Olefin production method and polymer production method

Abstract

The present invention provides a method for producing an olefin, which suppresses the formation of alkanes accompanying the production of an olefin from carbon dioxide and hydrogen, and increases the conversion rate of carbon dioxide in the production of an olefin. [Solution] A method for producing olefins includes a step of producing olefins from a feed gas in the presence of a mixture of a first catalyst and a second catalyst. The first catalyst contains copper. The second catalyst contains porous crystals. The feed gas contains carbon dioxide and hydrogen. The olefin has a carbon number of 2 or more. The mass of the first catalyst is represented as M1. The mass of the second catalyst is represented as M2. M2 / M1 is 1.00 or more.

Description

[Technical Field]

[0001] The present disclosure relates to a process for producing olefins and a process for producing polymers. [Background technology]

[0002] Fossil fuels are the main energy source in industrial society, but carbon dioxide emitted into the atmosphere by the combustion of fossil fuels is a major cause of global warming. Therefore, as one method for reducing carbon dioxide emissions and preventing global warming, it is desirable to use carbon dioxide as a raw material for chemical products. For example, Patent Document 1 listed below discloses a method and catalyst for converting carbon dioxide and hydrogen into long-chain hydrocarbons. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Special Publication No. 2025-504395 Summary of the Invention [Problem to be solved by the invention]

[0004] An object of one aspect of the present disclosure is to provide a method for producing an olefin, which suppresses the production of alkanes accompanying the production of an olefin from carbon dioxide and hydrogen, and which increases the conversion rate of carbon dioxide in the production of an olefin, and a method for producing a polymer using the olefin. [Means for solving the problem]

[0005] For example, one aspect of the present disclosure relates to a method for producing an olefin as set forth in any one of [1] to

[12] below, and a method for producing a polymer as set forth in

[13] below.

[0006] [1] A method for producing olefins from a feed gas in the presence of a mixture of a first catalyst and a second catalyst, the first catalyst comprises copper; the second catalyst comprises porous crystals; the feed gas contains carbon dioxide and hydrogen, The olefin has 2 or more carbon atoms, The mass of the first catalyst is represented as M1; The mass of the second catalyst is represented as M2; M2 / M1 is 1.00 or more, A method for producing olefins.

[0007] [2] The M2 / M1 is 2.00 or more. [1] A method for producing an olefin according to the present invention.

[0008] [3] The reaction pressure of the reaction for producing the olefin from the raw material gas is 1 MPa or less. The method for producing an olefin according to [1] or [2].

[0009] [4] The first catalyst further contains zinc and aluminum. The method for producing an olefin according to any one of [1] to [3].

[0010] [5] The porous crystals are one or more zeolites selected from the group consisting of LTA zeolite, CHA zeolite, BEA zeolite, MOR zeolite, FER zeolite, MWW zeolite, FAU zeolite, and MFI zeolite. The method for producing an olefin according to any one of [1] to [4].

[0011] [6] The porous crystals are one or more zeolites selected from the group consisting of CHA-type zeolite, MOR-type zeolite, and MFI-type zeolite. The method for producing an olefin according to any one of [1] to [4].

[0012] [7] The olefin comprises ethylene. The method for producing an olefin according to any one of [1] to [6].

[0013] [8] The mixture is a molded body. The method for producing an olefin according to any one of [1] to [7].

[0014] [9] The raw material gas is derived from a reaction for producing propylene from ethanol. The method for producing an olefin according to any one of [1] to [8].

[0015]

[10] The raw material gas is derived from a reaction for producing isobutene from ethanol. The method for producing an olefin according to any one of [1] to [8].

[0016]

[11] The feed gas is derived from biomass. The method for producing an olefin according to any one of [1] to [8].

[0017]

[12] Methanol is synthesized from the raw material gas by the first catalyst; The olefin is synthesized from the methanol by the second catalyst. The method for producing an olefin according to any one of [1] to

[11] .

[0018]

[13] A step of producing a polymer from the olefin produced by the production method according to any one of [1] to

[12] . A method for producing polymers. [Effects of the Invention]

[0019] According to one aspect of the present disclosure, there are provided a method for producing an olefin, which suppresses the production of alkanes accompanying the production of an olefin from carbon dioxide and hydrogen and increases the conversion rate of carbon dioxide in the production of an olefin, and a method for producing a polymer using the olefin. [Brief explanation of the drawings]

[0020] [Figure 1]FIG. 1 is a graph showing CCO2, SCH4, SOLEFIN, and SALKANE in Examples 1, 2, and 3 and Comparative Examples 1 and 2, respectively. DETAILED DESCRIPTION OF THE INVENTION

[0021] Hereinafter, embodiments of the present disclosure will be described. However, the present disclosure is not limited to the following embodiments.

