Method for producing alcohol having 2-3 carbon atoms

Abstract

A method for producing an alcohol having 2-3 carbon atoms according to the present invention comprises: a step for preparing a mixed solution containing two or more metal salts having different types of metals; a step for mixing the mixed liquid obtained by the step for preparing the mixed liquid with a reducing agent-containing liquid containing a reducing agent to obtain a mixture containing a solid containing two or more metals; a step for separating a solid from the solid-containing mixture obtained by the step for obtaining the mixture; and a step for obtaining an alcohol having 2-3 carbon atoms by bringing the solid obtained by the step for separating the solid into contact with a carbon oxide gas and hydrogen gas.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the priority of Japanese Patent Application No. 2022-175445 and the priority of Japanese Patent Application No. 2023-128832, and the description of the present application specification is incorporated by reference. Technical Field

[0003] The present disclosure relates to a method for producing an alcohol having 2 to 3 carbon atoms. Background Art

[0004] Plastics are mass-produced because they are convenient, durable, and relatively inexpensive. However, since most of them are disposable and discarded as garbage, environmental pollution caused by microplastics obtained by micronizing plastics has become a problem.

[0005] Therefore, in recent years, methods such as reuse, material recycling, chemical recycling, and thermal recycling have been used to recycle waste plastics. Material recycling has the problem of performance degradation due to plastic recycling, and its improvement is limited. On the other hand, chemical recycling can chemically decompose plastics and regenerate them into petrochemical raw materials, so it has the potential to break the limitation of performance degradation caused by material recycling.

[0006] In the process of chemical recycling of waste plastics, alcohol is generated by carbon monoxide gas and hydrogen generated by decomposition of waste plastics. Moreover, a catalyst is used to generate the alcohol. For example, non-patent document 1 discloses the use of a catalyst prepared by an impregnation method on silica gel loaded with rhodium-iron-lithium to generate alcohol from carbon dioxide and hydrogen under high pressure. In addition, non-patent document 2 discloses the use of a catalyst loaded with rhodium-iron-cerium on titanium oxide to generate alcohol from a gas mixed with carbon monoxide and hydrogen under high pressure.

[0007] Prior art literature

[0008] Non-patent literature

[0009] Non-patent document 1: Chemistry and Industry, Vol. 47, No. 10, pp. 1314-1316 (1994)

[0010] Non-patent document 2: Catalysts Communications, 98, p90-93 (2017) Summary of the invention

[0011] Problems to be solved by the invention

[0012] However, in the conventional production method, although alcohol is produced, the selectivity of alcohol, especially the selectivity of alcohol having 2 to 3 carbon atoms, is insufficient. Therefore, a new production method having excellent selectivity of alcohol having 2 to 3 carbon atoms is required.

[0013] The present disclosure has been made in view of such circumstances, and an object of the present invention is to provide a method for producing an alcohol having 2 to 3 carbon atoms, which has a relatively excellent selectivity for the alcohol having 2 to 3 carbon atoms.

[0014] Means used to solve problems

[0015] The method for producing an alcohol having 2 to 3 carbon atoms disclosed herein comprises:

[0016] A step of preparing a mixed solution containing two or more metal salts of different metal types;

[0017] A step of mixing the mixed solution obtained by the step of preparing the mixed solution with a reducing agent-containing liquid containing a reducing agent to obtain a mixture containing a solid containing two or more metals;

[0018] A step of separating a solid from the mixture containing the solid obtained by the step of obtaining the mixture; and

[0019] A step of contacting the solid obtained in the step of separating the solid with carbon oxide gas and hydrogen gas to obtain an alcohol having 2 to 3 carbon atoms. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is a flow chart showing steps (1) to (3) of the method for producing an alcohol having 2 to 3 carbon atoms according to the present embodiment. DETAILED DESCRIPTION

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

[0022] <Method for producing alcohol having 2 to 3 carbon atoms>

[0023] The method for producing an alcohol having 2 to 3 carbon atoms according to the present embodiment includes the following steps (1) to (4). Figure 1 This is a flow chart showing steps (1) to (3) of the method for producing an alcohol having 2 to 3 carbon atoms according to the present embodiment.

[0024] Step (1): a step of preparing a mixed solution 1 containing two or more metal salts of different metal types

[0025] Step (2): A step of mixing the mixed solution 1 obtained in step (1) with a reducing agent-containing liquid 2 containing a reducing agent to obtain a mixture containing a solid containing two or more metals.

[0026] Step (3): A step of separating the solid 6 from the mixture containing the solid obtained in step (2)

[0027] Step (4): a step of contacting the solid 6 obtained in step (3) with carbon oxide gas and hydrogen gas to obtain an alcohol having 2 to 3 carbon atoms.

[0028] As a step of preparing a mixed solution, step (1) is a step of preparing a mixed solution 1 containing two or more metal salts of different metals. The metal salts contain two or more metals, preferably two to five, more preferably three to five, and even more preferably three to four.

[0029] The mixed solution 1 containing two or more metal salts is preferably a mixed solution 1 containing a metal salt of at least one metal selected from the group consisting of 3d metals, 4d metals and 5d metals. In addition, the mixed solution 1 may contain a metal salt of a f metal. It should be noted that 3d metals are Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn. 4d metals are Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag and Cd. 5d metals are Hf, Ta, W, Re, Os, Ir, Pt, Au and Hg. f metals are La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu. The mixed solution 1 more preferably contains a metal salt of at least one metal selected from the group consisting of Pd, Ru, Rh, Ag, Os, Ir, Pt, Au, Mo, Ce, Re, W and 3d metals, further preferably contains a metal salt of at least one metal selected from the group consisting of Pd, Ru, Rh, Ir, Pt, Au, Ag, Mo, Ce, Re, W, Fe, Co, Ni, Cu, Mn and Zn, and particularly preferably contains a metal salt of at least one metal selected from the group consisting of Pd, Ru, Rh, Ir, Pt, Au, Mo, Fe, Co, Ni and Cu.

[0030] The metal salt is preferably water-soluble. Examples of the metal salt include organic acid salts such as metal sulfates, nitrates, acetates, etc.; carbonates, halides (fluorides, chlorides, bromides, iodides), perchlorates, hydroxides, complexes, metal oxygen-containing acids (or their salts), etc. The metal salt is preferably a metal halide, nitrate, acetate, metal oxygen-containing acid (or its salt), and more preferably a metal halide, acetate, metal oxygen-containing acid (or its salt). There is no particular restriction on the metal salt as long as it is an available metal salt. In addition, there is no particular restriction on the valence of the metal in the metal salt, and it has nothing to do with whether the metal salt is a hydrate.

[0031] Examples of metal salts include the following:

[0032] Li salts: LiOH, LiCl, LiCH 3 COO, etc.

[0033] Mo salt: MoCl 3 、MoCl 5 、Mo(CH 3 COO 5 wait.

[0034] Mn salt: MnCl 2 、MnCl 2 ·4H 2 O、Mn(CH 3 COO 2 、Mn(CH 3 COO 2 ·4H 2 O、Mn(NO 3 ) 2 6H 2 O、Mn(SO 4 )·5H 2 O etc.

[0035] Fe salt: FeCl 2 、FeCl 2 ·4H 2 O, FeCl 3 、FeCl 3 6H 2 O, Fe(CH 3 COO 3 、Fe(NO 3 ) 2 6H 2 O, Fe(NO 3 ) 3 9H 2 O etc.

[0036] Ru salt: RuCl 3 、RuCl 3 ·nH 2 O.Ru(CH 3 COO 3 ,Ru(NO 3 ) 3 、Ru(acac) 3 (acac is acetylacetone ligand) etc.

[0037] Co salt: CoCl 2 、CoCl 2 6H 2 O、Co(CH 3 COO 2、Co(NO 3 ) 2 6H 2 O、Co(SO 4 )·7H 2 O etc.

[0038] Rh salt: RhCl 2 , RhCl 3 , RhCl 3 ·3H 2 O, Rh 2 (CH 3 COO 2 , Rh(C 2 H 4 O 2 ) x ·H 2 O (x represents a number from 3 to 4), Rh (NO 3 ) 3 ·2H 2 O, Rh 2 (CO 3 ) 3 , Rh 2 (SO 4 ) 3 ·4H 2 O etc.

[0039] Ir salt: IrCl 3 ·nH 2 O、IrCl 4 、IrCl 4 ·nH 2 O、Ir(CH 3 COO x (x represents a number from 3 to 4), Ir(acac) 3 (acac is acetylacetone ligand), Ir(NO 3 ) 3 wait.

[0040] Ni salt: NiCl 2 、NiCl 2 6H 2 O.Ni(CH 3 COO 2 ·4H 2 O.Ni(NO 3 ) 2 6H 2 O etc.

[0041] Pd salt: PdCl 2 , K 2 PdCl 4 、Pd(CH 3COO 2 、Pd(NO 3 ) 2 wait.

[0042] Pt salt: PtCl 2 、PtCl 4 , K 2 PtCl 4 , K 2 PtCl 6 、Pt(CH 3 COO 2 、Pt(NO 3 ) 2 wait.

