantageous.

[0146] The second embodiment may optionally further include a step (12') of cleaning the mixed gas after the step (12).

[0147] Step (12') is a step of cleaning the gas by removing impurities from the mixed gas, and is performed using a mixed gas cleaning device. In step (12'), the mixed gas is supplied to the mixed gas cleaning device. The mixed gas sometimes contains solid components such as coal and fly ash that poison the catalyst as impurities. In addition, as other impurities, reaction-inhibiting components such as sulfur components, chlorine components, and nitrogen components are sometimes contained. In such a case, it is preferred to clean the mixed gas before the step (14) described later. Step (12') can, for example, reduce the concentration of chlorides and sulfides in the mixed gas. As a result, the concentrations of chlorides and sulfides in the subsequent steps can be reduced to less than 1 ppm, preferably less than 100 ppb. Step (12') is usually performed based on the solid components or reaction-inhibiting components contained in the mixed gas. The cleaning in step (12') is performed by a known cleaning method. As a mixed gas cleaning device, for example, known devices such as a wet scrubber and an electrostatic precipitator can be used.

[0148] By purging the mixed gas in step (12') so that the concentrations of chloride and sulfide in the mixed gas are each 1 ppm or less, preferably 100 ppb or less, the degradation rate of the catalyst used in step (14) described later can be reduced, and the catalyst life can be extended.

[0149] 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, thereby obtaining a regulated gas in which the volume of hydrogen is 1.5 to 4.0 relative to the total volume of carbon monoxide and carbon dioxide. Step (13) is carried out using a gas composition regulating device, and may be further carried out using a CO2 separation device as needed.

[0150] Hereinafter, step (13) performed using the gas composition adjusting device and the CO 2 separation device will be described in detail.

[0151] In step (13), the mixed gas cleaned by the mixed gas cleaning device is supplied to the gas composition regulating device. Hydrogen can be supplied to the gas composition regulating device. As the gas composition regulating device, for example, a known device such as a partial oxidation reactor, a steam reforming reactor, a water gas shift reactor, etc. can be used.

[0152] Then, the regulated gas (hereinafter sometimes referred to as primary regulated gas) regulated in the gas component regulating device is supplied to the CO2 separation device. In the CO2 separation device, carbon dioxide is selectively separated (removed) from the supplied primary regulated gas to obtain a regulated gas (hereinafter sometimes referred to as secondary regulated gas). Examples of the CO2 separation device include a pressure swing adsorption device, an absorption stripping tower, a cryogenic carbon dioxide separation device, and a carbon dioxide separation membrane device.

[0153] Step (13) is a step of adjusting the composition of the mixed gas in the gas component adjusting device and selectively separating CO 2 from the adjusted gas in the CO 2 separation device. By passing through step (13), the mixed gas can be adjusted to a composition suitable for alcohol synthesis.

[0154] For every 1 mol of carbon monoxide (CO), 2 mol of hydrogen is required for the production of alcohol, and for every 1 mol of carbon dioxide (CO2), 3 mol of hydrogen is required for the production of alcohol. Therefore, it is desirable to adjust the volume fractions of hydrogen, carbon monoxide, and carbon dioxide in the regulating gas supplied to the reactor for the reaction in the step (14) described later so that the index SN represented by the following formula (9) is 2 or more. In the following formula (9), yH2, yCO2, and yCO are the volume fractions of hydrogen, carbon dioxide, and carbon monoxide in the regulating gas.

[0155] SN=(yH2-yCO2) / (yCO+yCO2)(9)

[0156] In the second embodiment, when the mixed gas obtained in step (12) contains hydrogen, carbon dioxide and carbon monoxide, it is desirable to obtain a regulated gas in which the carbon dioxide is regulated to a concentration of preferably 0.1% by volume to 20% by volume, more preferably 1% by volume to 10% by volume. Therefore, when the value of the above-mentioned index SN is low, it is preferred to pre-regulate the SN value of the mixed gas as the regulated gas before the step (14) described later.

[0157] Step (13) can be performed by implementing at least one of the following methods: (i) a method of 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. In this way, the volume amount of hydrogen relative to the total volume amount of carbon monoxide and carbon dioxide in the regulating gas (hereinafter sometimes described as H2 / (CO+CO2)) can be preferably adjusted to 1.5 to 4.0.

[0158] In step (13), for example, a water gas shift reaction may be performed after the hydrocarbons contained in the mixed gas are reformed into carbon monoxide and hydrogen by a partial oxidation reaction or a steam reforming reaction. Thus, H2 / (CO+CO2) can be more easily adjusted to be greater than 1.5 and less than 4.0.

[0159] Alternatively, in step (13), hydrogen (hydrogen gas) may be added (added) after the hydrocarbons contained in the mixed gas are reformed into carbon monoxide and hydrogen by partial oxidation reaction or steam reforming reaction. Thus, H2 / (CO+CO2) can be more easily adjusted to be greater than 1.5 and less than 4.0. As a method for obtaining the above-mentioned hydrogen, for example, known techniques such as reforming of fossil resources, reactions based on decomposition, decomposition reactions or dehydrogenation reactions of hydrocarbons, electrolysis of water or salt water, decomposition of water using a photocatalyst, and decomposition of ammonia can be utilized.

[0160] Examples of the above-mentioned hydrocarbon decomposition reaction include a method of producing lower olefins by decomposition reaction of naphtha, a method of obtaining hydrogen by thermal decomposition of methane, etc. Examples of the above-mentioned hydrocarbon dehydrogenation reaction include a method of producing ethylene by dehydrogenation reaction of ethane, a method of producing propylene by dehydrogenation reaction of propane, a method of producing toluene by dehydrogenation reaction of methylcyclohexane, and a method of producing cyclohexanone by dehydrogenation reaction of cyclohexanol.

[0161] As another method of adjusting the value of the index SN in step (13), at least a portion of the carbon monoxide contained in the mixed gas may be reformed or decomposed to change the ratio of carbon monoxide to carbon dioxide contained in the mixed gas.

[0162] As another method of adjusting the value of the index SN in step (13), a method of removing at least a portion of the carbon dioxide from the mixed gas can be cited. The carbon dioxide removed here can be used for other purposes. Specifically, for example, the mixed gas can be treated by a chemical adsorption method using an amine solution to remove carbon dioxide as an acidic gas, thereby obtaining a gas containing hydrogen and carbon monoxide. In addition to the above-mentioned chemical adsorption method, the mixed gas can also be treated by a cryogenic separation method to separate carbon dioxide, which has the highest boiling point among the above-mentioned three components, thereby obtaining a gas containing hydrogen and carbon monoxide. In addition, carbon dioxide can 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.

[0163] In the process of selectively separating CO2, for example, the primary regulating gas can be treated by a chemical absorption method using an amine solution, and carbon dioxide can be separated from the primary regulating gas to obtain an acidic gas. Thus, a secondary regulating gas with a concentration of carbon dioxide adjusted to 0.1% to 20% by volume, preferably 1% to 10% by volume, can be obtained. Alternatively, the primary regulating gas can be treated by a cryogenic separation method to separate the carbon dioxide with the highest boiling point among hydrogen, carbon monoxide, and carbon dioxide to obtain a secondary regulating gas. In addition, carbon dioxide can 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 to obtain a secondary regulating gas. The separated carbon dioxide can be used for other purposes.

[0164] It should be noted that, in the above description, the case of supplying hydrogen to the gas component regulating device is described, but carbon monoxide, carbon dioxide and / or hydrogen may also be supplied to the gas component regulating device. In addition, in the above description, the case of selectively separating (removing) carbon dioxide from the supplied primary regulating gas in the CO2 separation device is described, but carbon monoxide, carbon dioxide and / or hydrogen may also be selectively separated (removed) from the supplied primary regulating gas.

[0165] By adjusting the gas composition in step (13), the raw material composition can be adjusted to a composition suitable for the reaction in step (14) described later. This can increase the conversion rate to alcohol.

[0166] Step (14) is a step of obtaining alcohol by reacting carbon monoxide and carbon dioxide contained in the regulating gas with hydrogen. The alcohol obtained by the reaction in step (14) refers to all compounds in which one or more hydrogen atoms of hydrocarbons are replaced by hydroxyl groups (-OH). The alcohol may be any of linear, branched and cyclic, preferably a linear or branched saturated aliphatic alcohol. In addition, the alcohol is preferably a monohydric alcohol having one hydroxyl group. Moreover, 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, 2-methyl-2-propanol, and the like. Here, 1-propanol and 2-propanol are sometimes collectively referred to as propanols, and 1-butanol, 2-butanol, 2-methyl-1-propanol, and 2-methyl-2-propanol are sometimes collectively referred to as butanols.

[0167] The reaction of carbon monoxide, carbon dioxide and hydrogen contained in the regulating gas of step (14) is carried out in a reactor filled with a catalyst. As one mode, in the case of obtaining methanol, the reactor may be, for example, a fixed bed reactor. Various designs have been made for fixed bed reactors for methanol synthesis for the purpose of large-scale and energy saving (reference: Mitsubishi Heavy Industries Technology, Vol. 33, No. 5 (1996)). In addition, the reactor may also have a condensation surface for condensing high boiling point components including the generated alcohol and water in the reactor.

[0168] The reactor with a condensation surface has a catalyst layer, a permeable wall and a condensation surface in a reaction container, and the condensation surface is configured with a space separated from the permeable wall. The reaction container is, for example, a metal container made of stainless steel with pressure resistance. The catalyst layer is an area where the regulating gas contacts the catalyst and reacts. The catalyst layer is filled with a catalyst suitable for the reaction. The permeable wall includes a porous member that allows gas to pass through. The permeable wall utilizes a member through which the gas containing the alcohol generated by the reaction in the catalyst layer can pass, but the catalyst cannot pass. The space is a space formed between the permeable wall and the condensation surface. The condensation surface is a surface where the gas containing the alcohol after passing through the permeable wall is cooled to a temperature below its dew point to condense the high boiling point components containing methanol and water. It should be noted that the high boiling point component refers to a component with a high boiling point, and in this specification, it refers to a component with a high boiling point in the components contained in the gas generated in the methanol conversion reaction. That is, in this specification, the high boiling point component refers to a component condensed at a temperature below the dew point of the gas generated in the methanol conversion reaction, including methanol and water.

[0169] In order to keep the condensing surface at a temperature below the dew point, a first heat medium region for circulating the first heat medium may be provided in the reactor. In addition, a second heat medium region may also be provided for circulating the second heat medium for recovering the heat generated by the reaction in the catalyst layer.

[0170] As another embodiment, when obtaining an alcohol having 2 or more carbon atoms, the catalyst in the reactor may be set in a form other than a fixed bed, such as a fluidized bed or a moving bed.

[0171] 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 in the form of a single substance (Cu). The constituent components of the catalyst are not limited to the above components, and may contain other elements.

[0172] In addition, the catalyst for methanol production may contain an alkali metal. The lower limit of the content of the alkali metal in the catalyst may be 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 content of the alkali metal in the above-mentioned catalyst is 0.05% by mass or less, 0.04% by mass or less, or 0.03% by mass or less. When the content of the alkali metal is too much, it is sometimes easy to cause agglomeration of Cu crystals and reduce activity faster. The alkali metal content in the catalyst may be 0% by mass.

[0173] Examples of alkali metals include Na, K, and Rb. In one embodiment, the alkali metal is Na.

[0174] The method for producing the methanol production catalyst is not particularly limited and may be a known method. For example, the catalyst may be produced by precipitating an acid salt aqueous solution of each metal element constituting the catalyst using a precipitant, followed by drying and calcining (see Japanese Patent Application Publication No. 2010-194421).

[0175] The reaction conditions in the method for producing a catalyst for producing methanol may be, for example, a reaction temperature of 150° C. to 300° C. and a reaction pressure (gauge pressure) of 0.5 MPa-G to 10 MPa-G.

[0176] The catalyst for methanol production may be used directly or 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 preferred that the CuO-ZnO catalyst be brought into contact with a gas containing hydrogen to convert the catalyst into a reduced Cu-ZnO catalyst, and then brought into contact with a regulating gas.

[0177] In another embodiment, the catalyst used in step (14) may be a catalyst for producing alcohols having a carbon number of 2 or more. The catalyst for producing alcohols having a carbon number of 2 or more may be an aggregate of catalyst metals or a supported catalyst in which the catalyst metal is supported on a carrier, preferably a supported catalyst. By using a supported catalyst, the contact efficiency between the regulating gas and the catalyst metal is improved.

[0178] As a carrier, a carrier used in the catalyst in the past can be used, for example, a porous carrier is preferred. The material of the porous carrier is not particularly limited, and examples thereof include: silicon dioxide, zirconium oxide, titanium dioxide, magnesium oxide, aluminum oxide, activated carbon, zeolite, etc. In addition, as a catalyst, a known catalyst can be used. For example, reference can be made to: Catalyst 2022, 64, 33, Catalyst 2020, 62, 133, Chem. Soc. Rev. 2017, 46, 1358, Journal of Petroleum Society 1990, 33, 1 and other documents.

[0179] The catalyst may be in the form of a powder or a molded body, without any particular limitation. The molded body may be in the form of a granular, cylindrical, or annular shape, without any particular limitation. The catalyst may be molded by tablet molding, compression molding, and extrusion molding, without any particular limitation.

[0180] When the catalyst is filled into the reactor, various diluents inert to the raw gas and the reaction product may be mixed with the catalyst. Examples of the diluent include copper, alumina, zirconium oxide, quartz, glass, silicon carbide, etc. Examples of the shape of the diluent include diluents formed into granular, spherical, cylindrical, etc., and diluents of irregular shapes, etc.

[0181] In addition, the usage amount of the catalyst is not particularly limited, and other reaction conditions can be considered and appropriately adjusted. In addition, the catalyst can be used alone or in combination of two or more. In the case of using two or more, its combination and ratio can be appropriately adjusted according to the purpose.

[0182] The regulating gas in step (14) contains carbon oxide and hydrogen. Carbon oxide refers to at least one of carbon monoxide and carbon dioxide. When both carbon monoxide and carbon dioxide are used as carbon oxide, carbon monoxide and carbon dioxide may be contained in an arbitrary ratio.

[0183] The conditioning gas may contain components other than carbon oxide and hydrogen as long as they do not affect the production of alcohol. Examples of such components include saturated / unsaturated hydrocarbons such as methane, ethane, propane, ethylene, and propylene, nitrogen, and rare gas elements.

[0184] The conditioning gas may also contain water. Originally, in the production of methanol, the less water in the raw gas, the better. However, in step (14), even if a conditioning gas containing a certain amount of water is used, the stability of the catalyst can be maintained.

[0185] From the viewpoint of more efficiently obtaining alcohol, the total content of carbon oxide and hydrogen in the adjustment gas is preferably 50 vol % or more, more preferably 80 vol % or more, further preferably 90 vol % or more, and may be 100 vol %.

[0186] From the viewpoint of further improving the space-time yield of alcohol, the H 2 / (CO+CO 2 ) of the regulating gas in step (14) is preferably 1.5 or more and 4.0 or less.

[0187] The reaction in step (14) is preferably carried out under pressure, and the pressure during the reaction is preferably 1 MPa to 12 MPa. In addition, the above reaction is preferably carried out under heating conditions, and the temperature during the reaction is preferably 150°C to 500°C, and more preferably 200°C to 400°C.

[0188] When the step (14) is carried out using a fixed bed reactor, for example, a regulating gas as a raw material can be supplied from the inlet side of the reactor while adjusting the temperature to carry out the reaction, and the reaction product and unreacted raw material can be recovered from the outlet side of the reactor. The target product and unreacted raw material are usually recovered in the form of a mixed gas, but the alcohol as the target product can be separated by, for example, cooling the gas.

[0189] The alcohol obtained in step (14) may be used in the next step after being separated, or may be used directly in the state of a mixture.

[0190] In addition, in step (14), products other than alcohols are also generated (e.g., oxidation products such as acetic acid and acetaldehyde; esters such as ethyl acetate, methyl acetate, and methyl formate). Therefore, the second embodiment may include a step (14') of hydrogenating the products other than alcohols to convert them into alcohols (alcoholization step). As step (14'), for example, a method of converting oxidation products including acetaldehyde, acetic acid, etc. into alcohols by contacting them with a hydrogenation catalyst may be cited.

[0191] As the hydrogenation catalyst in step (14'), a known catalyst can be used. For example, copper, copper-zinc, copper-chromium, copper-zinc-chromium, iron, rhodium-iron, rhodium-platinum, palladium, palladium-iron, palladium-platinum, iridium-iron, rhodium-iridium-iron, iridium-platinum, rhenium-zinc, platinum, nickel, cobalt, ruthenium, rhodium oxide, palladium oxide, platinum oxide, ruthenium oxide, etc. These hydrogenation catalysts can be supported on a carrier similar to the carrier used in the above catalyst.

[0192] Alternatively, step (14) may include a step of contacting at least a portion of the product containing alcohol with an aqueous sodium hydroxide solution to remove the acidic substance.

[0193] 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. It should be noted that the unsaturated hydrocarbons having 2 to 8 carbon atoms obtained in step (15) are, as described above, olefins having 2 to 5 carbon atoms such as ethylene, propylene, butene, and pentene; diolefins 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, preferably olefins having 2 to 4 carbon atoms.

[0194] In step (15), the unsaturated hydrocarbon having 2 to 8 carbon atoms can be obtained by a known method.

[0195] The temperature of the step of obtaining olefins from a raw material containing an alcohol is not particularly limited as long as it is in the range of 300°C to 700°C, but is preferably 350°C to 600°C. By conducting the reaction at a temperature within this range, the selectivity of olefins can be prevented from decreasing. The pressure of the step of obtaining olefins from a raw material containing an alcohol is preferably 50 kPa or more in terms of gauge pressure, more preferably 150 kPa or more in terms of gauge pressure, further preferably 150 kPa to 20000 kPa in terms of gauge pressure, and particularly preferably 450 kPa to 1000 kPa in terms of gauge pressure.

[0196] As a first method for obtaining olefins from a raw material containing alcohol, for example, the method described in Japanese Patent Publication No. 02-000121 can be used, which uses a non-zeolite molecular sieve as a catalyst. Examples of non-zeolite molecular sieves include SAPO-34, SAPO-17, and mixtures thereof.

[0197] As a second method for obtaining olefins from a raw material containing an alcohol, for example, a method described in Japanese Patent No. 3844734, which uses a shape selective catalyst, can be used. Examples of the shape selective catalyst include a proton-containing Pentasil type catalyst having an alkali content of less than 380 ppm, preferably less than 200 ppm.

[0198] As a third method for obtaining olefins from a raw material containing an alcohol, for example, a method described in JP-A-2014-46273 using a catalyst obtained by subjecting CHA-type aluminosilicate to a silylation step can be used.

[0199] As a fourth method for obtaining olefins from a raw material containing an alcohol, for example, a method described in Japanese Patent Re-Publication No. 2007 / 083684 can be used, which uses a catalyst obtained by supporting one or more selected from the group consisting of nickel, aluminum, manganese, iron and copper on a regular mesoporous porous body, etc. Examples of the regular mesoporous porous body include MCM-41, etc.

[0200] As a fifth method for obtaining olefins from a raw material containing an alcohol, for example, a method described in International Publication No. 2012 / 077723 using a catalyst containing zirconium oxide having a surface ratio of 50 area % or more can be used.

[0201] As a sixth method for obtaining olefins from a raw material containing an alcohol, for example, a method described in Japanese Patent Publication No. 2012-136516 can be used, which uses a catalyst for olefin production containing an oxide of at least one element selected from the group consisting of metal elements of Groups 2 to 3, Groups 5 to 9, Groups 11 and Group 12 in the periodic table, titanium, nickel, boron, gallium, thallium, germanium, tin, lead and bismuth.

[0202] As a seventh method for obtaining olefins from a raw material containing an alcohol, for example, a method described in International Publication No. 2012 / 077724 using a catalyst for producing olefins containing an indium oxide or the like can be used.

[0203] As an eighth method for obtaining olefins from a raw material containing an alcohol, for example, a method described in Japanese Patent Gazette No. 2013-43794 can be used, which uses a silicoaluminophosphate molecular sieve and the like, and comprises hydrothermally treating a mixture containing (i) a silicon source, (ii) an aluminum source, (iii) a phosphorus source, (iv) a structure directing agent, and (v) 0.001 mol to 0.1 mol of an inorganic or organic magnesium salt or manganese salt relative to 1 mol of the aluminum source.

[0204] As a ninth method for obtaining olefins from a raw material containing an alcohol, for example, a method described in Japanese Patent Application Laid-Open No. 2010-18556 can be used, which uses a catalyst obtained by supporting one or more metals selected from Group 4 metals of the periodic table on an aluminosilicate having an MFI structure.

[0205] As the tenth method of the process of obtaining olefins from a raw material containing alcohol, in the case of dehydration reaction of alcohol, a solvent or gas inert to the catalyst and alcohol can be added into the reaction system, thereby dehydration reaction is carried out in a diluted state. The dehydration method of alcohol can be any method in batch, semi-batch or continuous flow. In addition, it can be any form in liquid phase, gas phase, gas-liquid mixed phase. As the filling method of the catalyst, various methods such as fixed bed, fluidized bed, suspended bed, tray fixed bed can be adopted, and any method can be adopted.