[0022] The olefin production method according to the present disclosure includes a step of producing an olefin from a feed gas in the presence of a mixture of a first catalyst and a second catalyst. The first catalyst includes copper. The second catalyst includes porous crystals. The feed gas includes carbon dioxide (CO2) and hydrogen (H2). The olefin has two or more carbon atoms. The mass of the first catalyst is represented as M1, the mass of the second catalyst is represented as M2, and M2 / M1 is 1.00 or more. For example, the units of M1 and M2 are the same, and may be g or kg. According to the olefin production method of the present disclosure, the generation of alkanes accompanying the production of olefins from carbon dioxide and hydrogen is suppressed, and the conversion rate of carbon dioxide in the production of olefins is increased. In other words, according to the olefin production method of the present disclosure, olefins are easily synthesized selectively from carbon dioxide and hydrogen. Furthermore, according to the olefin production method of the present disclosure, carbon dioxide produced by the combustion of fossil fuels can be used as a raw material for olefins, thereby reducing the emission of carbon dioxide derived from fossil fuels into the atmosphere.

[0023] The number of carbon atoms in the olefin is not limited as long as the number of carbon atoms in the olefin is 2 or more. For example, the number of carbon atoms in the olefin, n, may be 2 or more and 10 or less, or 2 or more and 4 or less. The olefin may be C n H 2nFor example, the olefin may be one or more unsaturated hydrocarbons selected from the group consisting of ethylene, propylene (propene), 1-butene, 2-butene, pentene, hexene, heptene, octene, nonene, and decene. The olefin may include one or more structural isomers. The olefin may include one or more stereoisomers. The olefin may be referred to as an alkene. The alkane that may be produced in the production of olefins is not limited. For example, the alkane that may be produced in the production of olefins may be one or more saturated hydrocarbons selected from the group consisting of methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, and decane. The alkane may contain one or more structural isomers.

[0024] In the present disclosure, the chemical mechanism (reaction mechanism) for producing olefins from a feed gas is not limited. For example, methanol (a reaction intermediate) may be synthesized from the feed gas by a first catalyst, and olefins may be synthesized from methanol by a second catalyst. For example, when the olefin contains ethylene, the reaction for producing ethylene from the feed gas may be represented by the following chemical formula 1. 2CO2+6H2→C2H4+4H2O-128kJ (1) For example, when the olefin contains ethylene, methanol may be synthesized from the feed gas by the first catalyst, and ethylene may be synthesized from methanol by the second catalyst. That is, the reaction represented by the following chemical formula R1 (hydrogenation of carbon dioxide) may occur by the first catalyst, and the reaction represented by the following chemical formula R2 (dehydration of methanol) may occur by the second catalyst. 2CO2+6H2→2CH3OH+2H2O-98.6kJ (R1) 2CH3OH→C2H4+2H2O-29.2kJ (R2)

[0025] Because the first and second catalysts are mixed and located close to each other, the synthesis of methanol from the feed gas (e.g., the reaction represented by the above chemical formula R1) and the synthesis of olefins from methanol (e.g., the reaction represented by the above chemical formula R2) proceed in parallel without equilibrium constraints. In other words, the methanol produced by the first catalyst is immediately converted into olefins by the second catalyst. Therefore, as shown in the above chemical formula 1, it appears that olefins are directly synthesized from carbon dioxide and hydrogen. If the first and second catalysts were not mixed, it would be difficult for the methanol derived from carbon dioxide to be converted into olefins, and alkanes would be more likely to be produced. In other words, if the first and second catalysts were not mixed, it would be difficult for the methanol synthesized from carbon dioxide and hydrogen by the first catalyst to be immediately converted into olefins by the second catalyst.

[0026] As described above, M2 / M1 is 1.00 or more. M2 / M1 may be 2.00 or more. When M2 / M1 is 1.00 or more, the synthesis of alkanes is suppressed, and olefins are likely to be selectively synthesized. When M2 / M1 is less than 1.00 (i.e., when the amount of the second catalyst is too small or when there is no second catalyst), carbon dioxide is easily converted to methane and alkanes are easily synthesized. In other words, when M2 / M1 is less than 1.00, carbon dioxide is hardly converted to methanol and the reaction of synthesizing olefins from methanol hardly occurs. If M2 / M1 is too large (that is, if there is too much second catalyst or if there is no first catalyst), carbon dioxide is hardly converted to methanol, and the reaction of synthesizing olefins from methanol hardly occurs. The production of alkanes accompanying the production of olefins from carbon dioxide and hydrogen is likely to be suppressed, and the conversion rate of carbon dioxide in the production of olefins is likely to be increased. For these reasons, M2 / M1 is preferably 1.00 or more and 200.00 or less, 2.00 or more and 200.00 or less, 3.00 or more and 200.00 or less, 1.00 or more and 100.00 or less, 2.00 or more and 100.00 or less, 3.00 or more and 100.00 or less. or less, 1.00 or more and 10.00 or less, 2.00 or more and 10.00 or less, 3.00 or more and 10.00 or less, 1.00 or more and 9.00 or less, 2.00 or more and 9.00 or less, 3.00 or more and 9.00 or less, 1.00 or more and 8.00 or less, 2.00 or more and 8.00 or less, 3.00 or more and 8.00 or less, 1.05 or more and 9.05 or less, 2.99 or more and 9.05 or less, or 2.99 or more and 8.00 or less.