[0043] Cu salts: CuCl, CuCl 2 , CuCl 2 ·2H 2 O、Cu(CH 3 COO 2 、Cu(CH 3 COO 2 ·H 2 O, Cu(NO 3 ) 2 ·3H 2 O etc.

[0044] Ag salt: Ag(CH 3 COO), AgNO 3 wait.

[0045] Au salt: AuCl 3 HAuCl 4 ·3H 2 O、Au(CH 3 COO 3 、Au(NO 3 ) 3 wait.

[0046] Ce salt: CeCl 3 7H 2 O etc.

[0047] Na salt: NaOH, NaCl, etc.

[0048] La salt: LaCl 3 7H 2 O etc.

[0049] Zn salt: Zn(NO 3 ) 2 6H 2 O etc.

[0050] The metal salt is preferably selected from LiCl, MnCl 2 ·4H 2 O, FeCl 2 ·4H 2 O、RuCl 3 ·nH 2 O、CoCl 2 6H 2 O、RhCl 3 ·3H 2 O, Rh 2 (CH 3 COO 2 、IrCl 3 ·nH 2 O、IrCl 4 ·nH 2 O、NiCl 2 、NiCl 2 6H 2 O.K 2 PdCl 4 , K 2 PtCl 4 , K 2 PtCl 6 , CuCl 2 ·2H 2 O、AgNO 3 、CeCl 3 7H 2 O、NaCH 3 COO、Na 2 MoO 4 ·2H 2 O、Na 2 WO 4 ·2H 2 O、LaCl 3 7H 2 O and Zn(NO 3 ) 2 6H 2 At least one of the group consisting of O.

[0051] The mixed solution 1 may also contain a solvent that dissolves two or more metal salts. Examples of the solvent include water, alcohol (methanol, ethanol, 1-propanol, 2-propanol, etc.), polyols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, glycerol, etc.), polyethers (polyethylene glycol, etc.), acetonitrile, acetone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and other polar solvents. Among them, the solvent is preferably water or alcohol. These solvents may be used alone or in combination of two or more.

[0052] The concentration of each metal salt in the mixed solution 1 is preferably 0.001 mol / L to 1 mol / L, and more preferably 0.025 mol / L to 0.1 mol / L.

[0053] The mixed solution 1 containing two or more metal salts can be prepared by, for example, dissolving the two or more metal salts together in the above-mentioned solvent, or by dissolving each metal salt in a solvent and then mixing the solutions in which the metal salts are dissolved to prepare the mixed solution 1. In addition, an acid or a base can be added to adjust the pH. As an acid, hydrochloric acid, sulfuric acid, acetic acid, nitric acid, etc. can be used, preferably hydrochloric acid can be used. As an alkali, sodium hydroxide, potassium hydroxide, cesium hydroxide, ammonia water, etc. can be used, preferably sodium hydroxide can be used.

[0054] As a step of obtaining a mixture, step (2) is a step of mixing the mixed solution 1 obtained in step (1) with a reducing agent-containing liquid 2 containing a reducing agent to obtain a mixture containing a solid containing two or more metals. More specifically, Figure 1 As shown, step (2) is a step of supplying the mixed liquid 1 and the reducing agent-containing liquid 2 to the mixing unit 3 and mixing them to obtain a mixture containing a solid containing two or more metals.

[0055] In step (2), as one embodiment, the mixed solution 1 and the reducing agent-containing liquid 2 are mixed and reacted under pressure. When the boiling point of at least one selected from the group consisting of the solvent contained in the mixed solution 1, the solvent contained in the reducing agent-containing liquid 2, and the reducing agent is lower than the reaction temperature, the reaction is carried out under pressure so that it can be heated to an appropriate reaction temperature.

[0056] In one embodiment, the mixed solution 1 and the reducing agent-containing liquid 2 are preferably supplied to the mixing section 3 to react in a continuous flow manner. The mixed solution 1 and the reducing agent-containing liquid 2 may also be supplied to the mixing section 3 separately. The mixed solution 1 and the reducing agent-containing liquid 2 are preferably pressurized and supplied to the mixing section 3. In addition, the mixed solution 1 and the reducing agent-containing liquid 2 may also be supplied to the mixing section 3 continuously or intermittently. As an apparatus having a mixing section 3, for example, a microreactor and a continuous reactor can be cited. In another embodiment, the reducing agent-containing liquid 2 may be heated in advance and the mixed solution 1 may be added dropwise using a pump or sprayed using a spray device for mixing.

[0057] In order to adjust the pH, an alkali can be supplied to the mixing section 3. As the alkali, sodium hydroxide, potassium hydroxide, cesium hydroxide, ammonia water, etc. can be used, and sodium hydroxide can be preferably used. These alkalis can be used in the form of an aqueous solution or an alcohol solution, and an aqueous solution is preferably used. The alkali can be pre-mixed into the reducing agent-containing liquid 2, or it can be directly continuously or intermittently supplied to the mixing section 3. As another mode, the alkali can be supplied from another pipeline before the mixed liquid 1 or the reducing agent-containing liquid 2 is about to flow into the mixing section 3, or it can flow into the mixing section 3 in a state after being mixed with the mixed liquid 1 or the reducing agent-containing liquid 2.

[0058] The pressure applied to the mixed liquid 1 and the reducing agent-containing liquid 2 supplied to the mixing section 3 is preferably 0MPa-G to 40MPa-G, more preferably 0MPa-G to 35MPa-G. In addition, the pressure in the mixing section 3 is preferably 0MPa-G to 40MPa-G, more preferably 0MPa-G to 35MPa-G. The temperature (reaction temperature) of the solution obtained by mixing the mixed liquid 1 and the reducing agent-containing liquid 2 in the mixing section 3 is preferably 100°C to 500°C, more preferably 150°C to 400°C, and further preferably 200°C to 400°C. It should be noted that the mixing section 3 preferably has a heater and is heated to the reaction temperature. The set temperature of the heater can be set in such a way that the temperature of the mixing section 3 reaches the desired temperature.

[0059] In one embodiment, the mixed liquid 1 and the reducing agent-containing liquid 2 may be prepared in advance and supplied under pressure to the mixing section 3. The supply to the mixing section 3 may be performed using a pump, for example.

[0060] In step (2), the reducing agent-containing liquid 2 before being supplied to the mixing unit 3 may be preheated in the heating unit 4. It is preferred that the reducing agent-containing liquid 2 is preheated under normal pressure or under pressure, and it is more preferred that the reducing agent-containing liquid 2 is preheated to the reaction temperature under pressure. When the boiling point of the reducing agent is higher than the reaction temperature, the reducing agent may be heated under normal pressure. When the boiling point of the reducing agent is lower than the reaction temperature, the reducing agent cannot be heated to the reaction temperature under normal pressure, so it is heated under pressure. In addition, when the reducing agent is volatile, the evaporation of the reducing agent can be prevented by pressurization.

[0061] In step (2), the temperature of the mixed liquid 1 before being supplied to the mixing section 3 may be room temperature, but may be preliminarily heated to a temperature higher than room temperature in a heating section (not shown).

[0062] In the method for producing an alcohol having 2 to 3 carbon atoms of the present embodiment, it is important to control the temperature of the solution obtained by mixing the mixed liquid 1 and the reducing agent-containing liquid 2 in the mixing section 3. It is preferred to adjust the temperature of the heater in the mixing section 3, the temperature of the mixed liquid 1 supplied to the mixing section 3, and the temperature of the reducing agent-containing liquid 2 so that the temperature of the solution is maintained within an appropriate range.

[0063] The temperature of the mixed liquid 1 supplied to the mixing section 3 is preferably 5° C. to 200° C., more preferably 10° C. to 150° C., further preferably 15° C. to 100° C., and particularly preferably 15° C. to 50° C. In addition, the temperature of the reducing agent-containing liquid 2 supplied to the mixing section 3 is preferably 100° C. to 500° C., more preferably 150° C. to 400° C., and further preferably 200° C. to 400° C. In one embodiment, at least one selected from the group consisting of the mixed liquid 1 obtained in step (1) and the reducing agent-containing liquid 2 is preferably mixed in a state heated to 100° C. or higher.

[0064] In terms of reducing agent components, 1 equivalent or more of the reducing agent-containing liquid 2 can be used relative to the metal salt. In terms of reducing agent components, preferably 2 equivalents or more of the reducing agent-containing liquid 2 can be used, more preferably 3 equivalents or more of the reducing agent-containing liquid 2 can be used, and even more preferably 5 equivalents or more of the reducing agent-containing liquid 2 can be used.

[0065] It should be noted that when solids are precipitated in the mixing section 3, the reaction solution containing the solids can be extracted from the mixing section 3, the solids can be recovered by filtration, centrifugation, etc., and the reaction solution from which the solids have been removed can be returned to the mixing section 3 for further reaction.