[0206] As a catalyst, it can be used together with a known catalyst or a molding agent (binder) etc. that can be usually used in a dehydration reaction. When the catalyst is used together with a molding agent, they can be mixed and extruded to form a molded body with improved mechanical strength. Usually, as a catalyst or a molding agent that can be used in a dehydration reaction, for example, silicon dioxide, aluminum oxide, clay, titanium dioxide, zirconium oxide, zinc oxide, cerium oxide, lanthanum oxide, graphite and ethyl cellulose etc. can be cited.

[0207] The temperature during the dehydration reaction of alcohol is preferably 450°C or less, more preferably 400°C or less, further preferably 300°C or less, and particularly preferably 200°C or less. The lower limit of the above temperature is not particularly limited as long as it is the temperature at which the dehydration reaction is carried out or more, but from the viewpoint of improving the activity of the obtained catalyst, it may be 160°C or more, or 180°C or more. The temperature of the above catalyst layer can be appropriately adjusted by changing the temperature of the device used in the dehydration treatment, etc.

[0208] 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. In addition, when the catalyst activity decreases, it can be regenerated using a known method to restore the activity of the dehydration catalyst.

[0209] The reaction pressure during the dehydration reaction is not particularly limited, but is preferably 0 KPa to 100000 KPa (gauge pressure), more preferably 0 KPa to 5000 KPa (gauge pressure), and even more preferably 0 KPa to 4000 KPa (gauge pressure).

[0210] In addition, the dehydration reaction can be carried out without pressurization, but the unsaturated hydrocarbons having 2 to 8 carbon atoms obtained by the dehydration reaction are gaseous at normal temperature and pressure when the carbon number is low, and therefore need to be liquefied for purification such as distillation. Therefore, when the unsaturated hydrocarbons having 2 to 8 carbon atoms are gaseous, they need to be liquefied by cooling, pressurization, etc., which makes the production of unsaturated hydrocarbons having 2 to 8 carbon atoms complicated.

[0211] The alcohol in the above-mentioned raw material containing alcohol may be purified alcohol, or the alcohol obtained in the process of obtaining alcohol may be used directly. In addition, it may be a mixture of alcohols obtained in the process of obtaining multiple alcohols. The alcohol in the raw material containing alcohol may contain water and / or other oxygen-containing compounds, and water and / or other oxygen-containing compounds may be intentionally added.

[0212] The reaction product containing unsaturated hydrocarbons having 2 to 8 carbon atoms is separated and purified into a plurality of products having different boiling point differences by purification. The purification can be provided in the process of the method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms of the second embodiment, or can be universalized in a complex plant that integrates different technologies. When a naphtha cracker and an ethane cracker are adjacent to each other, the reaction product can be introduced into a distillation column group of the naphtha cracker and the ethane cracker for separation and purification.

[0213] [Third Embodiment of the Method for Producing Unsaturated Hydrocarbons Having 2 to 8 Carbon Atoms]

[0214] The method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms of the third embodiment comprises the following steps: step (1), wherein a plastic mixture (A) and a residue (B) are separated from waste plastics, wherein the content of polyolefin plastic in the plastic mixture (A) is 50% by mass or more; step (2), wherein the plastic mixture (A) is decomposed to obtain a reaction product containing unsaturated hydrocarbons having 2 to 8 carbon atoms; step (3), wherein the reaction product is washed and purified to separate the unsaturated hydrocarbons having 2 to 8 carbon atoms; step (12), wherein the residue (B) is heated to obtain a reaction product containing carbon monoxide, carbon dioxide and A mixed gas of hydrogen; a step (13), wherein the mixed gas is mixed with at least one gas selected from the group consisting of carbon monoxide, carbon dioxide and hydrogen, or a part of at least one gas selected from the group consisting of carbon monoxide, carbon dioxide and hydrogen is removed from the mixed gas, thereby obtaining a regulating gas in which the volume amount of hydrogen is 1.5 to 4.0 relative to the total volume amount of carbon monoxide and carbon dioxide; a step (14), wherein the carbon monoxide, carbon dioxide and hydrogen contained in the regulating gas are reacted to obtain alcohol; and a step (15), wherein an unsaturated hydrocarbon having 2 to 8 carbon atoms is obtained using the alcohol as a raw material.

[0215] The steps (1) to (3) and (12) to (15) of the third embodiment are the same as the steps (1) to (3) of the first embodiment and the steps (12) to (15) of the second embodiment. It should be noted that the unsaturated hydrocarbons having 2 to 8 carbon atoms obtained by the steps (3) and (15) are, as described above, olefins having 2 to 5 carbon atoms such as ethylene, propylene, butene, and pentene; diolefins 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, preferably olefins having 2 to 4 carbon atoms.

[0216] In the method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms of the third embodiment, the reaction product obtained in the above step (2) preferably further contains paraffins. As a method for increasing the content of paraffins, there is a method of setting the temperature condition of the pyrolysis device in the pyrolysis step to, for example, 450°C to 750°C to carry out a pyrolysis reaction, that is, a method of carrying out a high severity pyrolysis reaction. In addition, in the case where step (2) includes a catalytic cracking step, a method of selecting a catalyst with high acidity from catalysts such as non-bound (non-loaded) zeolite catalysts, zeolite catalysts combined with a binder or a carrier, etc. is also suitable. As a binder, for example, silica, alumina, silica-alumina, silica-titania, silica-thoria, silica-magnesia, silica-zirconia, silica-beryllia, and a ternary composition of silica and other refractory oxides can be listed. Examples of the binder or matrix material include clays such as montmorillonite, kaolin, bentonite, halloysite, dickite, nacrite, and anthracite.

[0217] The reaction product containing unsaturated hydrocarbons having 2 to 8 carbon atoms is separated and purified into a plurality of products having different boiling point differences by purification. The purification can be provided in the process of the method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms of the third embodiment, or can be universalized in a complex plant that integrates different technologies. When a naphtha cracker and an ethane cracker are adjacent to each other, the reaction product can be introduced into a distillation column group of the naphtha cracker and the ethane cracker for separation and purification.

[0218] [Fourth Embodiment of the Method for Producing Unsaturated Hydrocarbons Having 2 to 8 Carbon Atoms]

[0219] The fourth embodiment of the method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms comprises the following steps: step (21), in which carbon dioxide and hydrogen are reacted to obtain a reaction mixture containing alcohol, carbon dioxide and carbon monoxide; and step (22), in which unsaturated hydrocarbons having 2 to 8 carbon atoms are obtained from the alcohol and / or carbon monoxide contained in the reaction mixture.

[0220] Step (21) is a step of reacting carbon dioxide with hydrogen to obtain a reaction mixture containing 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.

[0221] Hydrogen that can be used may be hydrogen obtained by a known method, such as hydrogen generated by a steam reforming reaction, hydrogen generated by an electrolysis 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.

[0222] Hydrogen can be produced using a hydrogen production system, which includes, for example, a pyrolysis reaction device, a solid separation device, and a gas purification device.

[0223] The hydrocarbon decomposition reaction device is a device for decomposing a gas containing hydrocarbons to generate hydrogen and solid carbon. Examples of hydrocarbons to be decomposed include methane, ethane, butane, hexane, ethylene, propylene, acetylene, etc., and methane is preferred.

[0224] One method is to decompose methane. As the raw gas containing methane, natural gas, biogas (methane) obtained by anaerobic fermentation of biomass, and waste gas containing methane produced as a by-product of hydrocarbon pyrolysis processes such as naphtha crackers or ethane crackers (pyrolysis) can be used.

[0225] Methane decomposes into hydrogen and solid carbon according to equation (10).

[0226] CH4→C+2H2(10)

[0227] As the methane decomposition reaction apparatus, known apparatuses such as a tubular reaction apparatus, a fixed bed reaction apparatus, a fluidized bed reaction apparatus, a bubbling fluidized bed reaction apparatus, a circulating fluidized bed reaction apparatus, a moving bed reaction apparatus, and a circulating moving bed reaction apparatus can be used. In addition, the decomposition method used in the methane decomposition reaction apparatus can use known methods such as a catalyst-free pyrolysis method, a decomposition method using a solid catalyst, and a decomposition method using a liquid catalyst such as a molten salt or a molten metal.

[0228] As solid catalyst, as long as it is a catalyst that can decompose hydrocarbon and produce by-product hydrogen and carbon, there is no particular restriction, and can include any numbered metals selected from various lUPAC families of the periodic table, such as the 10th family (such as nickel), the 8th family (such as iron or ruthenium), the 9th family (such as cobalt) or the 6th family (such as chromium or molybdenum). Other metals that can exist include the 7th family metal (such as manganese) or the 5th family metal (such as cobalt). The above-mentioned metals are only illustrative, and other metals of these families can also be included. In addition, the catalyst obtained by mixing more than one of these catalysts can be used as a catalyst, and it is also possible to be loaded on a catalyst carrier.

[0229] The decomposition reaction of hydrocarbons containing methane is an endothermic reaction, so the decomposition reaction device has a heating device for supplying reaction heat. As the heating device for decomposition, a heating furnace, a heat exchange device using steam or molten salt as a heat medium, a microwave heating device, a plasma heating device, an induction heating device, a resistance heating device and other known devices can be used. In addition, by using renewable energy as the energy required in the manufacturing process of hydrogen, it is possible to become a method for manufacturing hydrogen that reduces carbon dioxide emissions.

[0230] The solid separation device is a device for separating the solid-gas mixture containing hydrogen, unreacted hydrocarbons and / or solid carbon discharged from the decomposition reaction device into a solid component and a gas component. The separation device used as the solid separation device can be any device that can separate solids and gases. For example, a cyclone separator, a bag filter, a ceramic filter, a sieve and other known separation units can be used.

[0231] The separated solid carbon is in the form of carbon black, graphite, carbon nanotubes, etc. Solid carbon can be used for battery materials, raw materials for chemicals, soil improvement materials, building materials, etc.

[0232] The gas purification device is a device for separating hydrogen from a gas containing hydrogen and unreacted hydrocarbons after solids have been removed by a solid separation device, and known gas separation devices such as PSA (Pressure Swing Adsorption), cryogenic separation devices, and membrane separation devices can be used.

[0233] At least a portion of the gas component containing hydrogen and unreacted hydrocarbons separated by the solid separation device can be separated into hydrogen and a gas component containing unreacted hydrocarbons by a gas purification device.

[0234] The hydrogen separated by the gas purification device can also be used as a raw material and fuel for other chemical products. The gas component containing unreacted hydrocarbons separated from the hydrogen by the gas purification device can be fed back to the decomposition reaction device as a raw material. This can improve the conversion rate of hydrocarbons.

[0235] For carbon dioxide, for example, carbon dioxide recovered from the atmosphere, carbon dioxide recovered from various factories, incinerators, etc. that emit carbon dioxide, etc., etc., can be cited. As examples of carbon dioxide recovered from various factories that emit carbon dioxide, carbon dioxide recovered from flue gas of a steam reformer by chemical absorption, membrane separation or pressure swing adsorption (PSA), carbon dioxide obtained by a carbon dioxide gas recovery process of an ammonia plant, carbon dioxide recovered from blast furnace gas or coke oven gas produced by a steel plant by chemical absorption, membrane separation or pressure swing adsorption (PSA), and carbon dioxide recovered from waste gas after fuel combustion in a thermal power plant by chemical absorption, membrane separation or pressure swing adsorption (PSA), in addition, carbon dioxide recovered from incineration facilities such as garbage by the above methods, obtained by a carbon dioxide gas recovery process of an ammonia plant, etc. It should be noted that in the case where the gas containing carbon dioxide contains impurities such as chlorine compounds, carbon dioxide from which the impurities have been removed in advance is used.

[0236] In step (21), carbon dioxide is reacted with hydrogen to obtain a reaction mixture containing alcohol, carbon dioxide and carbon monoxide. The alcohol contained in the reaction mixture refers to all compounds in which one or more hydrogen atoms of a hydrocarbon are replaced by a hydroxyl group (-OH). The alcohol may be any of linear, branched and cyclic, preferably a linear or branched saturated aliphatic alcohol. In addition, the alcohol is preferably a monohydric alcohol having one hydroxyl group. Moreover, an alcohol having 1 to 5 carbon atoms is preferred, and an alcohol having 1 to 4 carbon atoms is more preferred. Examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, and the like.

[0237] The raw materials in the process (21) are hydrogen and carbon dioxide. Therefore, the process (21) is substantially the same as the process (14) of the second embodiment, but in the case of using only carbon dioxide as a raw material, compared with the case of containing carbon monoxide, the reaction product contains a large amount of water and the equilibrium conversion is low. When there is a lot of water in the reaction product, the catalyst is easily deactivated, so it is necessary to use a catalyst with strong water resistance. In order to cope with the problem of low equilibrium conversion, it is preferred to actively remove the alcohol and water generated in the reaction. Therefore, the reactor preferably has a condensation surface for condensing the high-boiling-point components of the alcohol and water generated in the reactor. As a result, a reaction mixture containing alcohol, carbon dioxide and carbon monoxide can be obtained.

[0238] 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. It should be noted that the unsaturated hydrocarbons having 2 to 8 carbon atoms obtained by step (22) are, as described above, olefins having 2 to 5 carbon atoms such as ethylene, propylene, butene, and pentene; diolefins 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, preferably olefins having 2 to 4 carbon atoms.

[0239] The method for producing the unsaturated hydrocarbon having 2 to 8 carbon atoms from alcohol and / or carbon monoxide is not particularly limited, and a known method may be used.

[0240] The temperature of the step of producing unsaturated hydrocarbons having 2 to 8 carbon atoms from alcohols and / or carbon monoxide is preferably 200° C. to 400° C., more preferably 250° C. to 350° C. In addition, the pressure of 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 MPa to 10 MPa, and particularly preferably 0.3 MPa to 5 MPa.

[0241] As a method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms from alcohols and / or carbon monoxide, for example, the following methods can be used: a method described in Japanese Patent Publication No. 2014-55126 using a catalyst containing iron, cobalt, etc.; a method described in Japanese Patent Re-Publication No. 2014 / 024774 using a catalyst containing iron, cobalt and nickel or ruthenium, etc.; a method described in Japanese Patent Publication No. 2022-30433 using a catalyst having a core-shell structure with a solid containing at least iron and manganese as a core and a solid containing at least silicon and a zeolite of Group 13 elements as a shell, etc. In addition, the catalyst described in pages 210 to 214 of "Carbon Cycle Technology 2021 from the Perspective of Catalysts" (CMC Research, issued on April 20, 2021) can also be used appropriately.

[0242] The reaction product containing unsaturated hydrocarbons having 2 to 8 carbon atoms is separated and purified into a plurality of products having different boiling point differences by purification. The purification can be provided in the process of the method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms of the fourth embodiment, or can be universalized in a complex plant that integrates different technologies. When a naphtha cracker and an ethane cracker are adjacent to each other, the reaction product can be introduced into a distillation column group of the naphtha cracker and the ethane cracker for separation and purification.

[0243] [Fifth Embodiment of the Method for Producing Unsaturated Hydrocarbons Having 2 to 8 Carbon Atoms]

[0244] The method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms of the fifth embodiment is a method of combining the method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms of any one of the first to third embodiments and the method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms of the fourth embodiment.

[0245] One mode of the fifth embodiment includes the following steps: step (1), wherein a plastic mixture (A) and a residue (B) are separated from waste plastics, wherein the content of polyolefin plastic in the plastic mixture (A) is 50% by mass or more; step (2), wherein the plastic mixture (A) is decomposed to obtain a reaction product containing unsaturated hydrocarbons having a carbon number of 2 to 8; step (3), wherein the reaction product is cleaned and purified to separate the unsaturated hydrocarbons having a carbon number of 2 to 8; step (21), wherein carbon dioxide is reacted with hydrogen to obtain a reaction mixture containing alcohol, carbon dioxide and carbon monoxide; and step (22), wherein unsaturated hydrocarbons having a carbon number of 2 to 8 are obtained from the alcohol and / or carbon monoxide contained in the reaction mixture.

[0246] Another mode of the fifth embodiment includes the following steps: step (1), wherein a plastic mixture (A) and a residue (B) are separated from waste plastics, wherein the content of polyolefin plastic in the plastic mixture (A) is 50% by mass or more; step (12), wherein the residue (B) is heated to obtain a mixed gas containing carbon monoxide, carbon dioxide and hydrogen; and step (13), wherein the mixed gas is mixed with at least one gas selected from the group consisting of carbon monoxide, carbon dioxide and hydrogen, or at least one gas selected from the group consisting of carbon monoxide, carbon dioxide and hydrogen is removed from the mixed gas. a portion of the reaction mixture, thereby obtaining a regulating gas in which the volume amount of hydrogen is 1.5 to 4.0 relative to the total volume amount of carbon monoxide and carbon dioxide; step (14), wherein the carbon monoxide, carbon dioxide and hydrogen contained in the regulating gas are reacted to obtain alcohol; step (15), wherein unsaturated hydrocarbons having 2 to 8 carbon atoms are obtained using alcohol as a raw material; step (21), wherein carbon dioxide and hydrogen are reacted to obtain a reaction mixture containing alcohol, carbon dioxide and carbon monoxide; and step (22), wherein unsaturated hydrocarbons having 2 to 8 carbon atoms are obtained from the alcohol and / or carbon monoxide contained in the reaction mixture.

[0247] Another mode of the fifth embodiment includes the following steps: step (1), wherein a plastic mixture (A) and a residue (B) are separated from waste plastics, wherein the content of polyolefin plastic in the plastic mixture (A) is 50% by mass or more; step (2), wherein the plastic mixture (A) is decomposed to obtain a reaction product containing unsaturated hydrocarbons having a carbon number of 2 to 8; step (3), wherein the reaction product is cleaned and purified to separate the unsaturated hydrocarbons having a carbon number of 2 to 8; step (12), wherein the residue (B) is heated to obtain a mixed gas containing carbon monoxide, carbon dioxide and hydrogen; step (13), wherein the mixed gas is mixed with at least one gas selected from the group consisting of carbon monoxide, carbon dioxide and hydrogen. Mixing 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 a regulating gas in which the volume amount of hydrogen is 1.5 to 4.0 relative to the total volume amount of carbon monoxide and carbon dioxide; step (14), wherein the carbon monoxide, carbon dioxide and hydrogen contained in the regulating gas are reacted to obtain alcohol; step (15), wherein unsaturated hydrocarbons having 2 to 8 carbon atoms are obtained using alcohol as a raw material; step (21), wherein carbon dioxide and hydrogen are reacted to obtain a reaction mixture containing alcohol, carbon dioxide and carbon monoxide; and step (22), wherein unsaturated hydrocarbons having 2 to 8 carbon atoms are obtained from the alcohol and / or carbon monoxide contained in the reaction mixture.

[0248] Steps (1) to (3), steps (12) to (15), step (21), and step (22) in the fifth embodiment are respectively the same as 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.

[0249] The reaction product containing unsaturated hydrocarbons having 2 to 8 carbon atoms is separated and purified into a plurality of products having different boiling point differences by purification. The purification can be provided in the process of the method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms of the fifth embodiment, or can be universalized in a complex plant that integrates different technologies. When a naphtha cracker and an ethane cracker are adjacent to each other, the reaction product can be introduced into a distillation column group of the naphtha cracker and the ethane cracker for separation and purification.

[0250] [Sixth Embodiment of the Method for Producing Unsaturated Hydrocarbons Having 2 to 8 Carbon Atoms]

[0251] The sixth embodiment of the method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms is a method obtained by combining the method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms of any one of the first to fourth embodiments and a method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms comprising step (31), wherein at least one alcohol selected from the group consisting of ethanol, propanol and butanol is subjected to a dehydration reaction to obtain unsaturated hydrocarbons having 2 to 8 carbon atoms.

[0252] One mode of the sixth embodiment includes the following steps: step (1), wherein a plastic mixture (A) and a residue (B) are separated from waste plastics, wherein the content of polyolefin plastic in the plastic mixture (A) is 50% by mass or more; step (2), wherein the plastic mixture (A) is decomposed to obtain a reaction product containing unsaturated hydrocarbons having a carbon number of 2 to 8; step (3), wherein the reaction product is cleaned and purified to separate the unsaturated hydrocarbons having a carbon number of 2 to 8; and step (31), wherein at least one alcohol selected from the group consisting of ethanol, propanol and butanol is subjected to a dehydration reaction to obtain unsaturated hydrocarbons having a carbon number of 2 to 8.

[0253] Another mode of the sixth embodiment comprises the following steps: step (1), wherein a plastic mixture (A) and a residue (B) are separated from waste plastics, wherein the content of polyolefin plastic in the plastic mixture (A) is 50% by mass or more; step (12), wherein the residue (B) is heated to obtain a mixed gas containing carbon monoxide, carbon dioxide and hydrogen; step (13), wherein the mixed gas is mixed with at least one gas selected from the group consisting of carbon monoxide, carbon dioxide and hydrogen, or the mixed gas is removed from the mixed gas. and hydrogen, thereby obtaining a regulating gas in which the volume amount of hydrogen is 1.5 to 4.0 relative to the total volume amount of carbon monoxide and carbon dioxide; step (14), wherein the carbon monoxide, carbon dioxide and hydrogen contained in the regulating gas are reacted to obtain alcohol; step (15), wherein unsaturated hydrocarbons having 2 to 8 carbon atoms are obtained using alcohol as a raw material; and step (31), wherein at least one alcohol selected from the group consisting of ethanol, propanol and butanol is subjected to a dehydration reaction to obtain unsaturated hydrocarbons having 2 to 8 carbon atoms.