[0027] Copper (Cu) contained in the first catalyst is an essential active component for synthesizing methanol from the feed gas. Some or all of the copper contained in the first catalyst may be copper oxide. The first catalyst may further contain other active components in addition to copper. For example, the first catalyst may contain, as other active components, one or more metals or metal oxides selected from the group consisting of zinc (Zn), aluminum (Al), chromium (Cr), iron (Fe), zirconium (Zr), indium (In), nickel (Ni), palladium (Pd), platinum (Pt), gold (Au), ruthenium (Ru), and rhodium (Rh). The first catalyst may further contain zinc and aluminum in addition to copper as active components, because this tends to suppress the production of alkanes associated with the production of olefins from carbon dioxide and hydrogen and tends to increase the carbon dioxide conversion rate in the production of olefins. For example, the first catalyst containing copper, zinc, and aluminum may be an oxide (e.g., a composite oxide) containing copper, zinc, and aluminum. When the first catalyst is an oxide containing copper, zinc, and aluminum, the mass ratio of copper oxide (CuO) in the first catalyst may be 50 parts by mass to 70 parts by mass, or 25 parts by mass to 60 parts by mass. The mass ratio of zinc oxide (ZnO) in the first catalyst may be 20 parts by mass to 30 parts by mass, 20 parts by mass to 50 parts by mass, or 16 parts by mass to 50 parts by mass. The mass ratio of aluminum oxide (Al2O3) in the first catalyst may be 5 parts by mass to 20 parts by mass, 3 parts by mass to 20 parts by mass, or 1.6 parts by mass to 10 parts by mass. The first catalyst may be an oxide (composite oxide) containing silicon (Si) in addition to copper, zinc, and aluminum. When the first catalyst is an oxide containing copper, zinc, aluminum, and silicon, the mass ratio of silicon oxide (SiO2) in the first catalyst may be 0.05 parts by mass or more and 1.5 parts by mass or less. For example, the amount of copper in the first catalyst may be expressed as [Cu] moles, the amount of zinc in the first catalyst may be expressed as [Zn] moles, and the amount of aluminum in the first catalyst may be expressed as [Al] moles, with [Cu] / [Zn] being 15 / 85 or more and 85 / 15 or less, and [Zn] / [Al] being 60 / 40 or more and 80 / 20 or less. For example, the catalysts described in Japanese Patent Publication No. 6426750, Japanese Patent Publication No. 7485688, or International Publication No. 2011 / 048976 may be used as the first catalyst containing copper, zinc, and aluminum.

[0028] The first catalyst may include the active component and a support on which the active component is supported. For example, the support included in the first catalyst may be one or more components selected from the group consisting of magnesium oxide, silica, alumina, zirconium oxide, titanium oxide, cerium oxide, lanthanum oxide, silica-alumina composite oxide, zeolite, carbon, silicon carbide, silicon nitride, and boron nitride.

[0029] The first catalyst (e.g., the first catalyst before being mixed with the second catalyst) may be a powder (plurality of fine particles). The particle size (e.g., average particle size or median diameter) of the first catalyst may be 1 μm or more and 200 μm or less, preferably 1 μm or more and 100 μm or less, for reasons that the production of alkanes accompanying the production of olefins from carbon dioxide and hydrogen is likely to be suppressed and the conversion rate of carbon dioxide in the production of olefins is likely to be increased.

[0030] The porous crystals contained in the second catalyst are an essential active component for the synthesis of olefins from methanol. The porous crystals may be zeolite. The porous crystals contained in the second catalyst may be one or both of monocrystalline and polycrystalline. The porous crystals (zeolite) contained in the second catalyst are not limited. For example, the porous crystals may be one or more zeolites selected from the group consisting of LTA-type zeolite (A-type zeolite), CHA-type zeolite, BEA-type zeolite (beta-type zeolite), MOR-type zeolite (mordenite), FER-type zeolite (ferrierite), MWW-type zeolite (MCM-22), FAU-type zeolite (one or both of X-type zeolite and Y-type zeolite), and MFI-type zeolite (ZSM-5).

[0031] The porous crystals may be one or more zeolites selected from the group consisting of CHA-type zeolite, MOR-type zeolite (mordenite), and MFI-type zeolite (ZSM-5), because this tends to suppress the production of alkanes involved in the production of olefins from carbon dioxide and hydrogen and tends to increase the carbon dioxide conversion rate in the production of olefins. For example, the CHA-type zeolite may be one or more zeolites selected from the group consisting of SAPO-34 (silicon aluminophosphate), ALPO-34 (aluminophosphate), natural chabazite, SSZ-13, and ZK-14. SAPO-34 is a silicon aluminophosphate with a three-dimensional eight-membered ring pore structure, and among the above-mentioned zeolites, it is suitable for the second catalyst due to its excellent activity for selectively synthesizing olefins. For example, the catalyst described in JP-A-2015-533765 (WO 2014 / 047801) may be used as the second catalyst containing SAPO-34.

[0032] The second catalyst (e.g., the second catalyst before being mixed with the first catalyst) may be a powder (a plurality of fine particles). The particle size (e.g., average particle size or median diameter) of the second catalyst may be 0.05 μm or more and 100 μm or less, or 0.5 μm or more and 50 μm or less, because this tends to suppress the production of alkanes accompanying the production of olefins from carbon dioxide and hydrogen and tends to increase the conversion rate of carbon dioxide in the production of olefins.