[0066] Examples of the reducing agent contained in the reducing agent-containing liquid 2 include: NaBH 4 , LiBH 4 、LiAlH 4 ,LiBEt 3 H, DIBAL and other metal hydrides; alcohols, glycols, glycerols, nitrogen-containing compounds. As metal hydrides, NaBH 4 , LiBH 4 . Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and the like. Examples of diols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, and the like. Examples of glycerols include glycerol, diglycerol, triglycerol, decaglycerol, and the like. Examples of nitrogen-containing compounds include urea, oleylamine, and the like.

[0067] The reducing agent is preferably an alcohol or a diol. The boiling point of the reducing agent is preferably 10°C to 300°C, more preferably 40°C to 300°C, and further preferably 60°C to 300°C. Among them, the reducing agent is preferably ethanol, ethylene glycol, or triethylene glycol. The reducing agent may be used alone or in combination of multiple types.

[0068] The reducing agent-containing liquid 2 may be composed of a reducing agent and may further contain water. When the reducing agent-containing liquid 2 contains a reducing agent and water, the mixing ratio of the reducing agent to water is preferably reducing agent: water = 1% to 99%: 99% to 1%, more preferably reducing agent: water = 3% to 90%: 97% to 10%, and further preferably reducing agent: water = 5% to 80%: 95% to 20%, in terms of mass ratio.

[0069] In step (2), the mixture containing the solid containing two or more metals obtained by the reaction in mixing section 3 may be cooled in cooling section 5. In this case, the cooled mixture is used in step (23) or step (3) described later.

[0070] Solids containing two or more metals can be covered with a surface protective agent. Examples of the surface protective agent include polymers such as polyvinyl pyrrolidone (PVP) and polyethylene glycol (PEG), amines such as oleylamine, and carboxylic acids such as oleic acid. When a surface protective agent is used, the solution obtained by mixing the mixed solution 1 and the reducing agent-containing liquid 2 preferably contains the surface protective agent at a concentration of 0.01 to 100 times, more preferably at a concentration of 0.5 to 50 times, and further preferably at a concentration of 1 to 10 times, relative to the total amount of the metal salt, in terms of mass ratio. The surface protective agent may be contained in the mixed solution 1, may be contained in the reducing agent-containing liquid 2, or may be contained in both the mixed solution 1 and the reducing agent-containing liquid 2.

[0071] Step (3) is a step of separating the solid 6 from the mixture containing the solid obtained in step (2).

[0072] There is no limitation on the method of separating the solid 6. Examples of the separation method include drying under reduced pressure, centrifugal separation, filtration, sedimentation, reprecipitation, and separation using a powder separator (cyclone separator).

[0073] When the total amount of all metal atoms contained in the solid 6 is set to 100 mol%, the content of each metal atom contained in the solid 6 separated in step (3) is preferably 1 mol% or more. For example, when the solid 6 contains two metal atoms, the content of the two metal atoms in the solid 6 is preferably 1 mol% to 99 mol%, more preferably 5 mol% to 95 mol%, and further preferably 10 mol% to 90 mol%. When the solid 6 contains three metal atoms, the content of the three metal atoms in the solid 6 is preferably 1 mol% to 98 mol%, more preferably 5 mol% to 90 mol%, and further preferably 10 mol% to 80 mol%. When the solid 6 contains four metal atoms, the content of the four metal atoms in the solid 6 is preferably 1 mol% to 97 mol%, more preferably 5 mol% to 85 mol%, and further preferably 10 mol% to 70 mol%. When the solid 6 contains five metal atoms, the content of the five metal atoms in the solid 6 is preferably 1 mol% to 96 mol%, more preferably 5 mol% to 80 mol%, and further preferably 10 mol% to 60 mol%. The content of each metal atom contained in the solid 6 can be confirmed by ICP analysis, XRF analysis, or the like.

[0074] The solid 6 separated in step (3) may be supported on a carrier.

[0075] When the solid 6 separated in step (3) is supported on a carrier, in one embodiment, the following step (23) is included between steps (2) and (3) as a step of contacting the mixture containing the solid obtained in the step of obtaining the mixture with the carrier.

[0076] Step (23): a step of contacting the mixture containing the solid obtained in step (2) with a carrier.

[0077] In step (23), it is preferred that at least a part of the mixture cooled in the cooling section 5 is brought into contact with a carrier. The carrier to be brought into contact may be a shaped carrier.

[0078] When the solid 6 separated in step (3) is supported on a carrier, in another embodiment, at least one selected from the group consisting of the mixed solution 1 and the reducing agent-containing liquid 2 obtained in step (1) contains a carrier. Then, a dispersion in which the carrier is dispersed in at least one selected from the group consisting of the mixed solution 1 and the reducing agent-containing liquid 2 is supplied to the mixing unit 3. In this case, a surface protective agent may be used or may not be used.

[0079] The solid 6 supported on the carrier or the solid 6 not supported on the carrier can be recovered and dried by a conventionally known method such as reduced pressure drying, centrifugal separation, filtration, etc., to separate the solid 6.

[0080] Examples of the carrier include alumina, zirconia, titania, ceria, silica, silica-alumina, calcium oxide, magnesium oxide, ceria-zirconia, lanthanum oxide, lanthanum oxide-alumina, tin oxide, tungsten oxide, aluminosilicate, aluminum phosphate, borosilicate, phosphotungstic acid, hydroxyapatite, hydrotalcite, perovskite, cordierite, mullite, or a composite oxide containing one or more thereof, silicon carbide, activated carbon, carbon black, acetylene black, carbon nanotubes, and carbon nanohorns. The carrier may contain one or more thereof.

[0081] The average particle size of the carrier is preferably 10 nm or more, more preferably 15 nm or more, further preferably 50 nm or more, and particularly preferably 100 nm or more. In addition, the average particle size of the carrier is preferably 1000 μm or less, more preferably 800 μm or less, further preferably 500 μm or less, and particularly preferably 100 μm or less. When the average particle size of the carrier is within the above range, the solid 6 can be well dispersibly loaded on the carrier. The average particle size of the carrier can be measured using a conventional particle size distribution measuring device.

[0082] In the case where the solid 6 is loaded on the carrier, the mass of the solid 6 is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, relative to 100 parts by mass of the carrier. In addition, the mass of the solid 6 is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, further preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less, relative to 100 parts by mass of the carrier. If the mass of the solid 6 is above the above lower limit relative to 100 parts by mass of the carrier, a sufficient amount of the catalyst metal is loaded on the carrier to maintain the conversion rate of the raw gas. In addition, if the mass of the solid 6 is below the above upper limit relative to 100 parts by mass of the carrier, the catalyst metal can be made uniform and highly dispersed, the selectivity of the alcohol having 2 to 3 carbon atoms will not be reduced, and the conversion rate of the raw gas will not be reduced. It should be noted that in this specification, in this paragraph and thereafter, "solid 6" refers to either or both of the form in which the solid 6 is not loaded on the carrier or the form in which it is loaded on the carrier and contains the carrier.

[0083] As a step for obtaining an alcohol having 2 to 3 carbon atoms, step (4) is a step for obtaining an alcohol having 2 to 3 carbon atoms by contacting the solid 6 with carbon oxide gas and hydrogen gas. That is, step (4) is a step for obtaining ethanol and / or propanol (1-propanol and 2-propanol).

[0084] The carbon monoxide gas in step (4) is preferably at least one selected from the group consisting of carbon monoxide gas and carbon dioxide gas. When both carbon monoxide and carbon dioxide are used as the carbon monoxide gas, these gases can be contained in any ratio. Carbon monoxide gas, carbon dioxide gas and hydrogen gas as raw materials are actually not limited to waste plastics. Biomass or general waste can also be used as gasification raw materials. In addition, the raw materials are not limited to the above-mentioned gasified raw materials. For example, carbon dioxide can come from various waste gases, combustion gases, incineration gases, DAC. Hydrogen can also be gray hydrogen, blue hydrogen, green hydrogen, turquoise hydrogen.

[0085] In the environment in which step (4) is performed, components other than carbon oxide gas and hydrogen may be present to the extent that they do not affect the production of alcohol having 2 to 3 carbon atoms. Examples of such components include saturated / unsaturated hydrocarbons such as methane, ethane, propane, ethylene, and propylene, nitrogen, and rare gas elements.

[0086] In the environment in which step (4) is performed, water may be present in addition to the raw materials, namely, carbon oxide gas and hydrogen. Originally, in the production of alcohols having 2 to 3 carbon atoms, the less water, the better. However, in the environment in which step (4) is performed, even if water is present to a certain extent, the stability of solid 6 is maintained.

[0087] From the viewpoint of more efficiently obtaining alcohols having 2 to 3 carbon atoms, the total content of carbon oxide gas and hydrogen gas in the environment in which step (4) is carried out is preferably 50 volume % or more, more preferably 80 volume % or more, further preferably 90 volume % or more, and may also be 100 volume %.