[0254] Another mode of the sixth embodiment comprises the following steps: step (1), wherein a plastic mixture (A) and a residue (B) are separated from waste plastics, wherein the content of polyolefin plastic in the plastic mixture (A) is 50% by mass or more; step (2), wherein the plastic mixture (A) is decomposed to obtain a reaction product containing unsaturated hydrocarbons having 2 to 8 carbon atoms; step (3), wherein the reaction product is cleaned and purified to separate the unsaturated hydrocarbons having 2 to 8 carbon atoms; step (12), wherein the residue (B) is heated to obtain a mixed gas containing carbon monoxide, carbon dioxide and hydrogen; step (13), wherein the mixed gas is mixed with a hydrocarbon selected from the group consisting of carbon monoxide, carbon dioxide and hydrogen; At least one gas selected from the group consisting of carbon monoxide and hydrogen is mixed, or a part of at least one gas selected from the group consisting of carbon monoxide, carbon dioxide and hydrogen is removed from the mixed gas to obtain a regulating gas in which the volume amount of hydrogen is 1.5 to 4.0 relative to the total volume amount of carbon monoxide and carbon dioxide; step (14), wherein the carbon monoxide, carbon dioxide and hydrogen contained in the regulating gas are reacted to obtain alcohol; step (15), wherein unsaturated hydrocarbons having 2 to 8 carbon atoms are obtained using alcohol as a raw material; and step (31), wherein at least one alcohol selected from the group consisting of ethanol, propanol and butanol is subjected to a dehydration reaction to obtain unsaturated hydrocarbons having 2 to 8 carbon atoms.

[0255] Another mode of the sixth embodiment includes the following steps: step (21), wherein carbon dioxide and hydrogen are reacted to obtain a reaction mixture containing alcohol, carbon dioxide and carbon monoxide; step (22), wherein unsaturated hydrocarbons having 2 to 8 carbon atoms are obtained from the alcohol and / or carbon monoxide contained in the reaction mixture; and step (31), wherein at least one alcohol selected from the group consisting of ethanol, propanol and butanol is subjected to a dehydration reaction to obtain unsaturated hydrocarbons having 2 to 8 carbon atoms.

[0256] Steps (1) to (3), (12) to (15), (21) and (22) in the sixth embodiment are the same as 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.

[0257] Step (31) is a step of subjecting an alcohol to a dehydration reaction to obtain an unsaturated hydrocarbon having 2 to 8 carbon atoms. The alcohol used in step (31) is ethanol, propanol or butanol.

[0258] The ethanol, propanol and butanol used in step (31) may be those produced from synthesis gas by a chemical method using a metal catalyst, or may be those produced by a fermentation method.

[0259] Examples of the metal catalyst include: a hydrogenation active metal, or a combination of a hydrogenation active metal and a co-activating metal. The hydrogenation active metal may be any hydrogenation active metal that is known to be capable of synthesizing ethanol from a mixed gas, for example: 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; elements belonging to Group 10 of the periodic table such as nickel and palladium, etc.

[0260] These hydrogenation active metals may be used alone or in combination of two or more. As the hydrogenation active metal, from the perspective of further improving the carbon monoxide conversion rate and improving the selectivity of ethanol, for example, a hydrogenation active metal obtained by combining rhodium, manganese and lithium; a hydrogenation active metal obtained by combining ruthenium, rhenium and sodium; a hydrogenation active metal obtained by combining rhodium or ruthenium, an alkali metal and other hydrogenation active metals is preferred.

[0261] Examples of the co-activating metal include titanium, magnesium, and vanadium. By supporting the co-activating metal in addition to the hydrogenation active metal, the carbon monoxide conversion rate, the ethanol selectivity, and the like can be further improved.

[0262] The catalyst used in step (14) is also a catalyst suitable for this reaction.

[0263] In the manufacture of alcohol by fermentation, cultivation is typically carried out in a bioreactor. It should be noted that the term "bioreactor" includes: a continuous stirred tank reactor (CSTR), an immobilized cell reactor (ICR), a trickle bed reactor (TBR), a bubble tower, a gas lift fermenter, a static mixer, other containers suitable for gas-liquid contact, or other devices having more than one container, tower, pipeline structure, etc. Fermentation device. In one embodiment, the bioreactor may include a first proliferation reactor and a second fermentation reactor. The raw material of the alcohol is provided to one or both of these reactors.

[0264] The bioreactor may be of any shape, and examples thereof include stirred type, airlift type, bubble column type, ring type, open coupling type, photobiological type, etc. The bioreactor is preferably a known ring type reactor having a main tank portion and a reflux portion.

[0265] As raw materials used in the fermentation method, crops such as sugar cane, beet, corn, wheat, rice, sweet potato, and potato can be used; inedible lignocellulosic raw materials, preferably lignocellulosic raw materials. Lignocellulosic raw materials include cellulose and hemicellulose (hereinafter sometimes referred to as celluloses), and celluloses can be decomposed into sugars such as glucose and xylose by using saccharifying enzymes, and the obtained sugars are fermented to obtain alcohol.

[0266] Examples of lignocellulosic raw materials include wood, straw, wheat straw, bagasse, bamboo, corn (stems, leaves, cores, etc.), pulp, and waste products thereof (such as waste paper, etc.). The lignocellulosic raw materials may be used alone or in combination of two or more.

[0267] Examples of pulp include wood pulp obtained from conifers, broadleaf trees, forest residues, construction waste, etc.; non-wood pulp such as cotton lint or cotton wool, hemp, wheat straw, bagasse, etc.; waste paper pulp or deinked pulp made from waste paper, etc. As a method for making pulp, a method for highly removing lignin such as a chemical pulping method such as alkali extraction and alkali cooking is preferred. Among pulps made by chemical pulping methods, papermaking pulp is preferred from the perspective of easy availability. Examples of pulp for papermaking include: chemical pulps such as broadleaf kraft pulp (e.g., bleached kraft pulp (LBKP), unbleached kraft pulp (LUKP), and oxygen-bleached kraft pulp (LOKP)), coniferous kraft pulp (e.g., bleached kraft pulp (NBKP), unbleached kraft pulp (NUKP), and oxygen-bleached kraft pulp (NOKP)), sulfite pulp (SP), and alkaline pulp (AP); and semi-chemical pulps such as semi-chemical pulp (SCP) and chemical groundwood pulp (CGP). The pulp is preferably broadleaf kraft pulp, coniferous kraft pulp, sulfite pulp (SP), and semi-chemical pulp (SCP), and more preferably broadleaf bleached kraft pulp (LBKP) and coniferous oxygen-bleached kraft pulp (NOKP).

[0268] As the woody lignocellulose raw materials among the lignocellulose raw materials other than pulp, there can be listed: papermaking trees, forest residues, thinning wood, etc., debris or bark, sprouts from woody plant stumps, sawdust or sawdust from sawmills, etc., street tree pruning branches and leaves, construction waste, etc. As the above-mentioned woody lignocellulose raw materials, Eucalyptus (Eucalyptus), Salix (Salix), Poplar, Acacia (Acacia), Cryptomeria (Cryptomeria) and the like can be used. Among these, Eucalyptus, Acacia, and Willow are easy to collect in large quantities as raw materials, so they are preferred. As herbaceous lignocellulose raw materials, there can be listed: agricultural wastes such as kenaf, rice straw, wheat straw, corn cobs, and bagasse; residues and wastes of industrial crops such as oil crops and rubber (for example, EFB: Empty Fruit Bunch (palm empty fruit bunch)); sugarcane grass, Miscanthus, elephant grass, etc. as herbaceous energy crops.

[0269] In addition, the lignocellulosic raw materials other than pulp can be biomass. As biomass, paper, waste paper, pulp sludge, sludge, sewage sludge, food waste, etc. from wood can be listed. These biomasses can be used alone or in combination. In addition, biomass can be a dry solid substance, a solid substance containing water, or a slurry.

[0270] In addition, the lignocellulosic raw materials used for the fermentation method can be pretreated. Examples of pretreatments include coarse pulverization, blasting, and hydrolysis. In the coarse pulverization, the lignocellulosic raw materials are coarsely pulverized using a crusher or a grinder. At this time, it is preferred to make small pieces with an average diameter of 10 mm to 100 mm or less. The coarsely pulverized lignocellulosic raw materials are steamed using an aqueous solution of a metal hydroxide such as sodium hydroxide. The steaming treatment removes part of the lignin contained in the bagasse, and the reactivity of cellulose and hemicellulose with enzymes is improved. The biomass after the steaming treatment is neutralized using an acid.

[0271] In addition, during the blasting treatment, the hemicellulose component of the lignocellulosic raw material is saccharified and part of the lignin is removed. The lignocellulosic raw material treated by the blasting device contains C5 saccharification liquid from hemicellulose, lignin dissolved material and solid residue. When the C5 saccharification liquid and the C6 saccharification liquid are separated for hemicellulose sugar fermentation, the blasting product is subjected to solid-liquid separation by a filter press or the like, and is divided into a blasting liquid and a solid residue. For the solid residue, the sugars contained in the solid residue can be recovered by further washing with water. It should be noted that when C5 sugar fermentation and C6 sugar fermentation are carried out simultaneously, the implementation of solid-liquid separation is optional. It should be noted that the conditions for the blasting treatment are, for example, 200°C to 240°C, 1.5MPa to 4MPa, 1 minute to 15 minutes, preferably 225°C to 230°C, 2.5MPa to 3MPa, 1 minute to 5 minutes.

[0272] The solid residue obtained by the blasting treatment is washed with water to remove sugars and lignin dissolved products, and then immersed in an ethanol aqueous solution with an ethanol concentration of 30% or more, preferably 50% or more, at room temperature for 0.5 hours or more and 48 hours or less, preferably 1 hour or more and 24 hours or less, so as to dissolve and remove the lignin covering the cellulose. After immersion in ethanol, the solid residue is mechanically deethanolized or deethanolized by heating or reduced pressure heating. In the case of using a high concentration ethanol aqueous solution, the deethanolization treatment can be performed after washing with water.

[0273] For the hemicellulose contained in the lignocellulosic raw materials, it is hydrolyzed by high-temperature and high-pressure water or decomposed by hemicellulose hydrolyzing enzymes such as hemicellulase. In the case of hydrolysis by high-temperature and high-pressure water, if the temperature is above 140°C and below 180°C, the hemicellulose can be decomposed into sugars (mainly C5 monosaccharides). In the case of biomass with a high hemicellulose content, when treated at high temperature, C5 monosaccharides are excessively decomposed into organic acids, etc., so it is preferably decomposed under relatively mild conditions. It should be noted that when hemicellulose is hydrolyzed by high-temperature and high-pressure water, it is also preferred to add an acid such as phosphoric acid or hydrochloric acid as a catalyst. In addition, when hemicellulose is hydrolyzed by hemicellulose hydrolyzing enzymes, commercially available enzymes can be used, and microorganisms that produce hemicellulase can also be used.

[0274] The carbon source of the fermentation reaction in the fermentation method is a gaseous substrate containing carbon monoxide. The gaseous substrate can be a by-product of an industrial process, a waste gas containing carbon monoxide obtained from automobile exhaust. As industrial processes, there can be cited: ferrous metal product manufacturing, such as steel mills, non-ferrous product manufacturing, petroleum refining processes, coal gasification, power generation, carbon black generation, ammonia generation, methanol generation, coke manufacturing, etc. For the gaseous substrate, any convenient method can be used to capture it from the industrial process before releasing it into the atmosphere. Depending on the composition of the gaseous substrate, it is also desirable to treat the gaseous substrate before introducing it into the fermentation in order to remove any unwanted impurities such as dust particles. For example, the gaseous substrate can be filtered or cleaned using known methods.

[0275] In addition, the gaseous substrate can be supplied by the gasification of biomass. The gasification process involves the partial combustion of biomass under a limited supply of air or oxygen. The resulting gas typically contains mainly carbon monoxide and hydrogen, and contains minimal amounts of carbon dioxide, methane, ethylene and ethane. For example, biomass byproducts obtained during the extraction and treatment of foods such as sugar from sugar cane or starch from corn or cereals or non-food biomass waste produced by forestry can be gasified in order to generate gaseous substrates.

[0276] The gaseous substrate contains, for example, at least 20% to 100% by volume, 43% to 95% by volume, 60% to 90% by volume, or 70% to 90% by volume of carbon monoxide. In one embodiment, the gaseous substrate contains 25%, 30%, 35%, 40%, 45%, or 50% by volume of carbon monoxide. In particular, in the presence of hydrogen and carbon dioxide, a gaseous substrate having a lower concentration of carbon monoxide, such as 6% by volume, may also be appropriate.

[0277] In addition, industrial combustion waste gas containing carbon dioxide and hydrogen can also be used as a gaseous substrate. As an industrial combustion waste gas, for example, it is waste gas from a hydrogen manufacturing plant. The waste gas from a hydrogen manufacturing plant contains 50% to 60% carbon dioxide, 20% to 30% hydrogen, 5% to 15% carbon monoxide and 5% to 15% methane. In addition, the waste gas in ammonia production is rich in carbon dioxide and hydrogen. In addition, as industrial combustion waste gas, it can be listed: gas generated by the treatment of any carbon raw material, such as petroleum, coal and biomass.

[0278] Processes for producing ethanol and other alcohols from gaseous substrates are known. Exemplary processes include, for example, those described in International Publication No. 2007 / 117157, International Publication No. 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.

[0279] The gaseous substrate may be waste. The waste may be industrial waste such as industrial solid waste, or general waste such as municipal solid waste (MSW), including plastic waste, kitchen waste, discarded tires, biomass waste, food waste, building materials, wood, sawdust, fiber, paper and other combustible materials. Municipal solid waste (MSW) is preferred as the waste.

[0280] The gaseous substrate is preferably a synthesis gas containing carbon monoxide and hydrogen. Hereinafter, a case where the gas from waste is synthesis gas is described in detail. Synthesis gas can be obtained by performing a raw gas generation step, wherein the raw gas generation step generates the raw gas by gasifying the waste, and then performing a synthesis gas purification step, wherein the synthesis gas purification step removes or reduces specific substances such as various pollutants, smoke particles, impurities, and undesirable compounds from the generated raw gas.

[0281] In the raw gas generation process, the waste can be gasified using, for example, a gasifier. A gasifier is a furnace that burns (incompletely burns) a carbon source. Examples of gasifiers include vertical furnaces, kilns, fluidized bed furnaces, gasification reforming furnaces, plasma gasifiers, and the like. The temperature for gasifying the waste into raw gas is not particularly limited, but is generally 100°C to 2500°C, preferably 200°C to 2100°C.

[0282] The raw gas obtained by gasifying the waste may contain carbon monoxide and hydrogen, but may also contain carbon dioxide, oxygen, and nitrogen. In addition, the raw gas may also contain components such as coal, tar, nitrogen-containing compounds, sulfur-containing compounds, phosphorus-containing compounds, and organic compounds. The raw gas typically contains 0.1% to 80% by volume of carbon monoxide and 0.1% to 80% by volume of hydrogen. In addition, it may contain 0.1% to 70% by volume of carbon dioxide.

[0283] The raw gas can be generated in the form of a gas containing 0.1% by volume or more, preferably 10% by volume or more, and more preferably 20% by volume or more of carbon monoxide by performing a heat treatment (commonly known as gasification) to burn the waste (incomplete combustion), that is, by partially oxidizing the waste, but there is no particular limitation.

[0284] The raw gas is preferably produced into synthesis gas by removing or reducing specific substances such as various pollutants, soot particles, impurities, and undesirable compounds.

[0285] In the synthesis gas purification process, for example, the raw gas can be purified by treating with one or more of a water separation device such as a gas cooler, a separation device of a low-temperature separation method (cryogenic method), a cyclone separator, a particle separation device for separating particles of coal, etc. using various filters of a bag filter, a water-soluble impurity separation device such as a scrubber, a desulfurization device (sulfide separation device), a separation device of a membrane separation method, a deoxygenation device, a separation device of a pressure swing adsorption method (PSA), a separation device of a temperature swing adsorption method (TSA), a separation device of a pressure swing temperature swing adsorption method (PTSA), a separation device using activated carbon, a separation device using a deoxygenation catalyst, specifically, a copper catalyst or a palladium catalyst, etc., to obtain synthesis gas.

[0286] When alcohol is obtained by fermentation, it is preferred to reduce the concentration of carbon dioxide in the raw gas. Preferably, for example, a pressure swing adsorption separation device filled with a regenerative adsorbent containing zeolite is used to adsorb carbon dioxide in the synthesis gas on the regenerative adsorbent to reduce the concentration of carbon dioxide in the synthesis gas.

[0287] The obtained synthesis gas contains at least carbon monoxide and hydrogen, and may further contain carbon dioxide and nitrogen. The carbon monoxide concentration in the synthesis gas is 20% to 80% by volume, preferably 25% to 50% by volume, and more preferably 30% to 45% by volume relative to the total concentration of carbon monoxide, carbon dioxide, hydrogen and nitrogen in the synthesis gas.

[0288] The hydrogen concentration in the synthesis gas is generally 10 to 80% by volume, preferably 30 to 55% by volume, and more preferably 30 to 50% by volume relative to the total concentration of carbon monoxide, carbon dioxide, hydrogen and nitrogen in the synthesis gas.

[0289] The carbon dioxide concentration in the synthesis gas is not particularly limited, and is generally 0.1% by volume or more and 40% by volume or less, preferably 0.3% by volume or more and 30% by volume or less, relative to the total concentration of carbon monoxide, carbon dioxide, hydrogen and nitrogen in the synthesis gas. With respect to the carbon dioxide concentration, when ethanol is produced by microbial fermentation, it is particularly preferred to reduce the carbon dioxide concentration, and from such a viewpoint, it is more preferably 0.5% by volume or more and 25% by volume or less.

[0290] The nitrogen concentration in the synthesis gas is 40 vol% or less, preferably 1 vol% to 20 vol%, and more preferably 5 vol% to 15 vol%, relative to the total concentration of carbon monoxide, carbon dioxide, hydrogen and nitrogen in the synthesis gas.

[0291] The concentrations of carbon monoxide, carbon dioxide, hydrogen and nitrogen in the synthesis gas can be adjusted to a predetermined range by appropriately changing the type of waste, the gasification temperature in the raw gas generation process, the oxygen concentration of the supply gas during gasification and other combustion conditions. For example, the following methods are included: when it is desired to change the concentration of carbon monoxide and hydrogen, the waste is changed to a waste with a high ratio of hydrocarbons (carbon and hydrogen) such as waste plastics; when it is desired to reduce the nitrogen concentration, a gas with a high oxygen concentration is supplied in the raw gas generation process.

[0292] In addition, the concentration of each component of carbon monoxide, carbon dioxide, hydrogen and nitrogen can be appropriately adjusted for at least one of the raw gas and the synthesis gas. For concentration adjustment, at least one of these components can be added to the raw gas or the synthesis gas. The added amount is, for example, less than 50% by volume, preferably less than 30% by volume, and more preferably less than 10% by volume relative to the total amount of the raw gas or the synthesis gas.

[0293] The alcohol produced by fermentation differs depending on the microorganism. Ethanol, propanol, and butanol are described below.

[0294] The generation of ethanol in the fermentation method is described. As microorganisms that generate ethanol by fermentation, yeast and bacteria can be cited. Yeast is preferably capable of fermenting sugars (hexoses, pentoses). Specifically, yeasts include yeasts of the genus Saccharomyces such as Saccharomyces cerevisiae, yeasts of the genus Pichia such as Pichiastipitis, yeasts of the genus Candida such as Candida shihatae, yeasts of the genus Pachysolen tannophilus, yeasts of the genus Issatchenkia such as Issatchenkiaorientalis. As yeast, yeasts belonging to the genus Saccharomyces and Issatchenkia are preferred, and Saccharomyces cerevisiae and Issatchenkia orientalis are more preferred. In addition, genetically recombinant yeasts made using genetic recombination technology can also be used. As genetically recombinant yeasts, yeasts that can ferment hexoses and pentoses at the same time can be used without particular restrictions.

[0295] A certain anaerobic microorganism is cultured in a liquid culture medium. For example, a liquid culture medium and gas-utilizing bacteria can be supplied and stored, and in this state, the liquid culture medium is stirred while supplying synthesis gas into the bioreactor. Thus, the gas-utilizing bacteria can be cultured in the liquid culture medium, and ethanol can be generated from the synthesis gas through its fermentation.

[0296] In the bioreactor, the temperature of the culture medium (culture temperature) can be any temperature, and can be preferably set to 30°C to 45°C, more preferably to 33°C to 42°C, and further preferably to 36.5°C to 37.5°C. In addition, the culture time is preferably more than 1 hour in a continuous culture mode, more preferably more than 7 days, particularly preferably more than 30 days, and most preferably more than 60 days. The upper limit is not particularly set, but from the viewpoint of regular maintenance of the equipment, it is preferably less than 720 days, and more preferably less than 365 days. It should be noted that the culture time refers to the time from the addition of the inoculum to the culture tank to the discharge of the entire amount of the culture solution in the culture tank.

[0297] Some anaerobic bacteria are known to carry out fermentation of alcohols and acetic acid containing ethanol from carbon dioxide and hydrogen. Acetogenic bacteria have the ability to convert gaseous substrates into acetic acid, ethanol and other fermentation products through the Wood-Ljungdahl approach. As such bacteria, for example, strains of Acetobacter Woodii, which is a bacterium of the genus Acetobacter, can be cited (Demler, M., Weuster-Botz, "Reaction Engineering Analysis of Hydrogenotrophic Production of Acetic Acid by Acetobacterum Woodii", Biotechnology and Bioengineering, Vol. 108, No. 2, February 2011), etc. It is shown that Acetobacter Woodii produces acetate by fermentation of gaseous substrates containing carbon dioxide and hydrogen. Buschhorn et al. confirmed the ability of Acetobacter Woodii to produce ethanol in glucose fermentation using limited phosphate.