[0033] The second catalyst in the present disclosure may be any catalyst other than zeolite catalysts modified with an organic group (organic group-modified zeolite catalysts obtained by reacting zeolite catalysts with an organic compound). In other words, the surface of the crystalline porous body contained in the second catalyst may be exposed without being bonded to an organic group. Here, the organic compound may be at least one selected from the group consisting of organosilane compounds, organoboron compounds, organoaluminum compounds, organotin compounds, organic compounds containing oxygen (organic oxygen-containing compounds), aromatic compounds, heteroaromatic compounds, aliphatic unsaturated compounds, and alicyclic unsaturated compounds. When the second catalyst is a zeolite catalyst modified with an organic group, the activity of the second catalyst is likely to be inhibited, the carbon dioxide conversion rate in olefin production is likely to decrease, and alkanes and carbon monoxide are likely to be produced during olefin production. For example, when a zeolite modified with an organic group is used as the second catalyst, the organic groups introduced into the surface and pores of the zeolite make it difficult for methanol produced in the first catalyst to be rapidly and efficiently supplied to the surface and interior of the second catalyst. As a result, the conversion rate of methanol to olefins decreases, and methanol tends to remain in the reaction system. This reduces the conversion rate of carbon dioxide and increases the proportion of by-products such as carbon monoxide. The second catalyst in the present disclosure may be a catalyst other than beta zeolite (zeolite beta). When the second catalyst is beta zeolite (zeolite beta), the carbon dioxide conversion rate in the production of olefins is more likely to decrease and alkanes and carbon monoxide are more likely to be produced during the production of olefins than when the second catalyst is one or more zeolites selected from the group consisting of CHA zeolite, MOR zeolite, and MFI zeolite. The second catalyst in the present disclosure may be a catalyst other than a zeolite catalyst supported with one or more metals (active components) selected from the group consisting of palladium, nickel, and copper. When the second catalyst is a zeolite catalyst supported with one or more metals selected from the group consisting of palladium, nickel, and copper, olefins are unlikely to be produced, and alkanes (particularly paraffins) are likely to be produced.

[0034] The mixture of the first catalyst and the second catalyst may be a composite catalyst formed from the first catalyst and the second catalyst. The mixture of the first catalyst and the second catalyst may consist solely of the first catalyst and the second catalyst. The mixture of the first catalyst and the second catalyst may further contain other components (e.g., a promoter) in addition to the first catalyst and the second catalyst. The first catalyst and the second catalyst may be mixed in the same reactor. The mixture of the first catalyst and the second catalyst may be a powder. For example, the particle size of the powder consisting of the mixture of the first catalyst and the second catalyst may be 1 μm or more and 750 μm or less. The mixture of the first catalyst and the second catalyst may be a compact (e.g., pellet). For example, the dimension (maximum width) of the compact formed from the mixture of the first catalyst and the second catalyst may be several mm or more and several tens of mm or less. When the mixture of the first catalyst and the second catalyst is in the form of a powder rather than a compact, the large specific surface area of ​​the powder tends to improve the catalytic activity of the mixture, and the reaction rate tends to increase. When the mixture of the first catalyst and the second catalyst is in the form of a molded body rather than a powder, clogging of the reactor due to the powder is less likely to occur, channeling within the reactor (uneven distribution of the flow paths for the raw material gas and the olefin within the reactor) is less likely to occur, the raw material gas is more likely to come into even contact with the mixture within the reactor, pressure loss within the reactor is more likely to be suppressed, powder scattering is less likely to occur, and the mixture can be easily placed in the reactor and recovered from the reactor.

[0035] The method for producing the mixture of the first catalyst and the second catalyst (i.e., the method for mixing the first catalyst and the second catalyst) is not limited. For example, a powder of the first catalyst and a powder of the second catalyst may be simply mixed. A compact may be formed from the mixture (powder) of the first catalyst and the second catalyst. A compact formed from the mixture of the first catalyst and the second catalyst may be pulverized. Granules may be formed from the mixture of the first catalyst and the second catalyst. A compact formed from the first catalyst and a compact formed from the second catalyst may be mixed. A powder of the first catalyst, a powder of the second catalyst, and a solvent may be mixed to form a slurry in which the first catalyst and the second catalyst are dispersed, and the slurry may be dried to obtain a mixture of the first catalyst and the second catalyst. The mixture of the first catalyst and the second catalyst may be calcined in air or inert gas at a temperature (e.g., 250°C to 800°C) at which the composition and structure of the first catalyst and the second catalyst are unlikely to change. Prior to the production of olefins, the mixture of the first catalyst and the second catalyst may be reduced by heating the mixture with hydrogen.