[0088] From the viewpoint of further improving the space-time yield of alcohols having 2 to 3 carbon atoms, the ratio of hydrogen to carbon oxide gas (hydrogen / carbon oxide gas, volume ratio) in the environment in which step (4) is performed is preferably 1.0 to 4.0, more preferably 1.5 to 4.0. The adjustment of the ratio can be carried out by a conventionally known method, for example, at least one gas selected from the group consisting of carbon monoxide, carbon dioxide and hydrogen can be added to the mixed gas (a mixture of carbon oxide gas and hydrogen), or a portion of at least one gas selected from the group consisting of carbon monoxide, carbon dioxide and hydrogen can be removed from the mixed gas. A carbon dioxide separation device can also be used as needed.

[0089] The step (4) is preferably carried out in a reactor filled with the solid 6. Examples of the reactor include a fixed bed reactor, a fluidized bed reactor, and a moving bed reactor.

[0090] The solid 6 used in step (4) may be in the form of a powder or a molded body. The shape of the molded body may be granular, cylindrical, or annular, etc., without particular limitation. The molding method of the solid 6 may include tablet molding, compression molding, and extrusion molding, etc., without particular limitation.

[0091] When the solid 6 is filled into the reactor, various diluents inert to the carbon oxide gas, hydrogen gas and the reaction product may be mixed with the solid 6. Examples of the diluent include copper, aluminum oxide, 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.

[0092] In addition, the amount of solid 6 is not particularly limited and can be appropriately adjusted in consideration of other reaction conditions. In addition, solid 6 can be used alone or in combination of two or more. When two or more are used, the combination and ratio can be appropriately adjusted according to the purpose.

[0093] In step (4), solid 6 may be subjected to a reduction treatment before contacting solid 6 with carbon oxide gas and hydrogen. As a reduction treatment, contacting solid 6 with a gas containing hydrogen is a simple and preferred method. In this case, the treatment temperature is preferably 100°C to 600°C.

[0094] In step (4), the solid 6, carbon oxide gas and hydrogen are preferably contacted under heating conditions, more preferably at 150° C. or higher, and further preferably at 200° C. or higher. The contact temperature is preferably 150° C. to 500° C., and more preferably 200° C. to 400° C.

[0095] The reaction in step (4) can be carried out under normal pressure (0 MPa-G) or under pressure. When carried out under pressure, the pressure is preferably 0.1 MPa-G to 12 MPa-G, more preferably 0.1 MPa-G to 10 MPa-G, and even more preferably 0.1 MPa-G to 8 MPa-G.

[0096] For example, when a fixed bed reactor is used for step (4), the carbon monoxide gas and hydrogen gas can be supplied from the inlet side of the reactor while adjusting the temperature to react, and the reaction product and unreacted raw materials can be recovered from the outlet side of the reactor. The raw materials that have not reacted with the target product are usually recovered as a mixed gas, and for example, alcohols having 2 to 3 carbon atoms can be separated by cooling the gas. The unreacted raw material gas can be recycled to the reactor inlet again by adjusting the ratio of hydrogen to carbon monoxide gas as needed.

[0097] The alcohol having 2 to 3 carbon atoms obtained in step (4) can be converted into olefins by a conventionally known method. The alcohol having 2 to 3 carbon atoms as a raw material can be used after being purified and separated according to necessary components, or the alcohol obtained in step (4) can be used directly. In addition, an alcohol obtained by a method other than the method for producing the alcohol having 2 to 3 carbon atoms of the present embodiment can be added (supplemented). The alcohol in the raw material containing alcohol can contain water and / or other oxygen-containing compounds, and water and / or other oxygen-containing compounds can also be intentionally added.

[0098] In addition, in step (4), products other than alcohols having 2 to 3 carbon atoms (for example, oxygen-containing compounds such as acetic acid and acetaldehyde, esters such as ethyl acetate, methyl acetate, and methyl formate) may be produced. Therefore, the method for producing alcohols having 2 to 3 carbon atoms of the present embodiment may include a step (4') of hydrogenating products other than alcohols having 2 to 3 carbon atoms to convert them into alcohols (alcoholization step). As step (4'), for example, a method of converting oxygen-containing compounds such as acetaldehyde and acetic acid into alcohols by contacting them with a hydrogenation catalyst may be cited.

[0099] As the hydrogenation catalyst in step (4'), 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 the same carrier as the carrier used for the solid 6. The hydrogenation catalyst and the solid 6 used in step (4') can be mixed with each other and used, or they can be filled in the same reactor in multiple stages in layers, or the reactors filled with each can be connected and used.

[0100] In addition, step (4) may further include a step of contacting at least a part of the product containing alcohol with a base to remove the acidic substance.

[0101] By including steps (1) to (4), the method for producing an alcohol having 2 to 3 carbon atoms of the present embodiment can achieve a relatively excellent selectivity for alcohol having 2 to 3 carbon atoms. In addition, even if the reaction in step (4) is carried out under low pressure conditions of less than 1 MPa-G, the method for producing an alcohol having 2 to 3 carbon atoms of the present embodiment can achieve a relatively excellent selectivity for alcohol having 2 to 3 carbon atoms.

[0102] It should be noted that the method for producing an alcohol having 2 to 3 carbon atoms according to the present embodiment is not limited to the above-described embodiment, and various modifications can be made without departing from the gist of the disclosure in the present application.

[0103] The present disclosure includes the following aspects.

[0104] [1] A method for producing an alcohol having 2 to 3 carbon atoms, comprising the following steps (1) to (4).

[0105] Step (1): a step of preparing a mixed solution containing two or more metal salts of different metal types

[0106] Step (2): A step of mixing the mixed solution obtained in step (1) with a reducing agent-containing liquid containing a reducing agent to obtain a mixture containing a solid containing two or more metals.

[0107] Step (3): a step of separating a solid from the mixture containing the solid obtained in step (2)

[0108] Step (4): a step of contacting the solid obtained in step (3) with carbon oxide gas and hydrogen gas to obtain an alcohol having 2 to 3 carbon atoms.

[0109] [2] The method for producing an alcohol having 2 to 3 carbon atoms according to the above [1], wherein the following step (23) is included between the steps (2) and (3):

[0110] Step (23): a step of contacting the mixture containing the solid obtained in step (2) with a carrier.

[0111] [3] The method for producing an alcohol having 2 to 3 carbon atoms according to [1] above, wherein in the step (2), at least one selected from the group consisting of the mixed liquid obtained in the step (1) and the reducing agent-containing liquid contains a carrier.

[0112] [4] A method for producing an alcohol having 2 to 3 carbon atoms as described in any one of [1] to [3] above, wherein in the step (2), the mixing is performed while at least one selected from the group consisting of the mixed liquid obtained in the step (1) and the reducing agent-containing liquid is heated to 100° C. or above.

[0113] [5] The method for producing an alcohol having 2 to 3 carbon atoms according to any one of [1] to [4] above, wherein the reducing agent is an alcohol.

[0114] [6] The method for producing an alcohol having 2 to 3 carbon atoms as described in any one of [1] to [5] above, wherein the mixed solution containing two or more metal salts is a mixed solution containing metal salts of at least one metal selected from the group consisting of 3d metals, 4d metals and 5d metals.

[0115] [7] A method for producing an alcohol having 2 to 3 carbon atoms as described in any one of [1] to [6] above, wherein in the step (4), the solid obtained in the step (3) is contacted with carbon oxide gas and hydrogen gas at a temperature above 200°C.

[0116] [8] The method for producing an alcohol having 2 to 3 carbon atoms as described in any one of [1] to [7] above, wherein the carbon oxide gas is at least one selected from the group consisting of carbon monoxide gas and carbon dioxide gas.

[0117] It should be noted that the method for producing an alcohol having 2 to 3 carbon atoms disclosed in the present invention is not limited to the above-mentioned embodiments, and various changes can be made without departing from the main purpose of the present invention. In addition, the method for producing an alcohol having 2 to 3 carbon atoms disclosed in the present invention is not limited by the effects of the above-mentioned embodiments. That is, the embodiments disclosed this time should be considered to be illustrative rather than restrictive in all aspects. The scope of the present invention is indicated by the claims rather than the above description. In addition, the scope of the present invention is intended to include all changes within the meaning and scope equivalent to the claims.

[0118] Example

[0119] Hereinafter, the present disclosure will be described with reference to examples, but the present disclosure is not limited to these examples.

[0120] (Example 1)

[0121] <Preparation of catalyst (solid)>

[0122] 25 mL of dehydrated ethylene glycol and 0.113 mL of 35% by mass hydrochloric acid were mixed to prepare solution (1). 389.6 mg of iron (II) chloride tetrahydrate was mixed in 5.0 mL of the solution (1) to obtain solution (2). Then, 83.1 mg of lithium chloride was mixed in 5.0 mL of the solution (1) to obtain solution (3), and 516.1 mg of rhodium chloride trihydrate was mixed in 5.0 mL of the solution (1) to obtain solution (4). The entire amount of solution (2) was added to solution (4), and then the entire amount of solution (3) was added and mixed to obtain solution (5). 6.175 g of SiO 2 Carrier (specific surface area 250m 2 / g) was added with 10mL of solution (1), and then the whole amount of solution (5) was added to obtain a mixture (1). 4.0g of sodium hydroxide was added to 100mL of ethylene glycol heated to 195°C and dissolved, and the mixture (1) was added dropwise. Heating was stopped 1 minute after the end of the addition, and 100mL of ethylene glycol was added, and the mixture (2) was obtained by cooling to 50°C. The obtained mixture (2) was distributed into centrifuge tubes in portions of 10mL each, and 20mL of acetone was added to each centrifuge tube and centrifuged (7000rpm) to remove the supernatant. Then, 5mL of ion exchange water and 15mL of acetone were added, and the supernatant was removed again by centrifugation (7000rpm). This operation was performed 3 times in total. Then, 5mL of ethanol and 15mL of ether were added and centrifuged (7000rpm) to remove the supernatant to obtain a solid. The solids obtained in the centrifuge tubes were mixed and then dried at room temperature under reduced pressure for 12 hours to obtain FeLiRh / SiO 2 Catalyst (a).