[0298] In addition, some anaerobic bacteria are known to carry out fermentation to produce ethanol from carbon monoxide. Such bacteria are preferably bacteria having a metabolic pathway for acetyl COA. Examples of such bacteria include Clostridium autoethanogenum, Clostridium ljungdahlii, Clostridium aceticum, Clostridium carboxidivorans, Moorella thermoacetica, and Acetobacterium woodii. Among these, ethanologenic Clostridium is preferred.

[0299] Fermentation is expected to be carried out under appropriate conditions for fermentation to occur. As reaction conditions to be considered, pressure, temperature, gas flow, liquid flow, fermentation liquid pH, fermentation liquid redox potential, stirring speed (when using a continuous stirred tank reactor), inoculation material height, for ensuring that the carbon dioxide in the liquid phase does not become the maximum gas substrate concentration of the restriction and for avoiding the highest product concentration of product inhibition. Suitable conditions are recorded in International Publication No. 2002 / 08438, International Publication No. 2007 / 117157 and International Publication No. 2008 / 115080.

[0300] The optimal fermentation conditions depend in part on the specific microorganism used. However, it is usually preferred to ferment under a pressure higher than the ambient pressure. By operating under increased pressure, the carbon dioxide moving speed from the gas phase to the liquid phase can be greatly increased, and carbon dioxide can be introduced into the microorganism as a carbon source for generating ethanol. On the other hand, this means that when the bioreactor is kept under a pressure higher than atmospheric pressure, the holding time (defined as the value obtained by dividing the liquid volume in the bioreactor by the input gas flow rate) can be reduced.

[0301] Additionally, it is preferred that the rate of introduction of the gaseous substrate containing carbon dioxide and hydrogen is such that the concentration of carbon dioxide and hydrogen in the liquid phase does not become limiting. This is because, as a result of carbon dioxide and hydrogen limiting conditions, the ethanol product may be consumed by the culture.

[0302] The temperature of the fermentation liquid in the bioreactor is not particularly limited as long as it is within the optimal temperature range for fermentation, and is preferably 20°C to 40°C, and more preferably 30°C to 40°C. The optimal temperature for the fastest growth of bacteria and the highest production rate of acetate can be determined by operating the bioreactor at various temperatures. The bioreactor is first operated at 30°C, and the temperature is raised to a plurality of different temperatures. The optimal temperature for the fastest growth of bacteria 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.

[0303] The pH of the fermentation liquid in the bioreactor is not particularly limited, but is preferably maintained in the range of 3-10, and more preferably maintained in the range of 4-8.

[0304] Fermentation is carried out in a bioreactor to obtain a fermentation liquid containing ethanol. Next, the fermentation liquid containing ethanol is sent to a separation process. In the separation process, the fermentation liquid containing ethanol is heated to 23°C to 500°C, for example, under the condition of 0.01kPa to 1000kPa (absolute pressure), so as to be separated into a liquid or solid component containing microorganisms and a gas component containing ethanol. By implementing such a separation process, during the distillation operation during the separation and purification of ethanol described later, no foaming is generated in the distillation apparatus, so the distillation operation can be carried out continuously. In addition, the separation and purification of ethanol can be effectively carried out during the separation and purification described later.

[0305] In the separation step, from the viewpoint of effectively separating into a liquid or solid component containing microorganisms or their remains, proteins from microorganisms, etc. and a gas component containing ethanol, the culture solution containing ethanol is heated under conditions preferably of 10 kPa to 200 kPa, more preferably of 50 kPa to 150 kPa, further preferably at normal pressure, at a temperature preferably of 50°C to 200°C, more preferably of 80°C to 180°C, and further preferably of 100°C to 150°C.

[0306] The gas component containing ethanol obtained in the separation step can be liquefied by condensation to produce a liquid containing ethanol (liquefaction step). The device used in the liquefaction step is not particularly limited, and a heat exchanger, particularly a condenser (condenser) is preferably used. Examples of the condenser include water-cooled, air-cooled, and evaporative types, preferably water-cooled. The condenser may be single-stage or multi-stage.

[0307] In addition, in the separation step, a solid-liquid separation device such as a solid-liquid separation filter device may be used to separate a solid component containing microorganisms and a liquid component containing ethanol instead of separating into a liquid or solid component containing microorganisms and a gas component containing ethanol.

[0308] After the separation step, a purification step for further purifying the ethanol-containing liquid may be performed. In addition, when components such as microorganisms have been removed, the ethanol-containing liquid obtained by microbial fermentation may be subjected to a purification step without going through the above-mentioned separation step.

[0309] The purification process is a process for separating the liquid containing ethanol into a distillate with an increased concentration of ethanol and a bottom liquid with a reduced concentration of ethanol. For the device used in the purification process, for example, there can be listed: a distillation device, a treatment device including a pervaporation membrane, a treatment device including a zeolite membrane, a treatment device for removing low-boiling substances with a boiling point lower than ethanol, a treatment device for removing high-boiling substances with a boiling point higher than ethanol, a treatment device including an ion exchange membrane, etc. These devices can be single or in combination of two or more. As a unit operation, a distillation device or membrane separation can be used appropriately, and a distillation device is more preferred. In addition, as a membrane separation, a zeolite membrane can be used appropriately.

[0310] When a distillation apparatus is used, heating distillation is performed. In heating distillation, desired ethanol can be obtained as a distillate with high purity. The temperature in the distillation apparatus during the distillation of ethanol is not particularly limited, but is preferably 110° C. or less, and more preferably about 70° C. to about 105° C. By setting the temperature in the distillation apparatus within the above range, separation of ethanol from other components, that is, distillation of ethanol, can be performed more reliably.

[0311] In the heating distillation, the ethanol-containing liquid can be introduced into a distillation apparatus having a heater using steam at 100°C or higher, the temperature of the bottom of the distillation tower can be raised to 90°C or higher within 30 minutes, and then the ethanol-containing liquid can be introduced from the middle of the distillation tower. In the heating distillation using a distillation apparatus, it is preferred to perform the distillation process under the condition that the temperature difference between the bottom, middle and top of the tower is within ±15°C. When the temperature difference is within ±15°C, high-purity ethanol is easily obtained. The distillation temperature difference is preferably ±13°C, and more preferably ±11°C. With these distillation temperature differences, separation from other components, that is, purification by distillation of ethanol, can be performed more reliably.

[0312] The pressure in the distillation apparatus during ethanol distillation may be normal pressure, but is preferably less than atmospheric pressure, and more preferably about 60 kPa to about 95 kPa (absolute pressure). By setting the pressure in the distillation apparatus within the above range, the separation efficiency of ethanol can be improved, and thus the yield of ethanol can be improved.

[0313] The ethanol obtained in the purification step can be further distilled or concentrated using various separation membranes, such as zeolite membranes, to produce high-purity ethanol. In addition, the ethanol-containing liquid can be transported to a bioreactor after the ethanol is removed.

[0314] The ethanol obtained through the purification process is used as a raw material for obtaining a product containing ethylene in the production of ethylene described later. In the present invention, the "ethanol" used as a raw material does not refer to pure ethanol as a compound (ethanol represented by the chemical formula: CH3CH2OH), but a composition containing impurities, also referred to as "raw material ethanol". Impurities are impurities contained in the raw material ethanol produced through the above-mentioned processes, most of which are compounds derived from waste.

[0315] It should be noted that the purification step may be omitted. That is, after ethanol is generated, as a purification step, both the above-mentioned purification step and the purification of the later-described step (31') may not be performed, and only the purification of the step (31') may be performed. In this case, the liquid containing ethanol becomes raw material ethanol, and the purification of the step (31') is preferably performed by a distillation apparatus or membrane separation, and heating distillation using a distillation apparatus is particularly preferred. Of course, in the case of performing the purification of the later-described step (31"), both the purification step and the purification of the step (31') may be omitted. However, it is preferred to perform the purification step, and it is more preferred to perform the purification of the step (31') together.

[0316] The ethanol purity (i.e., ethanol content) of the raw material ethanol is, for example, 85% by volume or more. When the ethanol purity is above the lower limit, the polymerization reaction using ethylene as the raw material proceeds appropriately by at least one of the purification steps (31') and (31"), and the quality of the polymer obtained from ethylene becomes good. The ethanol purity of the raw material ethanol is preferably 90% by volume or more, more preferably 95% by volume or more, and further preferably 99.5% by volume or more. In addition, the raw material ethanol can be used as long as the ethanol purity is less than 100% by volume. In addition, as long as the raw material ethanol contains ethanol from waste, a commercially available product may also be used.

[0317] Next, the generation of propanol in the fermentation method is described. In the microbial fermentation of propanol, for example, any recombinant microorganism with propanol production capacity can be used. The propanol production capacity of the recombinant microorganism can be the ability obtained by changing (for example, enhancing) the propanol production pathway originally possessed by the microorganism, or can be the ability obtained by newly introducing the propanol production pathway into the microorganism. Such modification and introduction can be carried out by genetic recombination. Specifically, known methods such as plasmids can be used to modify or introduce DNA such as genes of enzymes related to the propanol production pathway, transcriptional regulatory factors.

[0318] As a recombinant microorganism, for example, the Escherichia coli having a propyl alcohol production system for producing propyl alcohol can be cited as a suitable recombinant microorganism. For example, the Escherichia coli producing propyl alcohol recorded in the communiques such as International Publication No. 2009 / 008377, International Publication No. 2011 / 034031, International Publication No. 2011 / 111638 and International Publication No. 2012 / 020833 can be cited. Escherichia coli does not originally have a system for producing propyl alcohol, so the Escherichia coli producing propyl alcohol is an Escherichia coli with the propyl alcohol production capacity introduced or modified by genetic recombination. Such a propyl alcohol production system can be any production system as long as it is a production system that makes the Escherichia coli as the object produce propyl alcohol. In addition, at least a part of the propyl alcohol production system can be introduced or modified by genetic recombination. The introduction or modification by genetic recombination can use known methods, for example, can be cited: homologous recombination in the genome, the introduction utilizing plasmid, etc.

[0319] The propanol-producing Escherichia coli is preferably an Escherichia coli in which the enzyme activity related to propanol production is enhanced. "By genetic recombination" means that as long as the base sequence of a natural gene is changed by the insertion of an exogenous base sequence having a different sequence, or the substitution, deletion or combination of a part of the gene, all changes in the base sequence are included, for example, genetic recombination resulting in a mutation.

[0320] It is preferred that the propanol-producing Escherichia coli be endowed with four enzyme activities of acetoacetate decarboxylase activity, propanol dehydrogenase activity, CoA transferase activity, and thiolase activity outside the cell, or that the expression of these four enzyme activities is enhanced inside the cell, or both.

[0321] Here, thiolase is a general term for enzymes classified as enzyme number 2.3.1.9 according to the report of the Enzyme Commission of the International Union of Biochemistry (IUB), and catalyzes the reaction of generating acetoacetyl CoA from acetyl COA. Acetoacetate decarboxylase is a general term for enzymes classified as enzyme number 4.1.1.4 according to the report of the Enzyme Commission of the International Union of Biochemistry (IUB), and catalyzes the reaction of generating acetone from acetoacetate.

[0322] Isopropanol dehydrogenase is a general term for enzymes classified as enzyme number 1.1.1.80 according to the report of the Enzyme Commission of the International Union of Biochemistry (IUB) and catalyze the reaction of generating isopropanol from acetone. CoA transferase is a general term for enzymes classified as enzyme number 2.8.3.8 according to the report of the Enzyme Commission of the International Union of Biochemistry (IUB) and catalyze the reaction of generating acetoacetate from acetoacetyl CoA.

[0323] As an example of a propanol-producing Escherichia coli having a propanol production system, the pIPA / B strain or the pIaaa / B strain described in WO2009 / 008377 can be exemplified. In addition, in the example of this Escherichia coli, among the enzymes related to the production of isopropanol, the enhancement of CoA transferase activity and thiolase activity is carried out by strengthening the expression of each gene on the genome of this Escherichia coli, and the enhancement of isopropanol dehydrogenase activity and acetoacetate decarboxylase activity includes a strain obtained by strengthening the expression of each gene using a plasmid (sometimes described as a pIa / B::atoDAB strain).

[0324] In addition, recombinant Escherichia coli that effectively improves the productivity of propyl alcohol can be used, as such examples, can enumerate: inactivated GntR activity, inactivated glucose-6-phosphate isomerase (Pgi) activity, inactivated phosphogluconate dehydrogenase (Gnd) activity and enhanced glucose-6-phosphate-1-dehydrogenase (Zwf) activity. By these combinations, compared with the combination of other factors or enzymes, the productivity of propyl alcohol can be improved.

[0325] Glucose-6-phosphate isomerase (Pgi) is a general term for enzymes classified as enzyme number 5.3.1.9 based on the report of the Enzyme Commission of the International Union of Biochemistry (IUB) and catalyzing the reaction of generating D-fructose-6-phosphate from D-glucose-6-phosphate.

[0326] Glucose-6-phosphate-1-dehydrogenase (Zwf) is a general term for enzymes classified as enzyme number 1.1.1.49 based on the report of the Enzyme Commission of the International Union of Biochemistry (IUB) and catalyzing the reaction of generating D-glucose-6-phosphate from D-glucose-1,5-lactone-6-phosphate.

[0327] As the gene of glucose-6-phosphate-1-dehydrogenase (Zwf), a DNA having a base sequence of a gene encoding a thiolase obtained from each of the above-mentioned source organisms or a synthetic DNA sequence synthesized based on the known base sequence can be used.

[0328] Phosphogluconate dehydrogenase (Gnd) is a general term for enzymes classified as enzyme number 1.1.1.44 based on the report of the Enzyme Commission of the International Union of Biochemistry (IUB) and catalyzing the reaction of generating D-ribulose-5-phosphate and carbon dioxide from 6-phospho-D-gluconic acid.

[0329] As propanol-producing Escherichia coli, for example, there can be listed: a strain in which the GntR activity of the pIPA / B strain, the pIaaa / B strain or the pIa / B::atoDAB strain is inactivated; a strain in which the GntR activity and the glucose-6-phosphate isomerase (Pgi) activity of the pIa / B::atoDAB strain are inactivated and the glucose-6-phosphate-1-dehydrogenase (Zwf) activity is enhanced; a strain in which the GntR activity, the glucose-6-phosphate isomerase (Pgi) activity and the phosphogluconate dehydrogenase (Gnd) activity of the pIa / B::atoDAB strain are inactivated and the glucose-6-phosphate-1-dehydrogenase (Zwf) activity is enhanced, etc.

[0330] The above-mentioned microorganisms are used to ferment in a bioreactor to obtain a fermentation liquid containing propanol. The fermentation liquid containing propanol is then subjected to the separation step and purification step described above for the production of ethanol by fermentation.

[0331] In addition to the above, propanol obtained by hydrogenating acetone obtained by fermentation with a microorganism described in Japanese Patent Application Laid-Open No. 2021-185862 can also be used as a suitable propanol.

[0332] Next, the production of butanol by fermentation is described. There are no particular limitations as long as the microorganism produces butanol by fermentation. Some anaerobic bacteria are known to be able to produce alcohols including n-butanol and butanol and acetic acid by fermentation from carbon monoxide. Examples of such bacteria include Clostridium including Clostridium ljungdahlii, Clostridium carboxidivorans (Liou et al., International Journal of Systematic and Evolutionary Microbiology 33: pp 2085-2091), Clostridium ragsdalei (International Publication No. 2008 / 028055), and Clostridium autoethanogenum (Abrini et al., Archives of Microbiology 161: pp 345-351); Moorella including Moorella species HUC22-1 (Sakai et al., Biotechnology Letters 29: pp 1607-1612); and Thermocarboxydosus bacteria (Svetlichny, VA, Sokolova, TG et al. (1991), Systematic and Applied Microbiology 14: 254-260), Moorella thermoacetica, Mooreella thermoautotrophica, Ruminococcus productus, Acetobacterium woodii, Eubacterium limosum, Butyribacterium methylotrophicum, Oxobacter pfennigii, Methanosarcina barkeri, Methanosarcina acetivorans, Desulfotomaculum kuznetsovii (Simpa et al., Critical Reviews in Biotechnology, 2006, Vol. 26, pp. 41-65), etc.

[0333] In addition, Clostridium species such as Clostridium acetobutylicum 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 known 1-butanol production pathways are disclosed in U.S. Patent No. 4,539,293 and U.S. Patent No. 5,753,474. In the methods disclosed in these patent documents, sugars are first used in the production of butyric acid, which is then converted into 1-butanol.

[0334] In addition, a method of using bacterial fermentation to produce acetone, n-butanol and ethanol from starch using a fermentation called ABE (acetone-butanol-ethanol) is also known. Industrial development of ABE fermentation began in 1916, and Chaim Weizmann recorded the isolation of Clostridium acetobutylicum in US Pat. No. 1,315,585 A. A mixture containing acetone, n-butanol and ethanol in a ratio of about 3:6:1 is produced by this method. The system of raw materials and microorganisms used directly affects the composition of the mixture taken out of the fermentation tank. For example, Cobalt Technologies recorded in US patent application US2010330633A1 that the yield of butanol obtained from fermentation raw materials and Clostridium saccharubutylium reached 80%. In addition, Lanzatech New Zealand Co., Ltd. recorded in US Pat. No. 8,119,844B2 that the yield reached 63% by glycerol and Clostridium pasteurianum. In order to optimize ABE fermentation, various methods have been developed for recovering products from the reaction solution, including distillation, pervaporation separation, membrane separation, adsorption and reverse osmosis.

[0335] The above-mentioned microorganisms are used to ferment in a bioreactor to obtain a fermentation liquid containing butanol. The fermentation liquid containing butanol is then subjected to the separation step and purification step described above for the production of ethanol by fermentation.

[0336] Step (31) is a step of subjecting an alcohol to a dehydration reaction to obtain an unsaturated hydrocarbon having 2 to 8 carbon atoms. In one embodiment, ethanol is subjected to a dehydration reaction to obtain ethylene. In another embodiment, propanol is subjected to a dehydration reaction to obtain propylene. In another embodiment, butanol is subjected to a dehydration reaction to obtain butene. In yet another embodiment, two or more of ethanol, propanol, and butanol are subjected to a dehydration reaction to obtain ethylene, propylene, and butene.

[0337] Hereinafter, as step (31), a method of obtaining ethylene by dehydrating ethanol as one embodiment and a method of obtaining propylene by dehydrating propanol as another embodiment will be described as examples.

[0338] The step of subjecting ethanol to a dehydration reaction to obtain ethylene as one embodiment of step (31) is described below. Ethanol is converted into ethylene by the ethylene production step, thereby obtaining a product containing ethylene. Specifically, ethanol can be contacted with a catalyst to be converted into ethylene. Ethanol is converted into ethylene by a dehydration reaction.

[0339] When the dehydration reaction of ethanol is carried out, a solvent or gas inert to the catalyst and the alcohol can be added to the reaction system, so that the dehydration reaction is carried out in a diluted state. The dehydration method of ethanol can be any method in a batch type, a semi-batch type or a continuous flow type. In addition, it can be any form in a liquid phase, a gas phase, or a gas-liquid mixed phase. As the filling method of the catalyst, various methods such as a fixed bed, a fluidized bed, a suspended bed, a tray fixed bed, etc. can be adopted, and any method can be used.

[0340] The catalyst used is not limited as long as it is a catalyst that can convert ethanol into ethylene. Examples of the catalyst include zeolite, modified zeolite such as P-modified zeolite, silica-alumina, alumina, silicated alumina, titanated alumina, zirconated alumina or fluorinated alumina, silicoaluminophosphate and other acid catalysts (hereinafter, they may be collectively referred to as "zeolite or alumina catalysts"). In addition, heteropolyacid supported catalysts and the like may also be mentioned.

[0341] As zeolite, zeolite containing at least one ten-membered ring in the structure is advantageous, and it is a microporous material containing silicon, aluminum, oxygen and boron as an optional component, for example, 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.

[0342] The zeolite is preferably a zeolite having a Si / Al ratio of 10 or more. The Si / Al ratio of the zeolite having a Si / Al ratio of 10 or more is preferably 100 or more. In addition, it is preferred that at least one selected from MFI and MEL is contained.

[0343] The zeolite is preferably a dealuminated zeolite. In the dealuminated zeolite, it is advantageous to remove about 10% by mass of aluminum. The dealumination is advantageously performed by steam treatment and then leaching is performed as required.

[0344] It is advantageous that the zeolite and the dealuminated zeolite are basically in the H type. In addition, as a minor component (component of about 50% or less), at least one selected from Na, Mg, Ca, La, Ni, Ce, Zn, and Co may be contained as a metal compensating ion.

[0345] Zeolite is mixed with a binder, preferably an inorganic binder, and molded into a desired shape such as granules. For the binder, a binder that is durable to the temperature and other conditions used in the dehydration process of the present invention is selected. The binder is at least one inorganic material selected from clay, silica, metal silicate, metal oxide (such as ZrO2) or a gel containing a mixture of silica and metal oxide.