[0036] For example, the reaction pressure of the reaction for producing olefins from a feed gas may be atmospheric pressure or higher and 1 MPa or lower. The reaction pressure may be rephrased as the atmospheric pressure within a reactor (i.e., a reactor containing a mixture of the first catalyst and the second catalyst) in which the reaction for producing olefins from a feed gas proceeds. Normal pressure may be rephrased as 101,325 Pa (0.1 MPa) or atmospheric pressure. If only the first catalyst is used instead of a mixture of the first catalyst and the second catalyst and the reaction pressure is less than 1 MPa, the reaction for converting carbon dioxide in the feed gas to methanol is unlikely to proceed. However, in the present disclosure, the feed gas reacts in the presence of a mixture of the first catalyst and the second catalyst, and therefore, even under a low reaction pressure of 1 MPa or lower (e.g., atmospheric pressure), carbon dioxide in the feed gas is converted to methanol with a high conversion rate, and olefins are easily synthesized from methanol. For example, the reaction temperature of the reaction for producing olefins from a feed gas may be 250° C. or higher and 550° C. or lower, or 350° C. or higher and 450° C. or lower. The reaction temperature may be expressed as the temperature of the mixture of the first catalyst and the second catalyst, or the air temperature inside a reactor in which the mixture of the first catalyst and the second catalyst is placed. For example, the reactor for producing olefins from a raw material gas may be a flow reactor or a fixed-bed reactor. As described above, since olefins can be produced under a low reaction pressure of 1 MPa or less, olefins can be produced using a simple and inexpensive reactor that is poor in pressure resistance.

[0037] The feed gas may consist only of carbon dioxide and hydrogen. The feed gas may further contain other components in addition to carbon dioxide and hydrogen. For example, the other components that may be contained in the feed gas may be one or more gases selected from the group consisting of carbon monoxide (CO), nitrogen (N2), helium (He), and argon (Ar). For example, the carbon dioxide (CO2) content in the feed gas may be 0.5 mol% or more and 35 mol% or less, and the hydrogen (H2) content in the feed gas may be 1 mol% or more and 90 mol% or less.

[0038] The raw material gas may be derived from a reaction for producing propylene from ethanol (ETP reaction). For example, propylene is produced from ethanol by the reaction represented by the following chemical formula α1, and CO and H produced in the propylene production process may be used as the raw material gas. 2CH3CH2OH → 3H2+CO2+CH2=CHCH3(α1)

[0039] The feed gas may be derived from a reaction for producing isobutene from ethanol (ETIB reaction). For example, isobutene is produced from ethanol by the reaction represented by the following chemical formula β1, and CO and H produced in the process of producing isobutene may be used as the feed gas. 3CH3CH2OH+H2O → 6H2+2CO2+CH2=C(CH3)2(β1)

[0040] The feed gas may be derived from biomass. Biomass is an organic resource derived from living organisms (excluding fossil fuels). For example, biomass gas containing methane and carbon dioxide as main components may be produced by fermentation (decomposition) of biomass by microorganisms. The carbon dioxide in the biomass gas may be used as the feed gas. For example, carbon monoxide and hydrogen may be produced from methane and water by a steam reforming reaction using methane in the biomass gas. The hydrogen produced by the steam reforming reaction may be used as the feed gas. For example, carbon dioxide and hydrogen may be produced from carbon monoxide and water by a water gas shift reaction using carbon monoxide produced by the steam reforming reaction. The carbon dioxide and hydrogen produced by the water gas shift reaction may be used as the feed gas.

[0041] The method for producing a polymer according to the present disclosure may include a step of producing a polymer from an olefin produced from a feed gas by the above-described production method. That is, the method for producing a polymer according to the present disclosure may include the method for producing an olefin according to the present disclosure. The polymer produced from the olefin is not limited. For example, the polymer may be one or more polyolefins selected from the group consisting of polyethylene, polypropylene, and poly-1-butene. That is, polyolefins may be produced by polymerizing olefins. For example, polyethylene may be produced from ethylene produced by the above-described production method. For example, polypropylene may be produced from propylene produced by the above-described production method. For example, poly-1-butene may be produced from 1-butene produced by the above-described production method. For example, in the reaction for producing a polymer from an olefin (olefin polymerization reaction), one or more catalysts selected from the group consisting of Ziegler-Natta catalysts and metallocene catalysts (Kaminsky catalysts) may be used.

[0042] The present disclosure is not necessarily limited to the above-described embodiments. Various modifications of the present disclosure are possible without departing from the spirit of the present disclosure, and these modifications are also included in the present disclosure. [Example]

[0043] The present disclosure will be described in detail with reference to the following examples and comparative examples, but the present disclosure is not limited to the following examples.

[0044] Example 1 <Catalyst production> A powder was obtained by crushing commercially available pellets of a catalyst for methanol synthesis. The powder was classified using a sieve to obtain a powder of the first catalyst. The particle size of the first catalyst was adjusted to 75 μm or less. The commercially available pellets were a catalyst (product number: ALFAA45776) manufactured by Thermo Fisher Scientific Chemicals, Inc. (formerly Alfa Aesar GmbH). The first catalyst consisted of copper oxide (CuO), zinc oxide (ZnO), aluminum oxide (Al2O3), and magnesium oxide (MgO). The copper oxide content in the first catalyst was 63.5 mass%. The zinc oxide content in the first catalyst was 25.0 mass%. The aluminum oxide content in the first catalyst was 10.0 mass%. The magnesium oxide content in the first catalyst was 1.5 mass%. The second catalyst used was a powder consisting of only SAPO-34, a commercially available catalyst (product number: Type A) manufactured by ACS Materials, LLC.