[0123] <Manufacturing of ethanol and / or propanol>

[0124] 1.0 g FeLiRh / SiO 2 The catalyst (a) was filled into a quartz reaction tube with an inner diameter of 12 mm to obtain a reaction bed. In the reaction bed, the catalyst was subjected to reduction treatment by setting the reduction temperature to 300°C and heating for 1 hour while nitrogen containing 10% by volume of hydrogen was circulated at 100 NmL / min under normal pressure. It should be noted that the unit NmL / min represents the flow rate converted to 0°C and 1 atmosphere. Next, the reaction temperature was set to 300°C, and the mixed gas (volume ratio: CO 2 / H 2 =1 / 3) circulation, thereby producing ethanol and / or propanol. It should be noted that G represents the gauge pressure. The gas flowing from the reaction bed was analyzed by gas chromatography. CO 2 The conversion (mol %) and selectivity (mol %, carbon basis) of the products (methane, CO, EtOH and PrOH) are shown in Table 1.

[0125] (Examples 2 to 4)

[0126] Ethanol and / or propanol were produced in the same manner as in Example 1 except that FeLiRh / catalyst (a) was used and the reduction temperature and reaction temperature were set to the reduction temperature and reaction temperature described in Table 1.

[0127] (Example 5)

[0128] <Preparation of catalyst (solid)>

[0129] 25 mL of dehydrated ethylene glycol and 0.113 mL of 35% by mass hydrochloric acid were mixed to prepare solution (1). 389.6 mg of iron (II) chloride tetrahydrate was mixed in 5.0 mL of the solution (1) to obtain solution (2). Then, 483.1 mg of cerium chloride was mixed in 5.0 mL of the solution (1) to obtain solution (3), and 516.1 mg of rhodium chloride trihydrate was mixed in 5.0 mL of the solution (1) to obtain solution (4). The entire amount of solution (2) was added to solution (4), and then the entire amount of solution (3) was added and mixed to obtain solution (5). 6.175 g of TiO 2 Carrier (specific surface area 92m 2 / g) was added with 10mL of solution (1), and then the whole amount of solution (5) was added to obtain a mixture (1). 4.0g of sodium hydroxide was added to 100mL of ethylene glycol heated to 195°C and dissolved, and the mixture (1) was added dropwise. Heating was stopped 1 minute after the end of the addition, and 100mL of ethylene glycol was added, and the mixture (2) was obtained by cooling to 50°C. The obtained mixture (2) was distributed into centrifuge tubes in portions of 10mL each, and 20mL of acetone was added to each centrifuge tube and centrifuged (7000rpm) to remove the supernatant. Then, 5mL of ion exchange water and 15mL of acetone were added, and the supernatant was removed again by centrifugation (7000rpm). This operation was performed 3 times in total. Then, 5mL of ethanol and 15mL of ether were added and centrifuged (7000rpm) to remove the supernatant to obtain a solid. The solids obtained in the centrifuge tubes were mixed and then dried at room temperature under reduced pressure for 12 hours to obtain CeFeRh / TiO 2 Catalyst (b).

[0130] <Manufacturing of ethanol and / or propanol>

[0131] 1.0g CeFeRh / TiO 2 The catalyst (b) was filled into a quartz reaction tube with an inner diameter of 12 mm to obtain a reaction bed. In the reaction bed, the catalyst was subjected to reduction treatment by setting the reduction temperature to 300° C. and heating for 1 hour while nitrogen containing 10% by volume of hydrogen was circulated at 100 NmL / min under normal pressure. Next, the reaction temperature was set to 300° C., and a mixed gas (volume ratio: CO / H) as a raw material gas was heated at 50 NmL / min and 0.8 MPa-G. 2=1 / 2) circulation, thereby producing ethanol and / or propanol. It should be noted that G represents the gauge pressure. The gas flowing from the reaction bed was analyzed by gas chromatography. The CO conversion rate (mol %) and the products (methane, CO 2 , EtOH and PrOH) (mol %), based on carbon, and these results are shown in Table 1.

[0132] (Examples 6 to 8)

[0133] Using CeFeRh / TiO 2 Ethanol and / or propanol were produced in the same manner as in Example 5 except that the reduction temperature and reaction temperature were set to those shown in Table 1 for the catalyst (b).

[0134] (Example 9)

[0135] <Preparation of catalyst (solid)>

[0136] 15 mL of ion exchange water and 60.4 mg of silver nitrate were mixed to obtain solution (1). Next, 99.6 mg of rhodium (III) acetate was mixed with 15 mL of ion exchange water to obtain solution (2). Solution (2) was mixed with solution (1) to obtain solution (3). 1.425 g of SiO 2 Carrier (specific surface area 250m 2 / g) was added with 10mL of ion exchange water, the entire amount of solution (3) was added thereto, and the mixture (1) was obtained by stirring for 15 minutes. The mixture (1) was sprayed into 300mL of ethylene glycol heated to 175°C. The heating was stopped 10 minutes after the spraying was completed and the mixture was cooled to 50°C to obtain a mixture (2). The obtained mixture (2) was distributed into centrifuge tubes in portions of 10mL each, 20mL of acetone was added to each centrifuge tube and centrifuged (7000rpm) to remove the supernatant. Then, 5mL of ion exchange water and 15mL of acetone were added, and the supernatant was removed again by centrifugation (7000rpm). This operation was performed 3 times in total. Then, 5mL of ethanol and 15mL of ether were added and centrifuged (7000rpm) to remove the supernatant to obtain a solid. The solids obtained in each centrifuge tube were mixed and then dried at room temperature and reduced pressure for 12 hours to obtain AgRh / SiO 2 Catalyst (c).

[0137] <Manufacturing of ethanol and / or propanol>

[0138] Using AgRh / SiO 2Ethanol and / or propanol were produced in the same manner as in Example 5 except that the reduction temperature and the reaction temperature were set to the reduction temperature and the reaction temperature described in Table 1 for the catalyst (c).

[0139] (Example 10)

[0140] <Preparation of catalyst (solid)>

[0141] 25 mL of dehydrated ethylene glycol and 0.113 mL of 35% by mass hydrochloric acid were mixed to prepare a solution (1). 232.3 mg of sodium molybdate dihydrate was mixed with 5.0 mL of the solution (1) to obtain a solution (2). Next, 228.2 mg of nickel (II) chloride was mixed with 5.0 mL of the solution (1) to obtain a solution (3), and 316.7 mg of sodium tungstate dihydrate was mixed with 5.0 mL of the solution (1) to obtain a solution (4). The entire amount of the solution (3) was added to the solution (2), and then the entire amount of the solution (4) was added and mixed to obtain a solution (5). 6.175 g of Al 2 O 3 Carrier (specific surface area 170m 2 / g), and then, the entire amount of solution (5) was added to obtain a mixture (1). 4.0 g of sodium hydroxide was added to 100 mL of ethylene glycol heated to 195°C and dissolved, and the mixture (1) was added dropwise. Heating was stopped 1 minute after the end of the dropwise addition, and 100 mL of ethylene glycol was added, and the mixture was cooled to 50°C to obtain a mixture (2). The obtained mixture (2) was distributed into centrifuge tubes in portions of 10 mL each and centrifuged (7000 rpm), and the supernatant was removed. Next, 5 mL of ion exchange water was added, and the supernatant was removed again (7000 rpm), and this operation was performed 3 times in total. Next, 5 mL of ethanol was added and centrifuged (7000 rpm), and the supernatant was removed to obtain a solid. The solids obtained in each centrifuge tube were mixed, and then dried at room temperature and reduced pressure for 12 hours to obtain MoNiW / Al 2 O 3 Catalyst (d).

[0142] <Manufacturing of ethanol and / or propanol>

[0143] Using MoNiW / Al 2 O 3 Ethanol and / or propanol were produced in the same manner as in Example 1 except that the reduction temperature and reaction temperature were set to those shown in Table 1 for the catalyst (d).

[0144] (Example 11)

[0145] <Preparation of catalyst (solid)>

[0146] In addition to using 433.6 mg of cobalt (II) chloride hexahydrate to obtain solution (2), 310.7 mg of copper (II) chloride dihydrate to obtain solution (3), 362.3 mg of iron (II) chloride tetrahydrate to obtain solution (4), and 6.175 g of SiO 2 Carrier (specific surface area 250m 2 / g) instead of Al 2 O 3 A catalyst (solid) was prepared in the same manner as in Example 10 except for the carrier, thereby obtaining CoCuFe / SiO 2 Catalyst (e).