[0346] P-modified zeolite is a phosphorus-modified zeolite. In the ethylene production process, it is also preferred to use a P-modified zeolite. The phosphorus-modified zeolite can be manufactured, for example, based on a zeolite having micropores with an initial atomic ratio Si / Al ratio of 4 to 500, specifically, MFI, MOR, MEL, clinoptilolite, FER, MWW, TON, EUO, MFS, ZSM-48, etc. The initial atomic ratio Si / Al ratio is preferably 100 or less, more preferably 4 to 30. The P-modified zeolite of the present preparation method can also be obtained based on an inexpensive zeolite with a low Si / Al ratio (less than 30).

[0347] In addition, the P-modified zeolite may be further modified using at least one metal selected from the group consisting of Mg, Ca, La, Ni, Ce, Zn, Co, Ag, Fe and Cu.

[0348] The phosphorus atom content in the P-modified zeolite is at least 0.05% by mass, preferably 0.3% to 7% by mass. In addition, it is advantageous to extract and remove at least 10% by mass of aluminum from the zeolite as a raw material by leaching.

[0349] The catalyst using the P-modified zeolite may be the P-modified zeolite itself or a complex-type P-modified zeolite obtained by combining the P-modified zeolite with other materials. By using a complex-type zeolite, the hardness and catalytic activity of the catalyst can be improved.

[0350] As materials that can be mixed with P modified zeolite, various inert or catalyst active materials, various binder materials, etc. can be listed. Specifically, kaolin, other clay and other compositions, various forms of rare earth metals, phosphates, alumina or alumina sol, titanium dioxide, zirconium oxide, quartz, silicon dioxide or silicon dioxide sol and mixtures thereof can be listed. These components are effective for increasing the compressive strength of the catalyst and the catalyst. The catalyst can be formed into particles, balls, or extruded into other shapes, or made into spray-dried particles. The amount of P modified zeolite contained in the final catalyst product is 10% to 90% by mass of the total catalyst, preferably 20% to 70% by mass of the total catalyst.

[0351] Suitable examples of P-modified zeolites are silicoaluminophosphates, more preferably silicoaluminophosphates 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 substantially 1 atom / atom. Silicon is inserted into the ALPO framework by adding a silicon precursor during synthesis, and acid sites can be formed on the surface of the micropores of the ten-membered ring zeolite. The content of silicon is 0.1 atomic % to 10 atomic % (Al+P+Si is 100).

[0352] It is also preferred to use alumina (especially γ-alumina) as a catalyst in the ethylene production step. In addition, it is also preferred to use silicated alumina, zirconated alumina, titanated alumina or fluorinated alumina. Alumina generally has the characteristics of having a wide range of acid strength distribution and Lewis-type and Bronsted-type acid sites. As alumina, activated alumina can be used.

[0353] Alumina is also preferably used to improve the selectivity of the catalyst by precipitating silicon, zirconium, titanium, fluorite, etc. on the surface. That is, the selectivity of the catalyst can be improved by silicating, zirconating, or titanating. In the production of such a catalyst, suitable commercially available alumina, preferably with a surface area of ​​10 m 2 / g~500m 2 / g and η-alumina or γ-alumina with an alkali content of 0.5% or less. In addition, it can be prepared by adding silicon, zirconium, titanium, etc. in an amount of 0.05% to 10% by mass in total. These metals can be added when the alumina is manufactured, or can be added to the alumina after manufacture. In addition, these metals can also be added in the form of a precursor. In addition, fluorinated alumina itself is well known and can be manufactured according to the prior art.

[0354] In the ethylene generation process, it is also preferred to use a heteropolyacid supported catalyst as a catalyst. The heteropolyacid supported catalyst comprises a heteropolyacid supported on a suitable catalyst carrier. It should be noted that the term "heteropolyacid" refers to a heteropolyacid compound in the form of a heteropolyacid salt such as a free acid form or an alkali metal salt, an alkaline earth metal salt, an ammonium salt, a large-volume cationic salt and / or a metal salt (in these cases, the salt can be any one of a complete salt or a partial salt).

[0355] The anion of heteropolyacid typically comprises a polyvalent metal atom bonded with 12 to 18 oxygens as a peripheral atom known to surround one or more central atoms in a symmetrical manner. The peripheral atoms are suitably selected from molybdenum, tungsten, vanadium, niobium, tantalum and their combination. The central atom is preferably silicon or phosphorus. In addition, the central atom can comprise any one of the atoms of Groups I to VIII selected from the periodic table, 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. As suitable heteropolyacid, Keggin, Wells-Dawson and Anderson-Evans-Perloff heteropolyacids can be cited.

[0356] The heteropolyacid component of the heteropolyacid-supported catalyst is preferably a tungsten heteropolyacid, which is a heteropolyacid whose peripheral atoms are tungsten atoms. A preferred tungsten heteropolyacid is any tungsten heteropolyacid having a Keggin or Wells-Dawson structure as a main component.

[0357] Examples of tungstic heteropoly acids include: 18-phosphotungstic acid (H6[P2W 18 O 62 ]·xH2O), 12-phosphotungstic acid (H3[PW 12 O 40 ]·xH2O), 12-silicotungstic acid (H4[SiW 12 O 40 ]·xH2O), cesium hydrogen silicotungstate (Cs3H[SiW 12 O 40 ]·xH2O), potassium phosphotungstate (KH5[P2W 18 O 62 ]·xH2O), 12-sodium silicotungstate (NaK3[SiW 12 O 40 ]·xH2O) and potassium phosphotungstate (K6[P2W 18 O 62 ]·xH2O). A mixture of two or more different tungstic heteropoly acids and salts may also be used.

[0358] More preferably, the heteropolyacid component of the heteropolyacid-supported catalyst is selected from silicotungstic acid, phosphotungstic acid and mixtures thereof, such as 12-silicotungstic acid (H4[SiW 12 O 40 ]·xH2O), 12-phosphotungstic acid (H3[PW 12 O 40 ]·xH2O) and mixtures thereof. The heteropoly acid is more preferably silicotungstic acid, and the most preferred heteropoly acid is 12-silicotungstic acid.

[0359] The molecular weight of the heteropolyacid is preferably greater than 700 and less than 8500, more preferably greater than 2800 and less than 6000. Such heteropolyacids also include their dimer complexes.

[0360] The catalyst carrier used in the heteropolyacid supported catalyst can be any known suitable catalyst carrier. As the raw material suitable for the catalyst carrier, include mordenite (such as montmorillonite), clay, bentonite, diatomite, titanium dioxide, activated carbon, aluminum oxide, silicon dioxide, silicon dioxide-alumina, silicon dioxide-titania co-gel, silicon dioxide-zirconia co-gel, carbon coating aluminum oxide, zeolite, zinc oxide and flame pyrolysis oxide. Preferred silica gel carriers and carriers manufactured by flame hydrolysis of SiCl4 are catalyst carriers with silicon dioxide as the main component.

[0361] The shape of the catalyst carrier is not particularly limited, and may be, for example, a powdery form, a granular form, a pelletized form, a spherical form, or an extruded form.

[0362] Ethanol is not particularly limited, but is preferably converted into ethylene by contacting with a catalyst in a gas phase. In addition, ethanol may be further mixed with water, and in addition to ethanol and water, an optional component may be appropriately mixed, and one or both of water and the optional component may be contacted with the catalyst in the form of a gas together with the raw material ethanol.

[0363] The catalyst may be filled in a reaction vessel, for example, and ethanol or ethanol and at least one selected from water and other optional components may be supplied in the form of gas to the reaction vessel filled with the catalyst to perform a gas phase dehydration reaction, thereby discharging the product containing ethylene from the reaction vessel in the gas phase. In the case where ethanol remains in the gas discharged from the reaction vessel, the component containing ethanol may be separated from the product containing ethylene and the component containing ethanol may be supplied to the reaction vessel again.

[0364] In the case of a zeolite or alumina catalyst, the temperature of the reaction vessel is, for example, 280° C. to 600° C., preferably 300° C. to 550° C., and more preferably 330° C. to 530° C. The pressure (absolute pressure) of the reaction vessel is, for example, 0.05 MPa to 3 MPa, preferably 0.05 MPa to 2.5 MPa, and more preferably 0.12 MPa to 2 MPa.

[0365] In the case of a heteropolyacid supported catalyst, the temperature of the reaction container is, for example, 170° C. or higher, preferably in the range of 180° C. to 270° C., more preferably in the range of 190° C. to 260° C., and further preferably in the range of 200° C. to 250° C. In addition, the pressure is preferably in the range of 0.1 MPa to 4.5 MPa, more preferably in the range of 1.0 MPa to 3.5 MPa, and further preferably in the range of 1.0 MPa to 2.8 MPa.

[0366] In the case of a heteropolyacid-supported catalyst, the heteropolyacid-supported catalyst may be heated to a temperature of 220° C. or higher and maintained at the temperature for a sufficient time before contacting with ethanol, thereby removing bound water from the heteropolyacid component of the heteropolyacid-supported catalyst.

[0367] In step (31), a step (31') of purifying ethanol may be performed before the ethylene production step, and a step (31") of purifying the product containing ethylene may be performed after the ethylene production step.

[0368] It should be noted that, when step (31") is performed, the product containing ethylene after purification by step (31") is regarded as the "ethylene" produced by the production method of the sixth embodiment, and when step (31") is omitted, the product containing ethylene obtained in the ethylene production step is regarded as the "ethylene" produced by the sixth embodiment. The "ethylene" produced by the sixth embodiment may be composed of ethylene alone, or may be a composition containing impurities that are inevitably mixed even after synthesis or purification.

[0369] In step (31'), 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 is preferably removed from ethanol.

[0370] When the raw material comes from waste, the waste contains various components. Therefore, the raw material ethanol generated from waste contains various organic compounds. In addition, among the organic compounds, the organic compounds with the above-mentioned carbon number often remain in the ethanol obtained through various processes. When such organic compounds remain in ethanol, the dehydration reaction in the ethylene production process is sometimes inhibited, and then the polymerization reaction using ethylene in the later stage is inhibited, or the quality of the polymer obtained from ethylene is reduced. Therefore, in step (31'), by removing hydrocarbons, alcohols, and ethers with specific carbon numbers, the polymerization reaction of ethylene is properly carried out, and the quality of the obtained polymer is also easily improved.

[0371] On the other hand, in step (31"), it is preferred to remove at least one of specific organic compounds selected from 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 generated ethylene-containing product.

[0372] It should be noted that the term "removal" in step (31') and step (31") includes not only a method of completely removing the target substance from ethanol or the ethylene-containing product, but also a method of reducing the content of the target substance.

[0373] In step (31"), as described in the description of step (31'), by removing hydrocarbons, alcohols and ethers having a specific number of carbon atoms, the polymerization reaction of ethylene is appropriately carried out, and the quality of the obtained polymer is also likely to be improved.

[0374] Carbon monoxide, carbon dioxide and oxygen sometimes inhibit the polymerization of ethylene.

[0375] In the ethylene manufactured by the manufacture method of the sixth embodiment, by removing carbon monoxide, the content of carbon monoxide is preferably below 100 volume ppm. The content of carbon monoxide is more preferably below 10 volume ppm, further preferably below 1 volume ppm. In addition, the ethylene manufactured in the present invention may not contain carbon monoxide at all, so the lower limit of the content of carbon monoxide is 0 volume %.

[0376] In the ethylene manufactured by the manufacture method of the sixth embodiment, by removing carbon dioxide, the content of carbon dioxide is preferably below 1 volume %. The content of carbon dioxide is more preferably below 0.5 volume %, further preferably below 0.1 volume %. In addition, the ethylene manufactured in the present invention can be free of carbon dioxide completely, so the lower limit of the content of carbon dioxide is 0 volume %.

[0377] In the ethylene manufactured by the manufacturing method of the sixth embodiment, by removing oxygen, the content of oxygen is preferably less than 1 volume %. The content of oxygen is more preferably less than 0.5 volume %, and further preferably less than 0.1 volume %. In addition, the ethylene manufactured in the present invention may not contain oxygen at all, so the lower limit of the content of oxygen is 0 volume %.

[0378] Aliphatic unsaturated hydrocarbons having 3 to 14 carbon atoms can be removed in step (31'), step (31") or both steps. When ethylene contains aliphatic unsaturated hydrocarbons having 3 to 14 carbon atoms, when the ethylene is used for polymerization, the aliphatic unsaturated hydrocarbons having 3 to 14 carbon atoms become branches of the polymer. Therefore, by removing the aliphatic unsaturated hydrocarbons having 3 to 14 carbon atoms, the branches can be reduced. Therefore, in the case of manufacturing high-density polyethylene (HDPE) from ethylene as described later, in the case where it is desired to reduce the branches of the polymer, it is particularly suitable to remove the aliphatic unsaturated hydrocarbons having 3 to 14 carbon atoms.

[0379] In the ethylene produced by the production method of the sixth embodiment, by removing aliphatic unsaturated hydrocarbons having 3 to 14 carbon atoms, the content of aliphatic unsaturated hydrocarbons having 3 to 14 carbon atoms is preferably 1% by volume or less. The content of aliphatic unsaturated hydrocarbons having 3 to 14 carbon atoms is more preferably 0.5% by volume or less, and further preferably 0.1% by volume or less. In addition, the ethylene produced in the present invention may not contain aliphatic unsaturated hydrocarbons having 3 to 14 carbon atoms at all, so the lower limit of the content of aliphatic unsaturated hydrocarbons having 3 to 14 carbon atoms is 0% by volume.

[0380] In addition, aliphatic saturated hydrocarbons having 3 to 14 carbon atoms may be removed in step (31'), step (31") or both steps, and preferably, the aliphatic saturated hydrocarbons having 3 to 14 carbon atoms removed in any 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. Specific examples of aliphatic saturated hydrocarbons having 6 to 14 carbon atoms are preferably at least one selected from n-hexane, n-heptane, n-octane, n-decane, n-dodecane and n-tetradecane.

[0381] Ethanol, a raw material derived from waste, may contain a large amount of these aliphatic saturated hydrocarbons having a relatively large carbon number (6 to 14 carbon atoms).

[0382] In the ethylene produced by the production method of the sixth embodiment, by removing aliphatic saturated hydrocarbons having 6 to 14 carbon atoms, the content of aliphatic saturated hydrocarbons having 6 to 14 carbon atoms is preferably 0.3 volume % or less, more preferably 0.2 volume % or less, and further preferably 0.1 volume % or less. In addition, the ethylene produced in the present invention may not contain aliphatic saturated hydrocarbons having 6 to 14 carbon atoms at all, so the lower limit of the content of aliphatic saturated hydrocarbons having 6 to 14 carbon atoms is 0 volume %.

[0383] In addition, the alcohol having 3 to 10 carbon atoms may be removed in step (31'), step (31"), or both steps. The alcohol having 3 to 10 carbon atoms removed in any step may contain, for example, at least one selected from 1-propanol, 2-propanol, 1-butanol, 2-butanol, and tert-butanol. These alcohols may be contained in large amounts in the raw material ethanol derived from waste.

[0384] In the ethylene produced by the production method of the sixth embodiment, by removing the alcohol having 3 to 10 carbon atoms, the content of the alcohol having 3 to 10 carbon atoms is preferably 0.3 volume % or less. The content of the alcohol having 3 to 10 carbon atoms is more preferably 0.1 volume % or less, and further preferably 0.05 volume % or less. In addition, the ethylene produced in the present invention may not contain the alcohol having 3 to 10 carbon atoms at all, so the lower limit of the content of the alcohol having 3 to 10 carbon atoms is 0 volume %.

[0385] Ethers having 3 to 10 carbon atoms may be removed in step (31'), step (31"), or both steps. The ethers having 3 to 10 carbon atoms removed in any one of the steps may contain, for example, at least one selected from diethyl ether and dibutyl ether. These ethers may be contained in large amounts in ethanol, a raw material derived from waste, and these ethers may be removed in step (31'), step (31"), or both steps.

[0386] In the ethylene produced by the production method of the sixth embodiment, by removing ethers having 3 to 10 carbon atoms, the content of ethers having 3 to 10 carbon atoms is preferably 0.3 volume % or less. The content of ethers having 3 to 10 carbon atoms is more preferably 0.1 volume % or less, and further preferably 0.05 volume % or less. In addition, the ethylene produced in the present invention may not contain ethers having 3 to 10 carbon atoms at all, so the lower limit of the content of ethers having 3 to 10 carbon atoms is 0 volume %.

[0387] In the ethylene production step, water is produced by a dehydration reaction, and therefore it is preferred to remove at least water in step (31") . In addition, unreacted ethanol generally remains in the ethylene-containing product produced in the ethylene production step, and therefore it is preferred to also remove the unreacted ethanol. By removing water and ethanol, the polymerization reaction using ethylene described later can be properly carried out, and the quality of the obtained polymer can be easily improved.

[0388] In the ethylene produced by the production method of the sixth embodiment, the water content is preferably 0.3 volume % or less by removing water in step (31") . By adjusting the water content to 0.3 volume % or less, the polymerization reaction using ethylene is easily and appropriately carried out, and the quality of the obtained polymer is also easily improved. From this point of view, the water content is more preferably 0.1 volume % or less, and further preferably 0.05 volume % or less. In addition, the ethylene produced in the present invention may be completely free of water, so the lower limit of the water content is 0 volume %.

[0389] In the ethylene produced by the production method of the sixth embodiment, the ethanol content is preferably 0.3 volume % or less by removing ethanol in step (31") . By adjusting the ethanol content to 0.3 volume % or less, the polymerization reaction using ethylene is easily and appropriately carried out, and the quality of the obtained polymer is also easily improved. From this viewpoint, the ethanol content is more preferably 0.1 volume % or less, and further preferably 0.05 volume % or less. In addition, the ethylene produced in the present invention may not contain ethanol at all, so the lower limit of the ethanol content is 0 volume %.

[0390] It should be noted that the ethylene produced by the production method of the sixth embodiment is usually a gas. For the ethylene as a gas, GC-TCD and GC-FID are used to analyze various inorganic gases (oxygen, carbon monoxide, carbon dioxide, etc.) and organic gases, thereby determining the volume % of the above-mentioned components.

[0391] Examples of the purification methods for each of step (31') and step (31") include a water separation device including a gas cooler, a separation device using an adsorbent such as activated carbon, a separation device using a pressure swing adsorption method (PSA), a separation device using a temperature swing adsorption method (TSA), a separation device using a pressure swing temperature swing adsorption method (PTSA), a separation device using a low temperature separation method (cryogenic method), a water-soluble impurity separation device such as a scrubber, a desulfurization device (sulfide separation device), a separation device using a membrane separation method, a distillation device, a separation device having a chromatography, a solution absorption device, and the like.

[0392] As a low temperature separation method, various methods can be used, for example, a method using a condenser can be cited. The solution absorption device is a device having an absorption solution that selectively absorbs a predetermined gas component by contacting the gas, and as the absorption solution, an alkaline solution such as an amine solution can be used. For example, when an alkaline solution is used in step (31'), carbon dioxide in the vaporized raw material ethanol can be absorbed.

[0393] In step (31'), as described above, it is preferred to remove any one 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. Among them, it is more preferred to remove substances having relatively large carbon atoms, and it is particularly preferred to remove aliphatic unsaturated hydrocarbons having 6 to 14 carbon atoms. Organic compounds having large carbon atoms are easily and simply removed in step (31') because they have a different molecular weight from ethanol. In addition, by removing organic compounds having large carbon atoms, the reaction in the ethylene production step can be easily carried out more appropriately.

[0394] In step (31'), the method for removing the aliphatic unsaturated hydrocarbons having 6 to 14 carbon atoms is not particularly limited, and the aliphatic unsaturated hydrocarbons may be removed by a separation device having a chromatogram. As the chromatogram, a reverse phase chromatography or the like may be used. Alternatively, the aliphatic unsaturated hydrocarbons may be removed by a distillation device, activated carbon adsorption, or the like.

[0395] In step (31"), it is preferred to remove any one of the water and unreacted ethanol generated in the ethylene production step, and it is preferred to remove both of them. In addition, in step (31"), as described above, it is preferred to remove at least one selected from specific organic compounds, carbon monoxide, carbon dioxide and oxygen, and among the specific organic compounds, it is more preferred to remove low-molecular-weight organic compounds with relatively low molecular weight (for example, carbon atoms of 3 to 5). That is, it is more preferred to remove aliphatic saturated hydrocarbons with carbon atoms of 6 to 14 in step (31'), and in step (31"), in addition to removing water and unreacted ethanol, at least specific low-molecular-weight organic compounds with relatively low molecular weight are removed. In step (31"), it is preferred to remove carbon monoxide, carbon dioxide and oxygen in addition to these substances.

[0396] Specifically, the specific organic compound removed in step (31") further preferably contains 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.

[0397] By using a specific separation device, low molecular weight organic compounds can be effectively removed from ethylene together with unreacted ethanol, carbon monoxide, carbon dioxide, oxygen, etc. In addition, diethyl ether can become a raw material for producing ethylene together with ethanol in the ethylene production process. Therefore, diethyl ether is preferably removed in a larger proportion in step (31") than in step (31'). It should be noted that the ratio in step (31') refers to the ratio relative to ethanol, and in step (31") refers to the ratio relative to the product containing ethylene.

[0398] In step (31"), there are no particular restrictions, but purification can preferably be performed using a separation device of a low-temperature separation method. Specifically, there can be mentioned a method of separating ethylene by solidifying ethylene using a condenser using a cooling medium (coolant) cooled to a temperature below the melting point of ethylene (below -170°C at normal pressure).