[0045] A mixed powder consisting of the first catalyst and the second catalyst was obtained by uniformly mixing 0.20 g of the first catalyst and 1.81 g of the second catalyst in a mortar and pestle for 10 minutes. The M2 / M1 ratio of the mixed powder in Example 1 was 9.05.

[0046] The mixed powder was molded into disk-shaped pellets using a tablet press (product name: P-16B) manufactured by Rikenkiki Co., Ltd. The molding pressure was 400 kg / cm. 2The pellets had a diameter of approximately 10 mm and a thickness of approximately 2 mm. The pellets were crushed using a mortar and pestle to obtain a powder. The powder was classified using a sieve to obtain a powder (catalyst α) consisting of the first catalyst and the second catalyst. The particle size of catalyst α was adjusted to be between 250 μm and 500 μm.

[0047] <Analysis of catalytic reactions> Reaction A using catalyst α was analyzed in the following experiment using a catalyst analyzer (product name: BELCAT II) manufactured by Microtrack-Bel Corporation.

[0048] 0.26 g of catalyst α was loaded into the reactor of the catalyst analyzer. The reactor was a quartz glass tube with an inner diameter of 13 mm. The reactor had a sheath tube for measuring the temperature inside the reactor. The reactor loaded with catalyst α was placed in the electric tubular furnace of the catalyst analyzer.

[0049] While continuously supplying helium into the reactor, the temperature inside the reactor was increased at a rate of 20°C / min. The flow rate (supply rate) of helium was 100 cm 3 (Absolute pressure at 0°C: 0.1013 MPa) / min. After the temperature inside the reactor reached 300°C, hydrogen was continuously supplied to the reactor in addition to helium for 2 hours while maintaining the temperature inside the reactor at 300°C. In other words, after the temperature inside the reactor reached 300°C, pretreatment of catalyst α using helium and hydrogen was carried out for 2 hours. The hydrogen flow rate during pretreatment was 10 cm 3 The helium flow rate during pretreatment was maintained at 90 cm (absolute pressure at 0°C: 0.1013 MPa) / min. 3 (Absolute pressure at 0°C: 0.1013 MPa) / min.

[0050] After the pretreatment, the temperature in the reactor was increased at a rate of 20°C / min while continuously supplying helium into the reactor. The helium flow rate was 100 cm 3 (Absolute pressure at 0°C: 0.1013 MPa) / min. After the temperature in the reactor reached 400°C, the following reaction A was carried out. In Reaction A, the temperature inside the reactor was maintained at 400°C (reaction temperature), while helium, carbon dioxide, and hydrogen were continuously fed into the reactor, and the product (gas) discharged from the reactor outlet was analyzed. Product analysis began simultaneously with the start of the feed of helium, carbon dioxide, and hydrogen into the reactor. The product was analyzed using a micro gas chromatograph installed on the reactor outlet gas line. The micro gas chromatograph was an Agilent Technologies, Inc. (product name: CP-4900 Micro GC) The flow rate of carbon dioxide in reaction A is 1 cm 3 The hydrogen flow rate in reaction A was maintained at 3 cm (absolute pressure at 0°C: 0.1013 MPa) / min. 3 The helium flow rate in reaction A was 96 cm (absolute pressure at 0°C: 0.1013 MPa) / min. 3 (Absolute pressure at 0°C: 0.1013 MPa) / min. The reaction pressure (air pressure inside the reactor) of Reaction A was 0.1013 MPa.

[0051] The conditions for analyzing the product using a micro gas chromatography device were as follows: Carrier gas: Helium Column used: 10m PPQ Unheated Column temperature: 80℃ Pressure: 190kPa

[0052] The components contained in the product of Reaction A above were identified from the chromatogram measured by the micro gas chromatography device. The components were identified based on the catalog provided by GL Sciences Inc., "High-Speed, Compact Gas Analyzer Agilent 990 Micro GC, March 2021 Revised Edition" (URL: https: / / www.gls.co.jp / brochure / individual_catalogues / Agilent990microGC.pdf). The component corresponding to the peak with a retention time of 15.15 to 15.60 seconds was identified as methane. The component corresponding to the peak with a retention time of 16:00 to 17:00 s was identified as carbon dioxide. The component corresponding to the peak with a retention time of 18.10 to 18.80 s was identified as ethylene. The component corresponding to the peak with a retention time of 19.40 to 20.60 s was identified as ethane. The component corresponding to the peak with a retention time of 35.80 to 37.50 s was identified as propylene. The component corresponding to the peak with a retention time of 38.50 to 40.80 s was identified as propane. From the above measurements, it was confirmed that the product of reaction A contained ethylene and propylene.

[0053] A linear baseline was set in the chromatogram within the range covering all of the above retention times, and the area of ​​the peak corresponding to each component (i.e., the area enclosed by each peak and the baseline) was calculated. If the area value was negative, it was considered to be "0."

[0054] Area value of olefins (A OLEFIN ) is defined by the following mathematical formula A. A OLEFIN =A C2H4 +A C3H6 (Formula A) A in formula A C2H4 is the area value of the peak corresponding to ethylene. A in formula A C3H6 is the area value of the peak corresponding to propylene.