[0147] <Manufacturing of ethanol and / or propanol>

[0148] Using CoCuFe / SiO 2 Ethanol and / or propanol were produced in the same manner as in Example 1 except that the reduction temperature and reaction temperature of the catalyst (e) were set to the reduction temperature and reaction temperature described in Table 1.

[0149] (Example 12)

[0150] <Preparation of catalyst (solid)>

[0151] A catalyst (solid) was prepared in the same manner as in Example 10, except that 349.7 mg of iron (II) chloride tetrahydrate was used to obtain solution (2), 299.8 mg of copper (II) chloride dihydrate was used to obtain solution (3), and 523.2 mg of zinc nitrate hexahydrate was used to obtain solution (4), thereby obtaining CuFeZn / Al 2 O 3 Catalyst (f).

[0152] <Manufacturing of ethanol and / or propanol>

[0153] Using CuFeZn / Al 2 O 3 Ethanol and / or propanol were produced in the same manner as in Example 1 except that the reduction temperature and the reaction temperature were set to the reduction temperature and the reaction temperature described in Table 1 for the catalyst (f).

[0154] (Example 13)

[0155] <Preparation of catalyst (solid)>

[0156] In addition to using 285.6 mg of copper (II) chloride dihydrate to obtain solution (2), 622.2 mg of lanthanum chloride heptahydrate to obtain solution (3), and 6.175 g of ZrO 2 Carrier (specific surface area 100m 2 / g) instead of Al 2 O 3 The catalyst (solid) was prepared in the same manner as in Example 10, except that 5.6 g of potassium hydroxide was used instead of sodium hydroxide as the carrier, thereby obtaining CuKLa / ZrO 2 Catalyst (g).

[0157] <Manufacturing of ethanol and / or propanol>

[0158] Using CuKLa / ZrO 2 Catalyst (g) was used, and except that the reduction temperature and the reaction temperature were set to the reduction temperature and the reaction temperature described in Table 1, the production of ethanol and / or propanol was carried out in the same manner as in Example 1.

[0159] (Example 14)

[0160] <Preparation of catalyst (solid)>

[0161] A catalyst (solid) was prepared in the same manner as in Example 10, except that 429.7 mg of copper (II) chloride dihydrate was used to obtain solution (2) and 749.8 mg of zinc nitrate hexahydrate was used to obtain solution (3), thereby obtaining CuZn / Al 2 O 3 Catalyst (h).

[0162] <Manufacturing of ethanol and / or propanol>

[0163] Using CuZn / Al 2 O 3 Catalyst (h) was used, and ethanol and / or propanol were produced in the same manner as in Example 1 except that the reduction temperature and the reaction temperature were set to the reduction temperature and the reaction temperature described in Table 1.

[0164] (Example 15)

[0165] <Preparation of catalyst (solid)>

[0166] A catalyst (solid) was prepared in the same manner as in Example 10, except that 631.4 mg of cobalt (II) chloride hexahydrate was used to obtain solution (2), and 452.3 mg of copper (II) chloride dihydrate was used to obtain solution (3), thereby obtaining CoCu / Al 2 O 3 Catalyst (i).

[0167] <Manufacturing of ethanol and / or propanol>

[0168] Using CoCu / Al 2 O 3 Ethanol and / or propanol were produced in the same manner as in Example 1 except that the reduction temperature and reaction temperature of the catalyst (i) were set to the reduction temperature and reaction temperature described in Table 1.

[0169] (Example 16)

[0170] <Preparation of catalyst (solid)>

[0171] In addition to using 483.3 mg of cobalt (II) chloride hexahydrate to obtain solution (2), 530.6 mg of ruthenium chloride n-hydrate to obtain solution (3), and 6.175 g of SiO 2 Carrier (specific surface area 250m 2 / g) instead of Al 2 O 3 Except for the support, a catalyst (solid) was prepared in the same manner as in Example 10 to obtain CoRu / SiO 2 Catalyst (j).

[0172] <Manufacturing of ethanol and / or propanol>

[0173] Using CoRu / SiO 2 Catalyst (j) was used, and except that the reduction temperature and the reaction temperature were set to the reduction temperature and the reaction temperature described in Table 1, the production of ethanol and / or propanol was carried out in the same manner as in Example 1.

[0174] (Example 17)

[0175] <Preparation of catalyst (solid)>

[0176] In addition to using 418.3 mg of cobalt (II) chloride hexahydrate to obtain solution (2), 417.0 mg of rhodium chloride trihydrate to obtain solution (3), and 6.175 g of SiO 2 Carrier (specific surface area 250m 2 / g) instead of Al 2 O 3 Except for the support, a catalyst (solid) was prepared in the same manner as in Example 10 to obtain CoNaRh / SiO 2 Catalyst (k).

[0177] <Manufacturing of ethanol and / or propanol>

[0178] Using CoNaRh / SiO 2Catalyst (k) was used, and except that the reduction temperature and the reaction temperature were set to the reduction temperature and the reaction temperature described in Table 1, the production of ethanol and / or propanol was carried out in the same manner as in Example 1.

[0179] (Example 18)

[0180] <Preparation of catalyst (solid)>

[0181] 150 mg of copper (II) chloride dihydrate and 325 mg of iridium chloride n-hydrate were mixed in 15 mL of water to obtain solution (1) and solution (2). 4.3 g of Al was mixed in 10 mL of water. 2 O 3 Carrier (specific surface area 170m 2 / g), solution (1) and solution (2) were added thereto, thereby obtaining a mixture (1). 240 mg of sodium hydroxide was dissolved in 2 mL of water, and the entire amount was added to 300 mL of triethylene glycol, thereby obtaining a mixture (2). Mixture (1) was sprayed onto the mixture (2) heated to 224°C. Heating was stopped 10 minutes after the end of spraying, and the mixture was naturally cooled to room temperature, thereby obtaining a mixture (3). The obtained mixture (3) was distributed into centrifuge tubes in portions of 10 mL each, 20 mL of acetone was added to each centrifuge tube and centrifuged (7000 rpm) to remove the supernatant. Subsequently, 5 mL of ion exchange water and 10 mL of acetone were added, and the mixture was centrifuged again (7000 rpm) to remove the supernatant. This operation was performed 3 times in total. Subsequently, 3 mL of ethanol was added and centrifuged (7000 rpm) to remove the supernatant to obtain a solid. The solids obtained in each centrifuge tube were mixed, and then dried at room temperature and reduced pressure for 12 hours to obtain CuIr / Al 2 O 3 Catalyst (1).

[0182] <Manufacturing of ethanol and / or propanol>

[0183] Using CuIr / Al 2 O 3 Catalyst (1) was used, and the reduction temperature and reaction temperature were set to the reduction temperature and reaction temperature described in Table 1. Ethanol and / or propanol were produced in the same manner as in Example 5.

[0184] (Example 19)

[0185] <Preparation of catalyst (solid)>

[0186] A catalyst (solid) was prepared in the same manner as in Example 10, except that 326.0 mg of copper (II) chloride dihydrate was used to obtain solution (2) and 624.2 mg of potassium chloride palladium oxide was used to obtain solution (3), thereby obtaining CuPd / Al 2 O 3 Catalyst (m).

[0187] <Manufacturing of ethanol and / or propanol>

[0188] Using CuPd / Al 2 O 3 Production of ethanol and / or propanol was carried out in the same manner as in Example 5 except that the reduction temperature and reaction temperature were set to those described in Table 1 for the catalyst (m).

[0189] (Example 20)

[0190] <Preparation of catalyst (solid)>

[0191] 234 mg of potassium chloropalladate and 189 mg of rhodium chloride trihydrate were mixed in 15 mL of water to obtain solution (1) and solution (2). 2.8 g of Al was mixed in 10 mL of water. 2 O 3 Carrier (specific surface area 170m 2 / g), solution (1) and solution (2) were added thereto, thereby obtaining a mixture (1). The mixture (1) was sprayed into 300mL of triethylene glycol heated to 224°C. The heating was stopped 10 minutes after the spraying was completed, and the mixture was naturally cooled to room temperature, thereby obtaining a mixture (2). The obtained mixture (2) was distributed into centrifuge tubes in portions of 10mL each, and 20mL of acetone was added to each centrifuge tube and centrifuged (7000rpm) to remove the supernatant. Subsequently, 5mL of ion exchange water and 10mL of acetone were added, and the mixture was centrifuged again (7000rpm) to remove the supernatant. This operation was performed 3 times in total. Subsequently, 3mL of ethanol was added and centrifuged (7000rpm) to remove the supernatant to obtain a solid. The solids obtained in each centrifuge tube were mixed, and then dried at room temperature and reduced pressure for 12 hours to obtain PdRh / Al 2 O 3 Catalyst (n).