[0399] In this case, substances such as water, carbon dioxide, ethanol and other organic compounds with higher melting points than ethylene can be removed using one or more front-stage condensers in which the temperature of the cooling medium is higher than that of the above-mentioned condenser. As the front-stage condenser, for example, a first condenser in which the temperature of the cooling medium is relatively high (for example, 0°C to 25°C at normal pressure) and a second condenser in which the temperature of the cooling medium is lower than that of the first condenser (for example, -50°C to -90°C at normal pressure) can be used in combination. In addition, the condenser can be of any type, and the gas-phase product containing ethylene can be brought into contact with a metal pipe or the like through which the cooling medium is circulated, or the product containing ethylene can be brought into direct contact with the cooling medium.

[0400] Another embodiment of step (31) is to subject propanol to a dehydration reaction to obtain propylene. Propanol is converted into propylene by a propylene production step to obtain a propylene-containing product. Specifically, propanol can be brought into contact with a catalyst to be converted into propylene. Propanol is converted into propylene by a dehydration reaction.

[0401] In the case of the dehydration reaction of propyl alcohol, it is possible to add a solvent or gas that is inert to the catalyst and propyl alcohol in the reaction system, thereby carry out the dehydration reaction under the dilution state. The dehydration reaction method of propyl alcohol can be any method in batch, semi-batch or continuous flow-through. In addition, it can be any form in liquid phase, gas phase, gas-liquid mixed phase. As the filling mode of catalyzer, various modes such as fixed bed, fluidized bed, suspended bed, tray fixed bed can be adopted, which can be any mode.

[0402] As the catalyst used, there is no limitation as long as it is a catalyst that can convert propanol into propylene, and examples thereof include acid catalysts such as zeolite, silica-alumina, and alumina. The above-mentioned acid catalysts can be used alone, or they can be used together with catalysts or molding agents (binders) that can be used in dehydration reactions. When the above-mentioned acid catalysts are used together with molding agents, they can be used in the form of a molded body with improved mechanical strength by kneading and extrusion molding. The shape of the molded body can be granular, cylindrical, and annular, etc., without particular limitation. As molding methods for the catalyst, examples thereof include tablet molding, compression molding, and extrusion molding, etc., but there are no particular limitations. As catalysts or molding agents that can be used in dehydration reactions, for example, examples thereof include silica, alumina, clay, titanium dioxide, zirconium oxide, zinc oxide, ceria, lanthanum oxide, graphite, and ethyl cellulose, etc.

[0403] In addition, regarding the combination of filled catalysts, as a dehydration reaction catalyst, only the above-mentioned acid catalyst can be filled and used, or a catalyst that can be generally used in a dehydration reaction can be partially contained. For example, as the reaction proceeds, the water content increases near the reactor outlet, so it is also useful to use a catalyst in the second half of the reactor. In the case where the catalyst activity decreases after a certain period of time, the activity of the above-mentioned dehydration catalyst can be restored by regeneration by a known method.

[0404] In order to maintain the production of propylene, a circulation method can be adopted in which two or three reactors are arranged in parallel and the reaction is carried out in the remaining one or two reactors during the regeneration of one reactor. In addition, in the case of three reactors, a method of connecting the other two reactors in series to reduce the fluctuation of the production amount can also be adopted. In addition, when the fluidized bed circulation reaction method or the moving bed reaction method is implemented, a constant activity can be maintained by continuously or intermittently extracting a part or all of the catalyst from the reactor and replenishing a corresponding amount of catalyst.

[0405] The temperature of the catalyst layer is preferably 450° C. or less, more preferably 400° C. or less, further preferably 300° C. or less, and particularly preferably 200° C. or less. The lower limit of the temperature is not particularly limited as long as it is the temperature at which the dehydration reaction is performed or higher, and may be 160° C. or more, or 180° C. or more from the viewpoint of increasing the activity of the obtained catalyst. The temperature of the catalyst layer may be appropriately adjusted by changing the temperature of the device used in the dehydration reaction, etc.

[0406] When the temperature of the catalyst layer is within the above range, the dehydration reaction can be carried out at a relatively low temperature, and thus the energy required for the reaction can be reduced.

[0407] The reaction pressure during the dehydration reaction is not particularly limited, but is preferably 0 MPa to 100 MPa (gauge pressure), more preferably 0 MPa to 5 MPa (gauge pressure), and even more preferably 0 MPa to 4 MPa (gauge pressure).

[0408] In addition, the dehydration reaction can be carried out without pressurization, but the propylene obtained by the dehydration reaction is a gas at normal temperature and pressure, so it needs to be liquefied for purification by distillation, etc. Therefore, when propylene is a gas, it needs to be liquefied by cooling, pressurization, etc., which makes the production of propylene complicated.

[0409] Catalyst weight g in the dehydration reaction step relative to propanol flow rate mol·hour -1 The ratio (W / F) is not particularly limited, but is preferably 0.01 g·hour·mole. -1 ~10000g·hour·mole -1 , more preferably 0.1 g·h·mole -1 ~5000g·hour·mole -1 , and more preferably 1 g·hour·mole -1 ~200g·hour·mole -1 .

[0410] In order to quickly discharge the propylene generated in the dehydration reaction from the reaction system, a gaseous substance that is inert to the dehydration reaction may be mixed. Examples of the gaseous substance include nitrogen, helium, argon, methane, ethane, propane, butane, and the like. In addition, even if the gaseous substance is in a liquid state before the dehydration reaction of propanol, it only needs to become a gaseous state 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 isopropylbenzene. When a gaseous substance is used, the gaseous substance is preferably in the range of 0.05 mol to 10 mol relative to 1 mol of propylene.

[0411] In addition, when the catalyst activity decreases, the activity of the dehydration catalyst can be restored by regeneration through a known method. Moreover, in order to maintain the production of propylene, a switching method can be adopted in which two or more reactors are arranged in parallel and the dehydration reaction is carried out in other reactors during the period when the activity of the catalyst is restored in one reactor. In addition, in the case of having three or more reactors, two or more reactors that have not been restored in the activity of the catalyst can be connected in series to reduce the fluctuation of the production volume. In addition, in the case where the reactor mode is a fluidized bed circulation reaction mode or a moving bed reaction mode, a constant catalyst activity can be maintained by continuously or intermittently extracting a part or all of the catalyst from the reactor and replenishing the catalyst in an amount equal to the amount extracted. After the above-mentioned dehydration reaction step, for example, a step of taking out the propylene as a product in a gas-liquid separation step and then purifying it by distillation or the like can be carried out.

[0412] The purification equipment can be set in the process of the manufacturing method of the sixth embodiment, or it can be commonly used in a complex plant that integrates different technologies. When the naphtha cracker and the ethane cracker are adjacent to each other, the reaction product can be introduced into the distillation column group of the naphtha cracker and the ethane cracker for separation and purification.

[0413] [Seventh Embodiment of the Method for Producing Unsaturated Hydrocarbons Having 2 to 8 Carbon Atoms]

[0414] The seventh embodiment of the method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms is a method obtained by combining the method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms of the fifth embodiment and a method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms comprising step (31), wherein at least one alcohol selected from the group consisting of ethanol, propanol and butanol is subjected to a dehydration reaction to obtain unsaturated hydrocarbons having 2 to 8 carbon atoms.

[0415] The step (31) in the method for producing an unsaturated hydrocarbon having 2 to 8 carbon atoms of the seventh embodiment is the same as the step (31) of the sixth embodiment.

[0416] [Method for producing a mixture of unsaturated hydrocarbons having 2 to 8 carbon atoms]

[0417] A method for producing a mixture of unsaturated hydrocarbons having 2 to 8 carbon atoms comprises a step (41), in which the unsaturated hydrocarbons having 2 to 8 carbon atoms obtained by the method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms using any one of the first to seventh embodiments are brought into contact with unsaturated hydrocarbons having 2 to 8 carbon atoms from fossil resources to obtain a mixture.

[0418] Step (41) is a step of obtaining a mixture of unsaturated hydrocarbons having 2 to 8 carbon atoms by contacting and mixing the unsaturated hydrocarbons having 2 to 8 carbon atoms produced in the present invention with unsaturated hydrocarbons having 2 to 8 carbon atoms derived from fossil resources.

[0419] In step (41), the contact mass of the unsaturated hydrocarbons with carbon numbers of 2 to 8 from fossil resources to be contacted is preferably 0.001 to 10000, and more preferably 0.01 to 10000, relative to the contact mass of the unsaturated hydrocarbons with carbon numbers of 2 to 8 produced by the method for producing a mixture of unsaturated hydrocarbons with carbon numbers of 2 to 8 of the present invention (the contact mass of the unsaturated hydrocarbons with carbon numbers of 2 to 8 from fossil resources / the contact mass of the unsaturated hydrocarbons with carbon numbers of 2 to 8 produced by the method for producing the mixture of unsaturated hydrocarbons with carbon numbers of 2 to 8 of the present invention).

[0420] The unsaturated hydrocarbon compounds having 2 to 8 carbon atoms produced in the present invention can be used for various purposes. In addition, various derivatives can be produced by using the compounds as starting materials. An example of the production process of the derivatives is shown in Figure 1 to Figure 5 The production methods of these derivatives can be made by known methods. Figure 1 to Figure 5 A component used in a synthesis reaction is described in.

[0421] In addition, in the manufacture of these derivatives, in addition to the various compounds manufactured in the present invention, compounds manufactured using fossil resources such as petroleum, coal, and natural gas as raw materials (compounds derived from fossil resources) can also be used, and compounds manufactured using plants such as sugar cane and corn as raw materials (compounds derived from biomass) can also be used. It is also possible to use both compounds derived from fossil resources and compounds derived from biomass.

[0422] Hereinafter, as derivatives, polymers using olefins as monomers (olefin-based polymers), polymers using butadiene as monomers (butadiene-based polymers), polymers using methyl methacrylate as monomers (methyl methacrylate-based polymers), methyl methacrylate, polymers using propylene oxide as monomers (propylene oxide-based polymers), propylene oxide, polymers using ethylene oxide as monomers (ethylene oxide-based polymers), ethylene oxide, polymers using ethylene glycol as monomers (ethylene glycol-based polymers), ethylene glycol, phenol, acetone, and isopropyl alcohol are described.

[0423] [Method for producing olefin polymer]

[0424] The method for producing an olefin polymer includes a step of polymerizing a monomer, wherein the monomer includes an unsaturated hydrocarbon having 2 to 8 carbon atoms obtained by the method for producing an unsaturated hydrocarbon having 2 to 8 carbon atoms in any of the first to seventh embodiments described above, or an 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.

[0425] The unsaturated hydrocarbon having 2 to 8 carbon atoms and the mixture of unsaturated hydrocarbon having 2 to 8 carbon atoms produced in the present invention are subjected to a polymerization step for producing an olefin polymer. In the polymerization step, a monomer containing an unsaturated hydrocarbon having 2 to 8 carbon atoms is polymerized to obtain a polymer.

[0426] In the manufacture 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 manufactured in the present invention, olefins manufactured using fossil resources such as petroleum, coal, and natural gas as raw materials (olefins from fossil resources) can also be used, and olefins manufactured using plants such as sugar cane and corn as raw materials (olefins from biomass) can also be used. Olefins from fossil resources and olefins from biomass can also be used. As polymers manufactured by the manufacturing method of olefin polymers, for example, ethylene polymers, propylene polymers, butadiene polymers, etc. can be listed. The following is an explanation using ethylene polymers, propylene polymers, and butadiene polymers as examples.

[0427] [Olefin polymers]

[0428] <Ethylene polymer>

[0429] By polymerizing the monomers of the ethylene produced in the present invention, it is possible to produce ethylene polymers such as high-density polyethylene, low-density polyethylene, linear low-density polyethylene, ultra-low-density polyethylene, and long-chain branched polyethylene. The polymer may be a homopolyethylene obtained by polymerizing ethylene monomers or a copolymer obtained by polymerizing ethylene and monomers other than ethylene.

[0430] 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 hydrocarbons 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 substances may be used alone or in combination of two or more.

[0431] As ethylene, in addition to the ethylene produced in the present invention, ethylene derived from fossil resources, ethylene derived from biomass, or both ethylene derived from fossil resources and ethylene derived from biomass may be used.

[0432] In addition, as monomers other than ethylene, monomers produced in the present invention (for example, propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, and 1-heptene) can be used, monomers derived from fossil resources (for example, propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, and 1-heptene) can be used, and monomers derived from biomass (for example, propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, and 1-heptene) can be used. Two or more of them can also be used in combination, for example, monomer produced in the present invention / monomer derived from fossil resources, monomer produced in the present invention / monomer derived from biomass, monomer derived from fossil resources / monomer derived from biomass, and monomer produced in the present invention / monomer derived from fossil resources / monomer derived from biomass.

[0433] Specific polymers include: ethylene homopolymers, ethylene-propylene copolymers, ethylene-1-butene copolymers, ethylene-1-hexene copolymers, ethylene-1-butene-1-hexene copolymers, ethylene-1-octene copolymers, ethylene-4-methyl-1-pentene copolymers, ethylene-vinyl acetate copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-methyl methacrylate copolymers, ethylene-ethyl methacrylate copolymers, ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers, ethylene-propylene-5-ethylidene-2-norbornene copolymers, and the like.

[0434] When the ethylene polymer is set to 100 mass %, the content of ethylene units in the ethylene polymer is usually 50 mass % or more, preferably 70 mass % or more. It should be noted that the content of the above ethylene units is determined by 13 Determined by C-NMR method.

[0435] The density of ethylene polymers depends on the content of ethylene units and is usually 870 kg / m 3 ~965kg / m 3 .

[0436] The melt flow rate (MFR) of the ethylene polymer is usually 0.01 g / 10 min to 1000 g / 10 min, preferably 0.05 g / 10 min to 100 g / 10 min. The MFR is measured under the conditions of a temperature of 190° C. and a load of 2.16 kg as specified in JIS K7210-1-2014.

[0437] The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the ethylene-based polymer is usually 2-15, preferably 3-10.

[0438] 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 Japanese Patent Application Laid-Open No. 2012-214780.

[0439] Examples of methods for producing ethylene-based polymers include a method of polymerizing ethylene monomer or ethylene and a monomer other than ethylene in the presence of a radical polymerization initiator (high-pressure radical polymerization method).

[0440] As a free radical polymerization initiator, an oxygen-based initiator such as an organic peroxide, a peroxyester, a dialkyl peroxide or a combination thereof can be used. As a free radical polymerization initiator, for example, tert-butyl peroxypivalate, di-tert-butyl peroxide (DTBP), tert-butyl peroxyacetate (TBPO), tert-butyl peroxy 2-ethylhexanoate, tert-butyl peroxyneodecanoate (PND), tert-butyl peroxyoctanoate and a combination of any two or more thereof can be cited. The polymerization pressure in the high-pressure free radical polymerization method is usually 50 MPa to 400 MPa, and the polymerization temperature is usually 100° C. to 350° C.

[0441] Examples of methods for producing ethylene-based polymers include methods of polymerizing ethylene monomers or ethylene and monomers 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.

[0442] As the Ziegler-Natta catalyst, for example, a triethylaluminum-titanium tetrachloride solid complex is used. For the Ziegler-Natta catalyst, for example, a titanium trichloride composition obtained by reducing titanium tetrachloride with an organic aluminum compound and then treating with various electron donors and electron acceptors, an organic aluminum compound and an aromatic carboxylic acid ester can be combined, or titanium tetrachloride and various electron donors can be contacted with a magnesium halide to prepare a supported catalyst.

[0443] Examples of metallocene catalysts include compounds such as bis(cyclopentadienyl) metal complexes having a structure in which a transition metal is sandwiched between unsaturated compounds of a π-electron system. More specifically, examples include compounds in which one or more cyclopentadienyl rings or their analogs exist as ligands on a tetravalent transition metal such as titanium, zirconium, nickel, palladium, hafnium, and platinum.

[0444] The Ziegler-Natta catalyst and the metallocene catalyst may be used in combination with a specific co-catalyst (co-catalyst). Specific examples of the co-catalyst include methylaluminoxane (MAO) and boron-containing compounds.

[0445] Examples of the Phillips catalyst include a catalyst system containing a chromium compound such as chromium oxide, and specifically, a catalyst in which a chromium compound such as chromium trioxide or chromate is supported on a solid oxide such as silica, alumina, silica-alumina, or silica-titania.

[0446] In addition, the standard catalyst is a known catalyst using molybdenum oxide, for example, γ-alumina-molybdenum oxide, etc. In addition, as a polymerization catalyst for producing long-chain branched polyethylene, polymerization catalysts described in Japanese Patent Publication No. 2004-292772, Japanese Patent Publication No. 2012-214780, Japanese Patent Publication No. 2015-189973, and Japanese Patent Publication No. 2017-20019 can be used.

[0447] Examples of the polymerization method include: a solvent polymerization method using aliphatic hydrocarbons such as butane, pentane, hexane, heptane, and octane; aromatic hydrocarbons such as benzene and toluene; and halogenated hydrocarbons such as dichloromethane as solvents; a slurry polymerization method, and a gas phase polymerization method in which polymerization is performed in a gaseous monomer. In addition, a method in which these methods are combined may be used, such as a method in which polymerization is performed by a solution polymerization method and then by a gas phase polymerization method; a method in which polymerization is performed by a slurry polymerization method and then by a gas phase polymerization method.

[0448] The polymerization pressure is usually normal pressure to 5 MPa. The polymerization temperature can be in the range of 0°C to 220°C. The polymerization temperature is preferably above 20°C, more preferably above 40°C, and further preferably above 50°C. In addition, the polymerization temperature is preferably below 130°C, more preferably below 100°C. The polymerization time is usually appropriately determined according to the type of target polymer and the reaction device, and is 1 minute to 20 hours. In addition, in order to adjust the molecular weight of the ethylene polymer, a chain transfer agent such as hydrogen may also be added.

[0449] In addition, any of continuous polymerization and intermittent polymerization can be used. In addition, it can be a single-step polymerization method or a multi-step polymerization method. In the case of polymerization by a multi-step polymerization method, a plurality of polymerization reactors can be connected in series or in parallel, and both polymerization reactors connected in series and polymerization reactors connected in parallel can be used.

[0450] In ethylene polymers, various known resins, rubbers, additives can be used. As resin and rubber, it can be olefin polymers (polyolefins from fossil resources) such as ethylene polymers (polyethylene from fossil resources) and propylene polymers (polypropylene from fossil resources) made with olefins from fossil resources as raw materials, or it can be olefin polymers (polyolefins from biomass) such as ethylene polymers (polyethylene from biomass) and propylene polymers (polypropylene from biomass) made with biomass olefins. In addition, it can also be olefin polymers (regenerated polyolefins) such as ethylene polymers (regenerated polyethylene) and propylene polymers (regenerated polypropylene) obtained by material recycling. In addition, it is also possible to combine these substances more than two.

[0451] As additives, one or more antioxidants (phenols, phosphorus, sulfur), ultraviolet absorbers, light stabilizers, lubricants, antistatic agents, antifogging agents, anti-blocking agents, mold release agents, processing aids, inorganic pigments, organic pigments, content dispersants, dyes, crosslinking agents, foaming agents, organic peroxides, neutralizers, adsorbents, weathering stabilizers, heat stabilizers, copper inhibitors, crystal nucleating agents, plasticizers, inorganic fillers or organic fillers, flame retardants, antibacterial agents, light diffusers and other known additives can be combined. As these known additives, compounds described in "Handbook of Rubber and Plastic Compound Chemicals" (Rubber Digest, Co., Ltd., issued on April 27, 2001), "Plastics Data Handbook" (Asahi Kasei Amidas Co., Ltd. and "Plastics" Editorial Department, Co., Ltd. Industrial Research Institute, issued on December 1, 1999) and the like can be cited.

[0452] Examples of organic fillers include carbon fibers, carbon black, carbon nanotubes, cellulose nanofibers, and wood powder. Examples of inorganic fillers include silicon dioxide, diatomaceous earth, aluminum oxide, titanium oxide, magnesium oxide, pumice powder, pumice balls, aluminum hydroxide, magnesium hydroxide, dolomite, calcium sulfate, potassium titanate, barium sulfate, talc, clay, mica, flaky glass, glass beads, glass fibers, aluminum silicate, calcium silicate, montmorillonite, bentonite, molybdenum sulfide, graphite, calcium carbonate, metal powders (aluminum, copper, iron, lead, etc.), and silica.

[0453] Ethylene polymers can be formed into various molded bodies (films, sheets, containers (bottles, trays, etc.)) by known molding processing methods, such as injection molding, extrusion molding, blow molding, compression molding, vacuum molding, calendar molding, foam molding, etc. As the film molding method, for example, there can be mentioned: extrusion lamination molding, T-die film molding, inflation molding (air cooling, water cooling, multi-stage cooling, high-speed processing) and the like.

[0454] The molded body using the ethylene polymer may be a single-layered molded body containing the ethylene polymer or a multi-layered molded body having layers other than the layer containing the ethylene polymer. Examples of the layer other than the layer containing the ethylene polymer include: vinyl polymers such as polyvinyl chloride, polyvinylidene chloride, polystyrene, polyacrylate, polyacrylonitrile, etc.; polyamide polymers such as nylon 6, nylon 66, nylon 10, nylon 11, nylon 12, nylon 610, poly(m-phenylene adipamide), etc.; polyester polymers such as polyethylene terephthalate, polyethylene terephthalate / isophthalate, polybutylene terephthalate, etc.; polyvinyl alcohol; ethylene-vinyl alcohol copolymer; polycarbonate polymers; paper; barrier films (aluminum foil, vapor-deposited film, coating film, etc.), etc.