[0055] Area value of alkanes (A' ALKANE ) is defined by the following formula B. A' ALKANE =A' C2H6 +A' C3H8 (Formula B) A' in formula BC2H6 is the area value of the peak corresponding to ethane. A' in formula B C3H8 is the area value of the peak corresponding to propane.

[0056] <Blank measurement> The empty reactor (the glass tube) was placed in the electric tubular furnace of the catalyst analyzer. Helium was continuously supplied into the empty reactor, while the temperature inside the reactor was increased at a rate of 20°C / min. The helium flow rate was 100 cm 3 (Absolute pressure at 0°C: 0.1013 MPa) / min. After the temperature in the reactor reached 400°C, the following blank measurement was carried out.

[0057] In the blank measurement, helium, carbon dioxide, and hydrogen were continuously fed into the empty reactor while maintaining the temperature inside the reactor at 400°C, and the chromatogram of the gas discharged from the reactor outlet was measured by the micro gas chromatography device. The flow rate of carbon dioxide during the blank measurement was 1 cm. 3 The hydrogen flow rate during the blank measurement was maintained at 3 cm (absolute pressure at 0°C: 0.1013 MPa) / min. 3 The helium flow rate during the blank measurement was 96 cm (absolute pressure at 0°C: 0.1013 MPa) / min. 3 The pressure was maintained at 0.1013 MPa (absolute pressure at 0°C) / min. A total of six chromatograms were measured within a period of 20 to 30 minutes from the start of the blank measurement, and the area value of the peak corresponding to carbon dioxide in each chromatogram was measured. The time required for measuring one chromatogram during the blank measurement was 80 seconds. Furthermore, the average value of the area values ​​of the peak corresponding to carbon dioxide in the blank measurement was calculated from the six measurements in total. The average value of the area values ​​of the peak corresponding to carbon dioxide in the blank measurement was A CO2-BLANK It is written as follows.

[0058] <Evaluation of catalytic activity> Within 5 minutes from the start of Reaction A, the chromatogram of the product of Reaction A was measured twice using the above method. Following these two measurements, the third to eighth chromatogram measurements were carried out. In other words, after 5 minutes had elapsed from the start of Reaction A, the chromatogram of the product of Reaction A was measured six times. The time required for measuring one chromatogram during Reaction A was 80 seconds. In each of the chromatograms from the third to eighth reactions in reaction A, the area value A of the peak corresponding to carbon dioxide CO2 A total of six A CO2 ΣA is the sum of the measurements of CO2 was calculated. In each of the chromatograms from the third to eighth runs of reaction A, the area value of the peak corresponding to methane (A CH4 ) were measured. A total of six A CH4 ΣA is the sum of the measurements of CH4 was calculated. In each of the chromatograms from the third to eighth runs of reaction A, the area values ​​of olefins (A OLEFIN ) were measured. A total of six A OLEFIN ΣA is the sum of the measurements of OLEFIN was calculated. In each of the chromatograms from the third to eighth runs of reaction A, the area values ​​of alkanes (A' ALKANE ) were measured. A total of six A' ALKANE ΣA' is the sum of the measurements of ALKANE was calculated.

[0059] Conversion rate C of carbon dioxide in reaction A CO2 (unit: %) is defined by the following formula C. C CO2 =100×{(A CO2-BLANK ×6)-ΣA CO2} / (A CO2-BLANK ×6) (Formula C) {(A CO2-BLANK ×6)-ΣA CO2} corresponds to the amount of carbon dioxide consumed during reaction A. In the following, {(A CO2-BLANK ×6)-ΣA CO2} is ΔA CO2It is written as follows.

[0060] Selectivity of methane in reaction A, S CH4 (unit: none) is defined by the following formula D. S CH4 =ΣA CH4 / ΔA CO2 (Formula D)

[0061] Selectivity S of olefins in reaction A OLEFIN (unit: none) is defined by the following mathematical formula E. S OLEFIN =ΣA OLEFIN / ΔA CO2 (Formula E)

[0062] Selectivity S of alkanes in reaction A ALKANE (unit: none) is defined by the following formula F. S ALKANE =ΣA' ALKANE / ΔA CO2 (Formula F)

[0063] C of Example 1 CO2 , S CH4 , S OLEFIN , and S ALKANE are shown in Table 1 below.

[0064] Example 2 In Example 2, 1.00 g of the first catalyst and 1.05 g of the second catalyst were uniformly mixed in a mortar and pestle for 10 minutes to obtain a mixed powder consisting of the first catalyst and the second catalyst. That is, the M2 / M1 ratio of the mixed powder in Example 2 was 1.05. In Example 2, 0.29 g of catalyst β produced from the mixed powder was loaded into the reactor of a catalyst analyzer. The same procedure as in Example 1 was repeated except that catalyst β was used instead of catalyst α. CO2 , S CH4 , S OLEFIN , and S ALKANE The results of the measurements in Example 2 are shown in Table 1 below. It was confirmed that the product of Reaction A in Example 2 also contained ethylene and propylene.