[0192] <Manufacturing of ethanol and / or propanol>

[0193] Using PdRh / Al 2 O 3Catalyst (n) was used, and except that the reduction temperature and the reaction temperature were set to the reduction temperature and the reaction temperature described in Table 1, the production of ethanol and / or propanol was carried out in the same manner as in Example 5.

[0194] (Example 21)

[0195] <Preparation of catalyst (solid)>

[0196] A catalyst (solid) was prepared in the same manner as in Example 18 except that 148 mg of copper (II) chloride dihydrate and 361 mg of potassium chloroplatinate were used to obtain CuPt / Al 2 O 3 Catalyst (o).

[0197] <Manufacturing of ethanol and / or propanol>

[0198] Using CuPt / Al 2 O 3 Catalyst (o) was used, and except that the reduction temperature and the reaction temperature were set to the reduction temperature and the reaction temperature described in Table 1, the production of ethanol and / or propanol was carried out in the same manner as in Example 5.

[0199] (Example 22)

[0200] <Manufacturing of ethanol and / or propanol>

[0201] Using the CuKLa / ZrO obtained in Example 13 2 Catalyst (g) was used, and except that the reduction temperature and the reaction temperature were set to the reduction temperature and the reaction temperature described in Table 1, the production of ethanol and / or propanol was carried out in the same manner as in Example 5.

[0202] (Example 23)

[0203] <Manufacturing of ethanol and / or propanol>

[0204] Using the CuZn / Al obtained in Example 14 2 O 3 Catalyst (h) was used, and except that the reduction temperature and the reaction temperature were set to the reduction temperature and the reaction temperature described in Table 1, the production of ethanol and / or propanol was carried out in the same manner as in Example 5.

[0205] (Example 24)

[0206] <Preparation of catalyst (solid)>

[0207] A catalyst (solid) was prepared in the same manner as in Example 10, except that 657.4 mg of cobalt (II) chloride hexahydrate was used to obtain solution (2), and 656.7 mg of nickel (II) chloride hexahydrate was used to obtain solution (3), thereby obtaining CoNi / Al 2 O 3 Catalyst (p).

[0208] <Manufacturing of ethanol and / or propanol>

[0209] Using CoNi / Al 2 O 3 Ethanol and / or propanol were produced in the same manner as in Example 5 except that the reduction temperature and the reaction temperature were set to the reduction temperature and the reaction temperature described in Table 1 for the catalyst (p).

[0210] (Example 25)

[0211] <Preparation of catalyst (solid)>

[0212] The catalyst was prepared in the same manner as in Example 18 except that 230 mg of copper (II) chloride dihydrate and 356 mg of rhodium chloride trihydrate were used to obtain CuRh / Al 2 O 3 Catalyst (q).

[0213] <Manufacturing of ethanol and / or propanol>

[0214] Using CuRh / Al 2 O 3 Catalyst (q) and the reduction temperature and reaction temperature were set to the reduction temperature and reaction temperature described in Table 1. Ethanol and / or propanol were produced in the same manner as in Example 5.

[0215] (Example 26)

[0216] <Manufacturing of ethanol and / or propanol>

[0217] Using the FeLiRh / SiO obtained in Example 1 2 Ethanol and / or propanol were produced in the same manner as in Example 5 except that the reduction temperature and reaction temperature were set to those shown in Table 1 for the catalyst (a).

[0218] (Example 27)

[0219] <Manufacturing of ethanol and / or propanol>

[0220] Using the CuFeZn / Al obtained in Example 12 2 O 3Catalyst (f), the reduction temperature and the reaction temperature were set to the reduction temperature and the reaction temperature shown in Table 1, and ethanol and / or propanol were produced in the same manner as in Example 5 except for this.

[0221] (Example 28)

[0222] <Preparation of catalyst (solid)>

[0223] A catalyst was prepared in the same manner as in Example 20 except that 313 mg of potassium chloroplatinate and 199 mg of rhodium(III) chloride trihydrate were used, thereby obtaining PtRh / Al 2 O 3 catalyst (r).

[0224] <Production of ethanol and / or propanol>

[0225] Using PtRh / Al 2 O 3 catalyst (r), the reduction temperature and the reaction temperature were set to the reduction temperature and the reaction temperature shown in Table 1, and ethanol and / or propanol were produced in the same manner as in Example 5 except for this.

[0226] (Example 29)

[0227] <Production of ethanol and / or propanol>

[0228] Using the CoRu / SiO 2 catalyst (j) obtained in Example 16, the reduction temperature and the reaction temperature were set to the reduction temperature and the reaction temperature shown in Table 1, and ethanol and / or propanol were produced in the same manner as in Example 5 except for this.

[0229] (Example 30)

[0230] <Preparation of catalyst (solid)>

[0231] Except for using 398.6 mg of cobalt(II) chloride hexahydrate to obtain solution (2), using 405.4 mg of sodium molybdate dihydrate to obtain solution (3), using 6.175 g of CeO 2 support (specific surface area 150 m 2 / g) instead of Al 2 O 3 support, and using 5.6 g of potassium hydroxide instead of sodium hydroxide, a catalyst (solid) was prepared in the same manner as in Example 10, thereby obtaining CoKMo / CeO 2 catalyst (s).

[0232] <Production of ethanol and / or propanol>

[0233] Using CoKMo / CeO 2Production of ethanol and / or propanol was carried out in the same manner as in Example 5 except that the catalyst (s) and the reduction temperature and the reaction temperature were set to the reduction temperature and the reaction temperature described in Table 1.

[0234] (Example 31)

[0235] <Preparation of catalyst (solid)>

[0236] The catalyst was prepared in the same manner as in Example 20 except that 188 mg of iridium chloride n-hydrate and 134 mg of rhodium chloride trihydrate were used to obtain IrRh / Al 2 O 3 Catalyst (t).

[0237] <Manufacturing of ethanol and / or propanol>

[0238] Using IrRh / Al 2 O 3 Ethanol and / or propanol were produced in the same manner as in Example 5 except that the catalyst (t) and the reduction temperature and the reaction temperature were set to the reduction temperature and the reaction temperature described in Table 1.

[0239] (Example 32)

[0240] <Preparation of catalyst (solid)>

[0241] A 0.1 mol / L aqueous hydrochloric acid solution (1) was prepared. 973.8 mg of cobalt (II) chloride hexahydrate was mixed in 15.0 mL of the solution (1) to obtain a solution (2), 615.3 mg of sodium acetate was mixed in 15.0 mL of the solution (1) to obtain a solution (3), and 395.0 mg of rhodium chloride trihydrate was mixed in 15.0 mL of the solution (1) to obtain a solution (4). 52 mL of the solution (1), 2.14 mL of the solution (2), 2.14 mL of the solution (3) and 10.71 mL of the solution (4) were mixed to obtain a mixed solution (5). Using a plunger pump, a 25 vol% aqueous ethanol solution (solution (6)) was heated to 350° C. using a heater in the middle of the flow channel and delivered to a continuous reactor at 100 mL / min. A 25 mol / L aqueous sodium hydroxide solution was delivered at 10 mL / min using another plunger pump to obtain a stream (1) mixed with the heated solution (6). The material stream (1) was mixed with the mixed solution (5) delivered by the syringe pump at 20 mL / min, and the obtained material stream (2) was rapidly passed through the cooling section to be quenched, and the mixture (1) was discharged from the continuous reactor through the back pressure valve. It should be noted that the back pressure valve was used to control the reaction section to maintain 30 MPa-G. The mixture (1) was mixed with TiO 2 Carrier (specific surface area 92m 2 / g) was contacted, and then the obtained mixture (2) was filtered to obtain a solid. The solid was washed with 50 mL of ion exchange water and dried at room temperature under reduced pressure for 12 hours, thereby obtaining CoNaRh / TiO 2 Catalyst (u).

[0242] <Manufacturing of ethanol and / or propanol>

[0243] Using CoNaRh / TiO 2 (u) Ethanol and / or propanol were produced in the same manner as in Example 5 except that the reduction temperature and the reaction temperature were set to the reduction temperature and the reaction temperature described in Table 1.

[0244] (Example 33)

[0245] <Manufacturing of ethanol and / or propanol>

[0246] Using the CoCu / Al obtained in Example 15 2 O 3 Ethanol and / or propanol were produced in the same manner as in Example 5 except that the reduction temperature and reaction temperature were set to those shown in Table 1 for the catalyst (i).

[0247] (Example 34)

[0248] <Preparation of catalyst (solid)>

[0249] A catalyst (solid) was prepared in the same manner as in Example 10, except that 398.6 mg of cobalt (II) chloride hexahydrate was used to obtain solution (2), 405.4 mg of sodium molybdate dihydrate was used to obtain solution (3), and 5.6 g of potassium hydroxide was used instead of sodium hydroxide, thereby obtaining CoKMo / Al 2 O 3 Catalyst (v).

[0250] <Manufacturing of ethanol and / or propanol>

[0251] Using CoKMo / Al 2 O 3 Ethanol and / or propanol were produced in the same manner as in Example 5 except that the reduction temperature and reaction temperature of the catalyst (v) were set to the reduction temperature and reaction temperature described in Table 1.