[0455] The molded article can be applied to various known uses. Specific uses include, for example, various packaging films such as food packaging, cling film, standard bags, heavy packaging bags, sugar bags, paper containers for liquids, laminated blanks, special-shaped liquid packaging bags (stand-up bags, etc.), infusion bags, liner bags in boxes, clean films for packaging semiconductor materials and medicines, protective films, blow bottles, squeeze bottles, caps, labels, short tubes, tubes, fuel tanks, agricultural materials, daily groceries, fibers, etc.

[0456] <Propylene polymer>

[0457] By polymerizing monomers including propylene produced in the present invention, propylene-based polymers such as homopolypropylene, random polypropylene, and block polypropylene (heterophasic polypropylene) can be produced.

[0458] 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 hydrocarbons 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.

[0459] As propylene, in addition to the propylene manufactured in the present invention, propylene from fossil resources can be used, propylene from biomass can be used, or both propylene from fossil resources and propylene from biomass can be used. In addition, as monomers other than propylene, monomers manufactured in the present invention (e.g., ethylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1-heptene) can be used, monomers from fossil resources (e.g., ethylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1-heptene) can be used, monomers from biomass (e.g., ethylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1-heptene) can be used, or two or more thereof, such as monomer manufactured in the present invention / monomer from fossil resources, monomer manufactured in the present invention / monomer from biomass, monomer from fossil resources / monomer from biomass, monomer manufactured in the present invention / monomer from fossil resources / monomer from biomass, can be used in combination.

[0460] Specific examples of polymers include propylene homopolymers, propylene-ethylene copolymers, propylene-1-butene copolymers, propylene-1-hexene copolymers, propylene-ethylene-1-butene copolymers, propylene-ethylene-1-hexene copolymers, propylene-ethylene-1-butene-1-hexene copolymers, etc. In addition, these copolymers may be random polypropylene or block polypropylene (heterogeneous polypropylene).

[0461] When the propylene polymer is set to 100 mass %, the content of the propylene unit in the propylene polymer is usually 50 mass % or more, preferably 70 mass % or more. It should be noted that the content of the propylene unit can be determined by IR method or 13 Determined by C-NMR method.

[0462] The melt flow rate (MFR) of the propylene polymer is usually 0.01 g / 10 min to 1000 g / 10 min, preferably 0.05 g / 10 min to 100 g / 10 min. The MFR is measured under the conditions of a temperature of 230° C. and a load of 2.16 kg as specified in JIS K7210-1-2014.

[0463] The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the propylene-based polymer is usually 2-15, preferably 3-10.

[0464] In the case where the propylene polymer is homopolypropylene, the isotactic pentad fraction of the homopolypropylene is preferably 0.9 to 0.999, more preferably 0.95 to 0.998. The above 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 continuous pentad units in the polymer chain. 13 In the measurement of C-NMR spectrum, 13 The intensity fraction of the mmmm peak in all absorption peaks in the methyl carbon region of the C-NMR spectrum was taken as the isotactic pentad fraction. The attribution of peaks in the NMR spectrum was based on the description in Macromolecules, Vol. 8, p. 687 (published in 1975).

[0465] When the propylene-based polymer is a random polypropylene obtained by random copolymerization of propylene and olefins, the content of the propylene unit in the random polypropylene is preferably 90% to 99.9% by mass, more preferably 92% to 99% by mass, and the content of the olefin unit is preferably 0.1% to 10% by mass, more preferably 1% to 8% by mass, when the random polypropylene is set to 100% by mass. 13 Determined by C-NMR method.

[0466] The melting point of random polypropylene is usually 100° C. to 160° C., preferably 115° C. to 155° C. When the melting point is within this range, transparency and sealing properties are excellent. The melting point is measured using a differential scanning calorimeter in accordance with JIS-K7121.

[0467] When the propylene-based polymer is a block polypropylene, the block polypropylene is preferably a propylene-ethylene block copolymer containing a polymer component (a) comprising a propylene homopolymer or a propylene-ethylene random copolymer containing 95% by mass to 100% by mass of propylene units and 0% by mass to 5% by mass of ethylene units (wherein the total amount of propylene units and ethylene units is 100% by mass), and a propylene-ethylene random copolymer component (b) containing 20% ​​by mass to 80% by mass of propylene units and 20% by mass to 80% by mass of ethylene units.

[0468] The intrinsic viscosity [η] of the polymer component (a) contained in the propylene-ethylene block copolymer is preferably 0.8 dl / g 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 dl / g to 10 dl / g. It should be noted that the above intrinsic viscosity is measured at a temperature of 135° C. in a tetralin solution.

[0469] The content of the polymer component (a) contained in the propylene-ethylene block copolymer is preferably 55% to 95% by mass, and more preferably 65% ​​to 90% by mass. In addition, the content of the propylene-ethylene random copolymer component (b) contained in the propylene-ethylene block copolymer is preferably 5% to 45% by mass, and more preferably 10% to 35% by mass. The total amount of the polymer component (a) and the propylene-ethylene random copolymer component (b) contained in the propylene-ethylene block copolymer is set to 100% by mass.

[0470] As a method for producing propylene-based polymers, there can be cited a method of polymerizing monomers containing propylene using a stereoregular olefin polymerization catalyst. As a polymerization catalyst, a known stereoregular olefin polymerization catalyst, for example, a polymerization catalyst described in the "New Edition of Polypropylene Handbook" (edited by Nero Pasquini, Nikkan Kogyo Shimbun, issued on September 28, 2012) can be used, and there can be cited a Ziegler-Natta catalyst system, a metallocene catalyst system, a catalyst system obtained by combining these catalyst systems, etc. As a polymerization method, for example, there can be cited a bulk polymerization method, a solution polymerization method, a slurry polymerization method, a gas phase polymerization method, or a polymerization method obtained by arbitrarily combining these polymerization methods, etc. These polymerization methods can be any of continuous polymerization methods and intermittent polymerization methods. In addition, the method for producing propylene-based polymers can be a single-step polymerization method or a multi-step polymerization method. In the case of polymerization by a multi-step polymerization method, a plurality of polymerization reactors can be connected in series or in parallel, and both polymerization reactors connected in series and polymerization reactors connected in parallel can be used. The process described in the "New Edition of Polypropylene Handbook" (published by Nikkan Kogyo Shimbun in 2012) can be used. The method for producing propylene polymers is preferably a continuous gas phase polymerization method. The polymerization conditions such as polymerization temperature, polymerization pressure, monomer concentration, catalyst input amount, polymerization time, etc. can be appropriately determined according to the composition and structure of the target propylene polymer.

[0471] Various known resins, rubbers, and additives can be used in conjunction with propylene polymers. As resins and rubbers, polymers exemplified as resins and rubbers that can be combined with ethylene polymers can be cited. In addition, ethylene-1-butene copolymers, ethylene-1-hexene copolymers, ethylene-1-octene copolymers, ethylene-propylene-5-ethylidene-2-norbornene copolymers, styrene-butadiene-styrene block copolymers, hydrogenated styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, hydrogenated styrene-isoprene-styrene block copolymers, etc. can be cited.

[0472] As additives, the additives exemplified as additives that can be incorporated into ethylene polymers can be cited. In addition, the additives and proportions described in the "New Edition Polypropylene Handbook" (edited by Nero Pasquini, 2012, Nikkan Kogyo Shimbun, issued on September 28, 2012) can be cited.

[0473] The propylene-based polymer can be molded into various molded products by a known molding method. Examples of the molding method include the molding methods exemplified for the ethylene-based polymer.

[0474] The molded article using propylene polymers can be a monolayer molded article containing propylene polymers, or can be a multilayer molded article having a layer other than the layer containing propylene polymers. As the layer other than the layer containing propylene polymers, the layer exemplified in the molded article using ethylene polymers can be enumerated.

[0475] The molded body can be applied to various known uses, automobile parts such as automobile interior parts and exterior parts, two-wheeled vehicle parts, food and medical containers, furniture and electrical product parts, civil engineering and building materials, etc. As automobile exterior parts, bumpers, fenders, wheel covers, etc. can be listed, as automobile interior parts, instrument panels, door trim panels, door panels, pillars, body guards, inter-seat storage boxes, column covers, etc. can be listed, as two-wheeled vehicle parts, covers, muffler covers, etc. can be listed. As food and medical containers, retort bags, retort containers, microwave heat-resistant containers, frozen food containers, special-shaped liquid packaging bags (self-supporting bags, etc.), plastic wrap, blow bottles, caps, labels, infusion bags, infusion bottles, medical containers, cosmetic containers, etc. can be listed. As furniture and electrical product parts, wallpaper, floor materials, decorative sheets, drainage hoses for washing machines, etc. can be listed. As civil engineering and building materials, for example, waterproof sheets, water retaining sheets, hoses, ducts, gaskets, etc. can be listed.

[0476] <Butadiene polymer>

[0477] By polymerizing the monomers including butadiene produced in the present invention, a butadiene homopolymer or a copolymer of butadiene and a monomer other than butadiene can be produced.

[0478] Examples of butadiene include 1,3-butadiene, 1,2-butadiene, etc. In addition to the butadiene produced in the present invention, butadiene produced using fossil resources such as petroleum, coal, and natural gas as raw materials (butadiene derived from fossil resources) may be used, butadiene produced using plants such as sugar cane and corn as raw materials (butadiene derived from biomass) may be used, and both butadiene derived from fossil resources and butadiene derived from biomass may be used.

[0479] Examples of the monomer 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.

[0480] Examples of aromatic vinyl compounds include styrene, p-methylstyrene, α-methylstyrene, vinyl ethylbenzene, vinyl xylene, vinyl naphthalene, diphenylethylene, etc. Examples of non-conjugated dienes include dicyclopentadiene, 5-ethylidene-2-norbornene, 1,5-hexadiene, etc. Examples of vinyl cyanide compounds include acrylonitrile, methacrylonitrile, etc. Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, etc. Examples of unsaturated carboxylic acid alkyl esters include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, etc. Examples of the unsaturated carboxylic acid amides include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, glycidyl methacrylate, and the like. Examples of the unsaturated carboxylic acid amides include acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N,N-dimethylacrylamide, N,N-dimethylaminopropyl acrylamide, and N,N-dimethylaminopropyl methacrylamide.

[0481] Furthermore, these copolymerizable monomers may be the compounds produced in the present invention or compounds derived therefrom, monomers derived from fossil resources, monomers derived from biomass, or monomers obtained by combining these monomers.

[0482] Specific examples of the polymer include 1,3-butadiene homopolymers, 1,3-butadiene-styrene copolymers, 1,3-butadiene-acrylonitrile copolymers, 1,3-butadiene-methyl methacrylate copolymers, 1,3-butadiene-styrene-acrylonitrile copolymers, 1,3-butadiene-acrylonitrile-acrylic acid copolymers, 1,3-butadiene-styrene-acrylonitrile-methyl methacrylate copolymers, 1,3-butadiene-styrene-acrylonitrile-acrylic acid copolymers, and 1,3-butadiene-styrene-acrylonitrile-methyl methacrylate-acrylic acid copolymers.

[0483] When the butadiene-based polymer is taken as 100% by mass, the content of the butadiene unit in the butadiene-based polymer is preferably 20% by mass or more.

[0484] Among butadiene polymers, copolymers of butadiene, unsaturated carboxylic acid and other copolymerizable monomers are suitable for latex for paper coating and adhesives. The content of butadiene units in the above copolymers 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. The above copolymer is set to 100% by mass.

[0485] The glass transition temperature of the butadiene polymer suitable for the latex preferably has at least two points between -100°C and 50°C, more preferably at least one point between -100°C and 0°C as the low glass transition temperature, and at least one point between -5°C and 50°C as the high glass transition temperature. The glass transition temperature is measured using a differential scanning calorimeter.

[0486] As a method for producing a butadiene polymer, there can be cited a method of polymerizing a monomer containing butadiene by an emulsion polymerization method using a known free radical polymerization initiator. In the emulsion polymerization method, a batch polymerization method is preferred, and a multi-step polymerization method and a seed polymerization method can be used. In addition, as a method for producing a butadiene polymer, there can be cited a method of polymerizing a monomer containing butadiene by a solution polymerization method using an organic alkali metal catalyst or a metallocene catalyst. In the solution polymerization method, it can be any of a continuous polymerization method and a batch polymerization method, and it can be any of a single-step polymerization method and a multi-step polymerization method.

[0487] Butadiene polymers suitable for latex are useful as binders for particles, powders or fillers containing metals, inorganic compounds, ceramics, pigments, fluorescent materials, glass, etc. In particular, they can be used as binders for paper coating compositions and binders for compositions for forming electrodes of electrochemical devices such as batteries, capacitors, and lithium ion capacitors. In addition, butadiene polymers can be used for various rubber applications such as tires, vibration-proof rubbers, belts, hoses, and industrial products such as seismic isolation rubbers, and shoes such as men's shoes, women's shoes, and sports shoes.

[0488] [Method for producing compound and method for producing polymer]

[0489] The method for producing the compound of the present embodiment comprises the following steps: using an unsaturated hydrocarbon having 2 to 8 carbon atoms obtained by the method for producing an unsaturated hydrocarbon having 2 to 8 carbon atoms of any one of the first to seventh embodiments or an unsaturated hydrocarbon mixture having 2 to 8 carbon atoms obtained by the method for producing the above-mentioned mixture of unsaturated hydrocarbons having 2 to 8 carbon atoms as a raw material, and synthesizing at least one compound selected from the group of compounds consisting of methyl methacrylate, propylene oxide, ethylene oxide, ethylene glycol, phenol, acetone and isopropanol.

[0490] The method for producing a polymer of the present embodiment is a method for producing a polymer comprising the step of polymerizing a monomer, wherein the monomer is produced by using as a raw material an unsaturated hydrocarbon having 2 to 8 carbon atoms obtained by a method for producing an unsaturated hydrocarbon having 2 to 8 carbon atoms in any of the first to seventh embodiments 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 as described above, and the monomer comprises at least one compound selected from the group consisting of methyl methacrylate, propylene oxide, ethylene oxide and ethylene glycol.

[0491] <Method for producing methyl methacrylate>

[0492] Methyl methacrylate, which is a monomer of methyl methacrylate polymers, can be produced by using the unsaturated hydrocarbon having 2 to 8 carbon atoms and the mixture of unsaturated hydrocarbon having 2 to 8 carbon atoms produced in the present invention as raw materials by a known method, for example, the production method described in pages 4 to 14 of "Sumitomo Chemical 2004-II". For example, as a method for producing methyl methacrylate from ethylene, there are BASF process and Alpha process. As a method for producing methyl methacrylate from isobutylene, there are direct oxidation method (direct oxidation method), methacrylonitrile method (MAN) method, and direct oxidation esterification method (direct Meta method). The isobutylene may be isobutylene produced by dehydrogenation of isobutane, or isobutylene produced from tert-butyl alcohol produced using isobutane, isobutylene, etc. as a starting material, or isobutylene produced from methyl tert-butyl ether (MTBE) produced using isobutane, isobutylene, etc. as a starting material. In addition, as a method for producing methyl methacrylate from acetone, there is acetone cyanohydrin (ACH) method. This acetone is produced using propylene, benzene, toluene, and the like as starting materials.

[0493] 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.

[0494] The method for producing methyl methacrylate using ethylene as a raw material is preferably the Alpha process. The Alpha process is a method for synthesizing methyl propionate by reacting ethylene, carbon monoxide and methanol, and then reacting methyl propionate with formaldehyde to produce methyl methacrylate. As a catalyst for the reaction of ethylene, carbon monoxide and methanol, a palladium complex catalyst can be cited, and as a catalyst for the reaction of methyl propionate and formaldehyde, a Cs / SiO2 solid base catalyst can be cited.

[0495] As a method for producing methyl methacrylate using propylene as a raw material, the acetone cyanohydrin (ACH) method using acetone synthesized using propylene as a raw material is preferred. Acetone can be synthesized by a known method using propylene as a raw material. For example, a method of directly oxidizing propylene by reacting propylene with oxygen can be cited. As a catalyst, palladium chloride-copper chloride catalysts can be cited. In addition, as a method for synthesizing acetone, a method of synthesizing cumene (isopropylbenzene) by reacting propylene with benzene, then oxidizing the cumene to synthesize cumene hydroperoxide, and decomposing the cumene hydroperoxide to produce acetone and phenol can be cited. Examples of the ACH method include: a method in which acetone is reacted with hydrogen cyanide to synthesize acetone cyanohydrin, acetone cyanohydrin is reacted with sulfuric acid to synthesize methacrylamide sulfate, and methacrylamide sulfate is reacted with methanol to produce methyl methacrylate; a method in which acetone is reacted with hydrogen cyanide to synthesize acetone cyanohydrin, acetone cyanohydrin is hydrated to synthesize α-hydroxyisobutyramide, α-hydroxyisobutyramide is reacted with methyl formate to synthesize methyl α-hydroxyisobutyrate, and methyl α-hydroxyisobutyrate is dehydrated to produce methyl methacrylate.

[0496] The method for producing methyl methacrylate using isobutylene as a raw material is preferably a direct oxidation method (direct oxidation method). As the direct oxidation method (direct oxidation method), there can be listed: a method in which isobutylene is oxidized with oxygen to synthesize methacrolein, and methacrolein is further oxidized with oxygen to synthesize methacrylic acid, and then methanol and methacrylic acid are reacted to produce methyl methacrylate; a method in which isobutylene is hydrated to synthesize tert-butyl alcohol, and tert-butyl alcohol is oxidized with oxygen to synthesize methacrolein, and methacrolein is further oxidized with oxygen to synthesize methacrylic acid, and then methacrylic acid is reacted with methanol to produce methyl methacrylate; a method in which isobutylene is hydrated to synthesize tert-butyl alcohol, and tert-butyl alcohol is then dehydrated to synthesize isobutylene, and then isobutylene is oxidized with oxygen to synthesize methacrolein, and methacrolein is further oxidized with oxygen to synthesize methacrylic acid, and methacrylic acid is reacted with methanol to produce methyl methacrylate.

[0497] The catalyst used in the oxidation reaction of isobutylene and tert-butyl alcohol is preferably a catalyst comprising molybdenum and bismuth, and more preferably a Mo-Bi-Fe-XAO type catalyst (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 comprising molybdenum and phosphorus, and more preferably a P-Mo-V-Cu-AO type catalyst (A represents at least one element selected from the group consisting of alkali metals, alkaline earth metals and thallium). As these catalysts, catalysts described in Japanese Patent Laid-Open No. 5-23596, International Publication No. 2019 / 013116, International Publication No. 2020 / 196853, and International Publication No. 2021 / 200689 can be used.

[0498] Examples of the catalyst used in the reaction of methacrylic acid and methanol include acid catalysts such as sulfuric acid and strongly acidic cation exchange resins. In addition, examples of the catalyst used in the hydration reaction of isobutylene include acid catalysts such as strongly acidic cation exchange resins and heteropoly acids. Examples of the catalyst used in the dehydration reaction of tert-butyl alcohol include solid acids such as solid phosphoric acid, activated alumina, and silica-alumina; strong acids such as sulfuric acid; and acid catalysts such as strongly acidic ion exchange resins containing sulfonic acid groups.

[0499] <Method for producing methyl methacrylate polymer>

[0500] The method for producing a methyl methacrylate polymer includes a step of polymerizing a monomer comprising methyl methacrylate produced using as a raw material an unsaturated hydrocarbon having 2 to 8 carbon atoms obtained by the method for producing an unsaturated hydrocarbon having 2 to 8 carbon atoms of any one of the first to seventh embodiments 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.

[0501] As a method for producing a methyl methacrylate polymer, there can be cited a method of polymerizing a monomer containing methyl methacrylate using a known free radical polymerization initiator. As a polymerization method, there can be cited a suspension polymerization method, a solution polymerization method, a bulk polymerization method, etc., preferably a bulk polymerization method. In addition, the method for producing a methyl methacrylate polymer can be any of a continuous polymerization method and an intermittent polymerization method, and can be any of a single-step polymerization method and a multi-step polymerization method. For example, the production methods described in Japanese Patent Publication No. 2011-168683, Japanese Patent Publication No. 2014-108988, International Publication No. 2017 / 010323, and Japanese Patent Publication No. 2021-155698 can be used.

[0502] (Methyl methacrylate polymer)

[0503] By polymerizing the monomers containing methyl methacrylate obtained by the above production method, a methyl methacrylate homopolymer or a copolymer of methyl methacrylate and a monomer other than methyl methacrylate can be produced.

[0504] As 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 a raw material (fossil resource-derived methyl methacrylate) can be used, methyl methacrylate produced using plants such as sugar cane and corn as a raw material (biomass-derived methyl methacrylate) can be used, and both fossil resource-derived methyl methacrylate and biomass-derived methyl methacrylate can be used.

[0505] Examples of the monomer copolymerizable with methyl methacrylate include acrylic acid esters, unsaturated carboxylic acids, unsaturated carboxylic acid amides, vinyl cyanide compounds, and aromatic vinyl compounds.

[0506] Examples of acrylic acid esters include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, cyclohexyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, cyclopentadienyl acrylate, etc. Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic anhydride, itaconic anhydride, etc. Examples of vinyl cyanide compounds include acrylonitrile, methacrylonitrile, etc. Examples of unsaturated carboxylic acid amides include acrylamide, methacrylamide, etc. Examples of aromatic vinyl compounds include styrene, α-methylstyrene, etc.

[0507] Furthermore, these copolymerizable monomers may be the compounds produced in the present invention or compounds derived therefrom, monomers derived from fossil resources, monomers derived from biomass, or monomers obtained by combining these monomers.