[0065] Example 3 In Example 3, 1.01 g of the first catalyst and 3.02 g of the second catalyst were uniformly mixed in a mortar and pestle for 10 minutes to obtain a mixed powder consisting of the first catalyst and the second catalyst. That is, the M2 / M1 ratio of the mixed powder in Example 3 was 2.99. In Example 3, 0.29 g of catalyst δ produced from the mixed powder was loaded into the reactor of a catalyst analyzer. C of Example 3 was prepared in the same manner as in Example 1, except that catalyst δ was used instead of catalyst α. CO2 , S CH4 , S OLEFIN , and S ALKANE The results of the measurements in Example 3 are shown in Table 1 below. It was confirmed that the product of Reaction A in Example 3 also contained ethylene and propylene.

[0066] (Comparative Example 1) In Comparative Example 1, 1.83 g of the first catalyst and 0.21 g of the second catalyst were uniformly mixed in a mortar and pestle for 10 minutes to obtain a mixed powder consisting of the first catalyst and the second catalyst. That is, the M2 / M1 ratio of the mixed powder in Comparative Example 1 was 0.11 (i.e., 1 / 8.71). In Comparative Example 1, 0.35 g of catalyst γ produced from the mixed powder was loaded into the reactor of a catalyst analyzer. The same procedure as in Example 1 was repeated except that catalyst γ was used instead of catalyst α. CO2 , S CH4 , S OLEFIN , and S ALKANE The results of the measurements of Comparative Example 1 are shown in Table 1 below.

[0067] (Comparative Example 2) In Comparative Example 2, only the second catalyst (i.e., SAPO-34) was used instead of catalyst α (a mixed powder consisting of the first catalyst and the second catalyst). In Comparative Example 2, 0.31 g of the second catalyst was loaded into the reactor of the catalyst analyzer. In Comparative Example 2, no pretreatment was performed before Reaction A. Except for the above-mentioned points, the same method as in Example 1 was used to prepare C of Comparative Example 2. CO2 , S CH4 , SOLEFIN , and S ALKANE The results of the measurements in Comparative Example 2 are shown in Table 1 below.

[0068] The contents of Table 1 below are shown in FIG.

[0069] [Table 1]

[0070] As is clear from Table 1 and Figure 1, it was confirmed that the olefin selectivity ratio (selectivity) increases by setting M2 / M1 to 1.00 or more. Furthermore, it was confirmed that by increasing M2 / M1, the carbon dioxide conversion rate increases while maintaining a high olefin selectivity ratio (selectivity). [Industrial Applicability]

[0071] For example, the process for producing olefins according to one aspect of the present disclosure may be applied to the production of ethylene, propylene, 1-butene, or 2-butene.

Claims

1. producing olefins from a feed gas in the presence of a mixture of a first catalyst and a second catalyst; the first catalyst is an oxide containing copper, the second catalyst is a porous crystal; the porous crystals are zeolite, the feed gas contains carbon dioxide and hydrogen, The olefin has 2 or more carbon atoms, The mass of the first catalyst is represented as M1; The mass of the second catalyst is represented as M2; M2 / M1 is 1.00 or more and 200.00 or less, A method for producing olefins.

2. The M2 / M1 is 2.00 or more and 200.00 or less, The method for producing an olefin according to claim 1.

3. the reaction pressure of the reaction for producing the olefin from the raw material gas is 0.1 MPa or more and 1 MPa or less; The method for producing an olefin according to claim 1.

4. The oxide further comprises zinc and aluminum. The method for producing an olefin according to claim 1.

5. the porous crystals are one or more zeolites selected from the group consisting of LTA zeolite, CHA zeolite, BEA zeolite, MOR zeolite, FER zeolite, MWW zeolite, FAU zeolite, and MFI zeolite; The method for producing an olefin according to claim 1.

6. The porous crystals are one or more zeolites selected from the group consisting of CHA-type zeolite, MOR-type zeolite, and MFI-type zeolite. The method for producing an olefin according to claim 1.

7. The olefin comprises ethylene. The method for producing an olefin according to claim 1.

8. The mixture is a molded body. The method for producing an olefin according to claim 1.

9. The raw material gas is derived from a reaction for producing propylene from ethanol. The method for producing an olefin according to claim 1.

10. The raw material gas is derived from a reaction for producing isobutene from ethanol. The method for producing an olefin according to claim 1.

11. The raw material gas is derived from biomass. The method for producing an olefin according to claim 1.

12. Methanol is synthesized from the raw material gas by the first catalyst; The olefin is synthesized from the methanol by the second catalyst. The method for producing an olefin according to claim 1.

13. The raw material gas is a gas consisting only of the carbon dioxide and the hydrogen, or a gas in which the carbon dioxide content is 0.5 mol% or more and 35 mol% or less and the hydrogen content is 1 mol% or more and 90 mol% or less. The method for producing an olefin according to claim 1.

14. The first catalyst is an oxide comprising copper oxide, zinc oxide, aluminum oxide, and magnesium oxide. The method for producing an olefin according to claim 1.

15. A step of producing a polymer from the olefin produced by the production method according to any one of claims 1 to 14. A method for producing polymers.

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