[0252] (Example 35)

[0253] <Preparation of catalyst (solid)>

[0254] In addition to using 499.3 mg of cobalt (II) chloride hexahydrate to obtain solution (2), 507.7 mg of sodium molybdate dihydrate to obtain solution (3), and 6.175 g of CeO 2 Carrier (specific surface area 150m 2 / g) instead of Al 2 O 3 A catalyst (solid) was prepared in the same manner as in Example 10 except for the carrier, thereby obtaining CoMo / CeO 2 Catalyst (w).

[0255] <Manufacturing of ethanol and / or propanol>

[0256] Using CoMo / CeO 2 Production of ethanol and / or propanol was carried out in the same manner as in Example 5 except that the reduction temperature and reaction temperature of the catalyst (w) were set to the reduction temperature and reaction temperature described in Table 1.

[0257] (Example 36)

[0258] <Preparation of catalyst (solid)>

[0259] In addition to using 83.6 mg of lithium chloride to obtain solution (2), 390.3 mg of manganese (II) chloride tetrahydrate to obtain solution (3), 519.3 mg of rhodium chloride trihydrate to obtain solution (4), and 6.175 g of SiO 2 Carrier (specific surface area 250m 2 / g) instead of Al 2 O 3 Except for the support, a catalyst (solid) was prepared in the same manner as in Example 10 to obtain LiMnRh / SiO 2 Catalyst (aa).

[0260] <Manufacturing of ethanol and / or propanol>

[0261] Using LiMnRh / SiO 2 Catalyst (aa) was used, and except that the reduction temperature and the reaction temperature were set to the reduction temperature and the reaction temperature described in Table 1, the production of ethanol and / or propanol was carried out in the same manner as in Example 5.

[0262] (Example 37)

[0263] <Manufacturing of ethanol and / or propanol>

[0264] Using the CoCuFe / SiO obtained in Example 11 2Production of ethanol and / or propanol was carried out in the same manner as in Example 5 except that the reduction temperature and reaction temperature were set to those shown in Table 1 for the catalyst (e).

[0265] (Example 38)

[0266] <Manufacturing of ethanol and / or propanol>

[0267] Using the CoNaRh / SiO obtained in Example 17 2 Ethanol and / or propanol were produced in the same manner as in Example 5 except that the reduction temperature and reaction temperature of the catalyst (k) were set to the reduction temperature and reaction temperature described in Table 1.

[0268] (Example 39)

[0269] <Preparation of catalyst (solid)>

[0270] In addition to using 351 mg potassium chloropalladate, 283 mg rhodium chloride trihydrate and SiO 2 Carrier (specific surface area 250m 2 / g), a catalyst was prepared in the same manner as in Example 20 to obtain PdRh / SiO 2 Catalyst (ab).

[0271] <Manufacturing of ethanol and / or propanol>

[0272] Using PdRh / SiO 2 Ethanol and / or propanol were produced in the same manner as in Example 5 except that the reduction temperature and reaction temperature were set to those shown in Table 1 for the catalyst (ab).

[0273] (Example 40)

[0274] <Preparation of catalyst (solid)>

[0275] A catalyst (solid) was prepared in the same manner as in Example 18 except that 230 mg of copper (II) chloride dihydrate and 356 mg of ruthenium chloride n-hydrate were used to obtain CuRu / Al 2 O 3 Catalyst (ac).

[0276] <Manufacturing of ethanol and / or propanol>

[0277] Using CuRu / Al 2 O 3 Catalyst (ac) and the reduction temperature and reaction temperature were set to the reduction temperature and reaction temperature described in Table 1. Ethanol and / or propanol were produced in the same manner as in Example 5.

[0278] (Example 41)

[0279] <Preparation of catalyst (solid)>

[0280] In addition to using 290 mg of rhodium chloride trihydrate, 288 mg of ruthenium chloride n-hydrate and SiO 2 Carrier (specific surface area 250m 2 / g), the catalyst was prepared in the same manner as in Example 20, RhRu / SiO 2 Catalyst (ad).

[0281] <Manufacturing of ethanol and / or propanol>

[0282] Using RhRu / SiO 2 Catalyst (ad) and the reduction temperature and reaction temperature were set to the reduction temperature and reaction temperature described in Table 1. Ethanol and / or propanol were produced in the same manner as in Example 5.

[0283] (Comparative Example 1)

[0284] <Preparation of Catalyst>

[0285] The catalyst was prepared according to the method described in Non-Patent Document 1 (Chemistry and Industry, Vol. 47, No. 10, pp. 1314-1316 (1994)). Specifically, 0.3430 g of rhodium nitrate n-hydrate, 0.4882 g of iron nitrate nonahydrate and 0.0570 g of lithium chloride were mixed in 5.3 mL of water to obtain an aqueous solution. The aqueous solution was dripped and impregnated into 3.78 g of SiO 2 Carrier (specific surface area 250m 2 The obtained product was transferred to an alumina dish, dried at 110°C for 19 hours in air, and then calcined at 500°C for 4 hours in air to obtain FeLiRh / SiO 2 Catalyst (x).

[0286] <Manufacturing of ethanol and / or propanol>

[0287] Using FeLiRh / SiO 2 Ethanol and / or propanol were produced in the same manner as in Example 1 except that the reduction temperature and reaction temperature of the catalyst (x) were set to the reduction temperature and reaction temperature described in Table 1.

[0288] (Comparative Example 2)

[0289] <Preparation of Catalyst>

[0290] The catalyst was prepared according to the method described in non-patent document 2 (Catalysts Communications, 98, pages 90-93 (2017)). Specifically, 0.1600 g of rhodium nitrate n-hydrate, 0.2727 g of iron nitrate nonahydrate, and 0.3023 g of cerium nitrate hexahydrate were mixed in 1.4 mL of water to obtain an aqueous solution. The aqueous solution was dripped and impregnated into 3.78 g of TiO 2 Carrier (specific surface area 92m 2 The obtained product was transferred to an alumina dish, dried at 110°C for 19 hours in air, and then calcined at 500°C for 4 hours in air to obtain CeFeRh / TiO 2 Catalyst (y).

[0291] <Manufacturing of ethanol and / or propanol>

[0292] Using CeFeRh / TiO 2 Ethanol and / or propanol were produced in the same manner as in Example 5 except that the reduction temperature and reaction temperature of the catalyst (y) were set to the reduction temperature and reaction temperature described in Table 1.

[0293]

[0294] As can be seen from the results in Table 1, Examples 1 to 41 are superior to Comparative Examples 1 and 2 in terms of selectivity for alcohols having 2 to 3 carbon atoms.

[0295] Description of symbols

[0296] 1…mixed liquid, 2…reducing agent-containing liquid, 3…mixing part, 4…heating part, 5…cooling part, 6…solid

Claims

1. A method for producing an alcohol having 2 to 3 carbon atoms, in, The method for producing an alcohol having 2 to 3 carbon atoms comprises: A step of preparing a mixed solution containing two or more metal salts of different metal types; A step of mixing the mixed solution obtained by the step of preparing the mixed solution with a reducing agent-containing liquid containing a reducing agent to obtain a mixture containing a solid containing two or more metals; A step of separating a solid from the mixture containing the solid obtained by the step of obtaining the mixture; and A step of contacting the solid obtained in the step of separating the solid with carbon oxide gas and hydrogen gas to obtain an alcohol having 2 to 3 carbon atoms.

2. The method for producing an alcohol having 2 to 3 carbon atoms according to claim 1, in, Between the step of obtaining a mixture and the step of separating the solid, the mixture containing the solid obtained by the step of obtaining a mixture is brought into contact with a carrier.

3. The method for producing an alcohol having 2 to 3 carbon atoms according to claim 1, in, In the step of obtaining a mixed solution, at least one selected from the group consisting of the mixed solution obtained by the step of preparing a mixed solution and the reducing agent-containing liquid contains a carrier.

4. The method for producing an alcohol having 2 to 3 carbon atoms according to any one of claims 1 to 3, in, In the step of obtaining the mixture, the mixing is performed in a state where at least one selected from the group consisting of the mixed solution obtained in the step of preparing the mixed solution and the reducing agent-containing liquid is heated to 100° C. or higher.

5. The method for producing an alcohol having 2 to 3 carbon atoms according to any one of claims 1 to 3, in, The reducing agent is alcohol.

6. The method for producing an alcohol having 2 to 3 carbon atoms according to any one of claims 1 to 3, in, The mixed solution containing two or more metal salts is a mixed solution containing metal salts of at least one metal selected from the group consisting of 3d metals, 4d metals, and 5d metals.

7. The method for producing an alcohol having 2 to 3 carbon atoms according to any one of claims 1 to 3, in, In the step of obtaining the alcohol having 2 to 3 carbon atoms, the solid obtained in the step of separating the solid is brought into contact with carbon oxide gas and hydrogen gas at 200° C. or higher.

8. The method for producing an alcohol having 2 to 3 carbon atoms according to any one of claims 1 to 3, in, The carbon monoxide gas is at least one selected from the group consisting of carbon monoxide gas and carbon dioxide gas.

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