[0508] 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.

[0509] When the methyl methacrylate polymer is 100 mass %, the content of methyl methacrylate units in the methyl methacrylate polymer is preferably 80 mass % or more, more preferably 90 mass % or more. It should be noted that the content of methyl methacrylate units is measured by pyrolysis gas chromatography.

[0510] The weight 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 to 10.

[0511] In the methyl methacrylate polymer, various known resins, rubbers, and additives can be used. As resins and rubbers, methyl methacrylate polymers (polymethyl methacrylate from fossil resources) manufactured using methyl methacrylate from fossil resources as raw materials can be used, and methyl methacrylate polymers (polymethyl methacrylate from biomass) manufactured using methyl methacrylate from biomass as raw materials can be used. In addition, methyl methacrylate polymers (regenerated polymethyl methacrylate) obtained by recycling can also be used. Two or more of these substances can also be combined.

[0512] Examples of the additives include those exemplified as the additives that can be blended into the ethylene-based polymer.

[0513] The methyl methacrylate polymer can be formed into various molded bodies by known molding methods, such as injection molding, extrusion molding, and press molding. In addition, the obtained molded body can be further subjected to secondary molding by compressed air molding, vacuum molding, and the like.

[0514] The molded article can be applied to various known uses, such as optical materials, vehicle parts, lighting materials, building materials, etc. Examples of vehicle parts for automobiles include rear light covers, optical components inside rear lights, inner lenses for headlights (sometimes referred to as searchlight lenses or PES lenses), instrument covers, door mirror housings, pillar covers (window frame covers), license plate ornaments, front grilles, fog light ornaments, and vehicle emblems.

[0515] <Method for producing propylene oxide>

[0516] Propylene oxide can be produced by using propylene as a raw material by a known method, for example, the production method described in pages 4 to 10 of "Sumitomo Chemical 2006-I" and pages 4 to 11 of Sumitomo Chemical "2019". For example, the chlorine method (chlorohydrin method), the isopropylbenzene method (POC method), the hydrogen peroxide method (HPPO method), the modified hydrogen peroxide method (modified HPPO method), the direct oxidation method, the Halcon method (ethylbenzene method (propylene oxide / styrene monomer (PO / SM) co-production method), and the isobutane method (propylene oxide / tert-butyl alcohol (PO / TBA) co-production method).

[0517] The chlorine method (chlorohydrin method) is a method for producing propylene oxide by synthesizing chloropropanol from propylene, chlorine gas and water, and then dehydrochlorinating the chloropropanol with calcium hydroxide. The hydrogen peroxide method (HPPO method) and the modified hydrogen peroxide method (modified HPPO method) are methods for producing propylene oxide from propylene and hydrogen peroxide. In addition, the cumene method is a method for producing propylene oxide by oxidizing cumene to synthesize cumene hydroperoxide, then epoxidizing propylene with cumene hydroperoxide to synthesize propylene oxide, and hydrogenating α-cumyl alcohol produced as a by-product in the epoxidation to synthesize cumene.

[0518] <Method for producing propylene oxide polymer>

[0519] The method for producing a propylene oxide-based polymer includes a step of polymerizing monomers including propylene oxide produced using propylene obtained by the production method of the present invention as a raw material.

[0520] (Propylene oxide polymer)

[0521] As propylene oxide polymers, there can be mentioned: polypropylene glycol, copolymers of polypropylene glycol and polyisocyanates. These polymers can be manufactured by known methods. For example, regarding polypropylene glycol, it can be manufactured by using polyols (ethylene glycol, dipropylene glycol, glycerol, sorbitol, sucrose, etc.), amines, polyamines, etc. as polymerization initiators to homopolymerize propylene oxide or copolymerize propylene oxide and ethylene oxide. As catalysts, there can be mentioned: alkaline catalysts such as potassium hydroxide. In addition, as catalysts for the copolymerization of polypropylene glycol and polyisocyanates, there can be mentioned: amine catalysts (triethylenediamine, bis(2-dimethylaminoethyl) ether, N,N,N',N'-tetramethylhexamethylenediamine, etc.), metal catalysts (dibutyltin dilaurate, stannous octoate, etc.).

[0522] Here, examples of the polyisocyanate include toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymethylene polyphenyl polyisocyanate (polymeric MDI), xylylene diisocyanate (XDI), naphthalene diisocyanate (NDI), p-phenylene diisocyanate (PPDI), tetramethylxylylene diisocyanate (TMXDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI), and the like.

[0523] <Method for producing ethylene oxide>

[0524] Ethylene oxide can be produced by a known method using ethylene produced in the present invention as a raw material. For example, it can be produced by a method of catalytic gas phase oxidation of ethylene oxide using a gas containing molecular oxygen. Examples of catalysts include silver catalysts. More specifically, examples include methods described in Japanese Patent Application Publication No. 62-103072, Japanese Patent Application Publication No. 2010-36104, Japanese Patent Application Publication No. 2014-198680, and International Publication No. 2020 / 032279.

[0525] <Method for producing ethylene oxide polymer>

[0526] The method for producing an ethylene oxide-based polymer includes a step of polymerizing monomers including ethylene oxide produced using ethylene obtained by the production method of the present invention as a raw material.

[0527] (Ethylene oxide polymer)

[0528] Ethylene oxide polymers can be produced by known methods. For example, they can be produced by a method of subjecting ethylene oxide to ring-opening polymerization. Examples of catalysts include metal alkoxide catalysts. In addition, examples of methods for producing ethylene oxide polymers include a method of polymerizing ethylene oxide using polyols (ethylene glycol, glycerol, sorbitol, sucrose, etc.), amines, polyamines, etc. as polymerization initiators. Examples of catalysts include alkaline catalysts such as potassium hydroxide.

[0529] <Method for producing ethylene glycol>

[0530] Ethylene glycol can be produced by a known method 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. The production is carried out in the presence or absence of an acid catalyst. In addition, as a method for producing ethylene glycol, there can be cited a method of reacting ethylene oxide with carbon dioxide to produce ethylene carbonate, and then reacting ethylene carbonate with water. As catalysts, there can be cited alkali metal bromides, alkali metal iodides, quaternary Halides, etc. More specifically, the methods described in Japanese Patent Application Laid-Open No. 54-16416, Japanese Patent Application Laid-Open No. 2001-316308, Japanese Patent Application Laid-Open No. 2000-128814, and Japanese Patent Application Laid-Open No. 2002-201148 can be cited.

[0531] <Method for producing ethylene glycol polymer>

[0532] The method for producing an ethylene glycol-based polymer comprises a step of polymerizing monomers including ethylene glycol produced using ethylene obtained by the production method of the present invention as a raw material.

[0533] (Ethylene glycol polymer)

[0534] Examples of ethylene glycol polymers include copolymers of ethylene glycol and dicarboxylic acids or dimethyl dicarboxylates. Examples of dicarboxylic acids include terephthalic acid, isophthalic acid, and 2,6-naphthalene dicarboxylic acid, and examples of dimethyl dicarboxylates include dimethyl terephthalate, dimethyl isophthalate, and dimethyl 2,6-naphthalene dicarboxylate. These polymers can be produced, for example, by subjecting dicarboxylic acids to direct esterification with ethylene glycol or subjecting dimethyl dicarboxylate to transesterification with ethylene glycol to synthesize bishydroxyethyl compounds (e.g., bishydroxyethyl terephthalate, bishydroxyethyl isophthalate, and bishydroxyethyl 2,6-naphthalene dicarboxylate), and subjecting the bishydroxyethyl compounds to polycondensation.

[0535] The direct esterification reaction is usually carried out without a catalyst, and an alkali metal, an amine compound, etc. are used as a diethylene glycol generation inhibitor as needed. In addition, as a catalyst for the transesterification reaction, there can be listed: weak acid salts of calcium, manganese, magnesium, zinc, lithium, etc.; titanates, etc., specifically, calcium acetate, magnesium acetate, lithium acetate, etc. can be used. As a catalyst for the polycondensation reaction, there can be listed: antimony compounds such as antimony trioxide, germanium compounds such as germanium dioxide; titanium compounds such as tetra-n-propyl titanate, tetra-isopropyl titanate, tetra-n-butyl titanate; aluminum compounds such as aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, and aluminum acetylacetonate.

[0536] <Method for producing phenol>

[0537] 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 and benzene can be reacted to synthesize cumene (isopropylbenzene), and then the cumene can be oxidized by a mixed gas containing oxygen and an inert gas, an oxygen-containing gas such as air, to synthesize cumene hydroperoxide, and the cumene hydroperoxide is decomposed to produce phenol and acetone. Here, as a catalyst for the reaction of propylene and benzene, aluminum chloride catalysts, zeolite catalysts, phosphoric acid catalysts, etc. can be listed. The oxidation reaction of cumene is carried out by auto-oxidation. The oxidation reaction can be carried out without using additives, or additives such as alkali can be used. As the additive, alkali metal compounds such as NaOH and KOH, alkaline earth metal compounds, alkali metal carbonates such as Na2CO3 and NaHCO3, ammonia, (NH4)2CO3, alkali metal ammonium carbonates, etc. can be listed. In addition, as a catalyst for the decomposition reaction of cumene hydroperoxide, acid catalysts such as sulfuric acid can be listed.

[0538] <Method for producing acetone>

[0539] Acetone can be produced by a known method using propylene obtained by the production method of the present invention as a raw material. For example, it can be produced by a method in which propylene is directly oxidized by reacting propylene with oxygen. As a catalyst, palladium chloride-copper chloride catalysts can be cited. In addition, as a method for producing acetone, the following method can be cited: as in the above-mentioned method for producing phenol, propylene and benzene are reacted to synthesize isopropylbenzene (isopropylbenzene), and then the isopropylbenzene is oxidized to synthesize isopropylbenzene hydroperoxide, and the isopropylbenzene hydroperoxide is decomposed to produce acetone and phenol.

[0540] <Method for producing isopropyl alcohol>

[0541] Isopropyl alcohol can be produced by a known method 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. As catalysts, there can be listed: strongly acidic cation exchange resins; acid catalysts such as heteropoly acids such as phosphotungstic acid, silicotungstic acid and silicomolybdic acid. Specifically, there can be listed: methods described in Japanese Patent Laid-Open No. 8-165259, Japanese Patent Laid-Open No. 8-165260, Japanese Patent Laid-Open No. 8-291092, and International Publication No. 2017 / 217279. In addition, as a method for producing isopropyl alcohol, the following method can be listed: as in the above-mentioned method for producing acetone, propylene and benzene are reacted to synthesize isopropylbenzene (isopropylbenzene), and then the isopropylbenzene is oxidized to synthesize isopropylbenzene hydroperoxide, and the isopropylbenzene hydroperoxide is decomposed to synthesize acetone and phenol, and then the acetone is reacted with hydrogen. As the catalyst for the reaction of acetone and hydrogen, there can be mentioned: hydrogenation catalysts such as copper oxide·chromium oxide catalysts, Raney nickel catalysts, platinum, palladium, ruthenium and other precious metal catalysts. Specifically, there can be mentioned: the methods described in Japanese Patent Publication No. 2002-121160 and Japanese Patent Publication No. 2002-128716. Copper oxide·chromium oxide catalysts and Raney nickel catalysts are preferred.

[0542] [Carbon concentration from plants]

[0543] In the production method of the present invention, raw materials based on fossil resources such as petroleum, coal, and natural gas (raw materials derived from fossil resources) and raw materials based on plants such as sugar cane and corn (raw materials derived from biomass) can be used in combination. Therefore, when raw materials derived from biomass are used in the production method of the present invention, the compound produced in the present invention and the derivative produced using the compound as a starting material (for example, the above-mentioned compound, Figure 1 to Figure 5 The compound described in the present invention has carbon from plants. In addition, by applying the mass balance method to the biomass, the biomass can be allocated to the compound produced in the present invention and the derivative produced using the compound as a starting material. Therefore, according to the biomass of the compounds and derivatives as a whole, any product among these compounds and derivatives can be made into a biomass product, so the production method of the present invention is useful.

[0544] The compounds produced in the present invention and the derivatives produced using the above compounds as starting materials (e.g., the above compounds, Figure 1 to Figure 5The carbon concentration from plants of the compound described in (compounds described in) can be changed by adjusting the amount ratio of the raw material from fossil resources to the raw material from biomass, etc., preferably 0.1pMC (%) ~ 99.9pMC (%), more preferably 0.3pMC (%) ~ 70pMC (%). From the viewpoint of reducing environmental load, the carbon concentration from plants is more preferably 0.5pMC (%) or more, more preferably 1pMC (%) or more, and particularly preferably 5pMC (%) or more. In addition, from the viewpoint of cost, the carbon concentration from plants is more preferably 60pMC (%) or less, more preferably 50pMC (%) or less, and particularly preferably 40pMC (%) or less.

[0545] In one embodiment, the plant-derived carbon concentration of the olefin 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 in the present invention is 0.1 pMC(%) to 99.9 pMC(%).

[0546] As another embodiment, the plant-derived carbon concentration of the 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 in the present invention is 0.1 pMC (%) to 99.9 pMC (%).

[0547] Carbon concentrations from plants can be determined by measuring radiocarbon ( 14 C). Since the carbon dioxide in the atmosphere contains a certain ratio (105.5 pMC) 14 C, so it is known that plants that absorb carbon dioxide from the atmosphere, such as corn, 14 The C content is also about 105.5 pMC. Moreover, it is known that fossil resources contain almost no 14 C. Therefore, by determining the total carbon atoms contained in the compounds and derivatives 14 C ratio, the plant-derived carbon concentration of the compound and derivative can be calculated. 14 The content of C is set as [ 14 C], the carbon concentration of compounds and derivatives from plants X bio It can be found as follows.

[0548] X bio (%)=[ 14 C] / 105.5×100

[0549] Theoretically, if all raw materials from plants are used as raw materials for compounds and derivatives, the carbon concentration from plants of the compounds and derivatives is 100%. In addition, the carbon concentration from plants of compounds and derivatives produced only from raw materials from fossil resources is 0%.

[0550] The carbon concentration derived from plants can be obtained in the form of pMC (percentage of modern carbon: unit %) by the AMS (Accelerator mass spectrometry) method specified in ISO 16620-2:2019.

Claims

1. A method for producing an unsaturated hydrocarbon having 2 to 8 carbon atoms, wherein: The manufacturing method comprises the following steps: Step (1), wherein a plastic mixture (A) and a residue (B) are separated from waste plastics, wherein the content of polyolefin plastic in the plastic mixture (A) is 50% by mass or more; Step (2), wherein the plastic mixture (A) is decomposed to obtain a reaction product containing an unsaturated hydrocarbon having 2 to 8 carbon atoms; and Step (3) in which the reaction product is washed and purified to separate unsaturated hydrocarbons having 2 to 8 carbon atoms.

2. A method for producing an unsaturated hydrocarbon having 2 to 8 carbon atoms, wherein: The manufacturing method comprises the following steps: Step (1), wherein a plastic mixture (A) and a residue (B) are separated from waste plastics, wherein the content of polyolefin plastic in the plastic mixture (A) is 50% by mass or more; Step (12), wherein the residue (B) is heated to obtain a mixed gas containing carbon monoxide, carbon dioxide and hydrogen; Step (13), wherein the mixed gas is mixed with at least one gas selected from the group consisting of carbon monoxide, carbon dioxide and hydrogen, or a portion of at least one gas selected from the group consisting of carbon monoxide, carbon dioxide and hydrogen is removed from the mixed gas, thereby obtaining a regulated gas in which the volume amount of hydrogen is 1.5 to 4.0 relative to the total volume amount of carbon monoxide and carbon dioxide; step (14), in which carbon monoxide, carbon dioxide and hydrogen contained in the regulating gas are reacted to obtain alcohol; and Step (15) in which an unsaturated hydrocarbon having 2 to 8 carbon atoms is obtained using an alcohol as a raw material.

3. A method for producing an unsaturated hydrocarbon having 2 to 8 carbon atoms, wherein: The manufacturing method comprises the following steps: Step (1), wherein a plastic mixture (A) and a residue (B) are separated from waste plastics, wherein the content of polyolefin plastic in the plastic mixture (A) is 50% by mass or more; Step (2), wherein the plastic mixture (A) is decomposed to obtain a reaction product containing an unsaturated hydrocarbon having 2 to 8 carbon atoms; Step (3), wherein the reaction product is washed and purified to separate unsaturated hydrocarbons having 2 to 8 carbon atoms; Step (12), wherein the residue (B) is heated to obtain a mixed gas containing carbon monoxide, carbon dioxide and hydrogen; Step (13), wherein the mixed gas is mixed with at least one gas selected from the group consisting of carbon monoxide, carbon dioxide and hydrogen, or a portion of at least one gas selected from the group consisting of carbon monoxide, carbon dioxide and hydrogen is removed from the mixed gas, thereby obtaining a regulated gas in which the volume amount of hydrogen is 1.5 to 4.0 relative to the total volume amount of carbon monoxide and carbon dioxide; step (14), in which carbon monoxide, carbon dioxide and hydrogen contained in the regulating gas are reacted to obtain alcohol; and Step (15) in which an unsaturated hydrocarbon having 2 to 8 carbon atoms is obtained using an alcohol as a raw material.

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

5. A method for producing an unsaturated hydrocarbon having 2 to 8 carbon atoms, wherein: The manufacturing method comprises the following steps: step (21), wherein carbon dioxide is reacted with hydrogen to obtain a reaction mixture containing alcohol, carbon dioxide and carbon monoxide; and Step (22) in which an unsaturated hydrocarbon having 2 to 8 carbon atoms is obtained from the alcohol and / or carbon monoxide contained in the reaction mixture.

6. A method for producing an unsaturated hydrocarbon having 2 to 8 carbon atoms, wherein: The production method includes the production method of an unsaturated hydrocarbon having 2 to 8 carbon atoms according to any one of claims 1 to 4 and the production method of an unsaturated hydrocarbon having 2 to 8 carbon atoms according to claim 5.

7. A method for producing an unsaturated hydrocarbon having 2 to 8 carbon atoms, wherein: The manufacturing method comprises: The method for producing an unsaturated hydrocarbon having 2 to 8 carbon atoms according to any one of claims 1 to 5; and A method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms, comprising the step (31), wherein in the step (31), at least one alcohol selected from the group consisting of ethanol, propanol and butanol is subjected to a dehydration reaction to obtain unsaturated hydrocarbons having 2 to 8 carbon atoms.

8. A method for producing an unsaturated hydrocarbon having 2 to 8 carbon atoms, wherein: The manufacturing method comprises: The method for producing an unsaturated hydrocarbon having 2 to 8 carbon atoms according to claim 6; and A method for producing unsaturated hydrocarbons having 2 to 8 carbon atoms, comprising the step (31), wherein in the step (31), at least one alcohol selected from the group consisting of ethanol, propanol and butanol is subjected to a dehydration reaction to obtain unsaturated hydrocarbons having 2 to 8 carbon atoms.

9. A method for producing a mixture of unsaturated hydrocarbons having 2 to 8 carbon atoms, wherein: The production method includes a step (41) of contacting 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 8 with an unsaturated hydrocarbon having 2 to 8 carbon atoms derived from a fossil resource to obtain a mixture.

10. The method for producing a mixture of unsaturated hydrocarbons having 2 to 8 carbon atoms according to claim 9, wherein The contact mass of the unsaturated hydrocarbons having 2 to 8 carbon atoms derived from fossil resources is 0.001 to 10,000 relative to the contact mass of the unsaturated hydrocarbons having 2 to 8 carbon atoms.

11. A method for producing an olefin polymer, wherein: The production method includes a step of polymerizing monomers, wherein the monomers include unsaturated hydrocarbons having 2 to 8 carbon atoms obtained by the production method of unsaturated hydrocarbons having 2 to 8 carbon atoms described in any one of claims 1 to 8, or an unsaturated hydrocarbon mixture having 2 to 8 carbon atoms obtained by the production method of an unsaturated hydrocarbon mixture having 2 to 8 carbon atoms described in claim 9 or 10.

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

13. A method for producing a compound, wherein: The production method comprises the following steps, wherein an unsaturated hydrocarbon with a carbon number of 2 to 8 obtained by the production method of an unsaturated hydrocarbon with a carbon number of 2 to 8 according to any one of claims 1 to 8 or an unsaturated hydrocarbon mixture with a carbon number of 2 to 8 obtained by the production method of an unsaturated hydrocarbon mixture with a carbon number of 2 to 8 according to claim 9 or 10 is used as a raw material to synthesize at least one compound selected from the group consisting of methyl methacrylate, propylene oxide, ethylene oxide, ethylene glycol, phenol, acetone and isopropanol.

14. A method for producing a polymer, wherein: The production method includes a step of polymerizing a monomer, wherein the monomer is produced by using as a raw material an unsaturated hydrocarbon with a carbon number of 2 to 8 obtained by the production method of an unsaturated hydrocarbon with a carbon number of 2 to 8 according to any one of claims 1 to 8 or an unsaturated hydrocarbon mixture with a carbon number of 2 to 8 obtained by the production method of an unsaturated hydrocarbon mixture with a carbon number of 2 to 8 according to claim 9 or 10, and the monomer includes at least one compound selected from the group consisting of methyl methacrylate, propylene oxide, ethylene oxide and ethylene glycol.

15. An olefin polymer obtained by the method for producing an olefin polymer according to claim 11 or 12, wherein: The plant-derived carbon concentration of the olefin polymer is 0.1 pMC to 99.9 pMC.

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

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