WO2022244797A1 - イソプロピルアルコールの製造方法 - Google Patents

イソプロピルアルコールの製造方法 Download PDF

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WO2022244797A1
WO2022244797A1 PCT/JP2022/020634 JP2022020634W WO2022244797A1 WO 2022244797 A1 WO2022244797 A1 WO 2022244797A1 JP 2022020634 W JP2022020634 W JP 2022020634W WO 2022244797 A1 WO2022244797 A1 WO 2022244797A1
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catalyst
acetone
isopropyl alcohol
reaction
gas
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French (fr)
Japanese (ja)
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淳志 岡村
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Nippon Shokubai Co Ltd
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Nippon Shokubai Co Ltd
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Priority to BR112023023966A priority Critical patent/BR112023023966A2/pt
Priority to US18/560,770 priority patent/US20240262768A1/en
Priority to JP2023522691A priority patent/JP7668352B2/ja
Publication of WO2022244797A1 publication Critical patent/WO2022244797A1/ja
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
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    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/009—Preparation by separation, e.g. by filtration, decantation, screening
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/08—Heat treatment
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalysts
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
    • C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/783—Separation; Purification; Stabilisation; Use of additives by gas-liquid treatment, e.g. by gas-liquid absorption
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation

Definitions

  • the present invention relates to a method for producing isopropyl alcohol.
  • Isopropyl alcohol is a key chemical widely used as a solvent, diluent, etc. in various industrial applications.
  • isopropyl alcohol is mainly produced by a method that utilizes the hydration reaction to propylene obtained by pyrolysis of petroleum (Patent Document 1), or by hydrogenating acetone, which is a by-product of the production of phenol from benzene and propylene. (Patent Document 2) has been used.
  • Patent Document 3 As a method for producing carbon-neutral isopropyl alcohol, a method for producing isopropyl alcohol from plant-derived raw materials using isopropyl alcohol-producing bacteria has been proposed (Patent Document 3). According to the method proposed in Patent Document 3, all the carbon in the obtained isopropyl alcohol is plant-derived, such as glucose, resulting in carbon-neutral isopropyl alcohol. However, isopropyl alcohol production using isopropyl alcohol-producing bacteria required several tens of hours of reaction time, and the accumulation concentration of isopropyl alcohol was insufficient, resulting in unsatisfactory production efficiency.
  • isopropyl alcohol obtained by conventional production methods is derived from fossil resources, so it was not possible to provide carbon-neutral isopropyl alcohol, which is considered essential for building a decarbonized society.
  • Isopropyl alcohol production using isopropyl alcohol-producing bacteria makes it possible to produce carbon-neutral isopropyl alcohol. was left.
  • the present invention has been made in view of these circumstances, and provides a production method that is applicable to the production of carbon-neutral isopropyl alcohol and that enables the production of isopropyl alcohol in an efficient and simple operation. intended to
  • the present invention comprises a step (1) of reacting ethanol and water in the presence of a catalyst to obtain acetone, a step (2) of purifying acetone, and a step (3) of reducing acetone to obtain isopropyl alcohol.
  • a method for producing isopropyl alcohol comprising:
  • the reducing agent used in step (3) preferably contains hydrogen obtained in step (1).
  • the reducing agent used in step (3) preferably contains hydrogen obtained in step (2).
  • the content of carbon dioxide in all components introduced in step (3) is less than 10 mol %.
  • ethanol is preferably derived from biomass as a raw material.
  • 1 is an example of a preferred embodiment of the isopropyl alcohol production process of the present disclosure.
  • 1 is an example of a preferred embodiment of the isopropyl alcohol production process of the present disclosure.
  • 1 is an example of a preferred embodiment of the isopropyl alcohol production process of the present disclosure.
  • the method for producing isopropyl alcohol (sometimes referred to as isopropanol) of the present disclosure includes a step of reacting ethanol and water in the presence of a catalyst to obtain acetone (hereinafter referred to as step (1)).
  • the catalyst also referred to as an acetone synthesis catalyst used in step (1) is not particularly limited as long as it contains various metal elements, preferably alkali metals, alkaline earth metals, iron, manganese, zinc, It preferably contains one or more elements selected from copper, aluminum, and zirconium.
  • the state of the metal element contained in the catalyst used in step (1) is not particularly limited. etc.
  • a metal oxide may be supported on a carrier.
  • the metal oxide may be a composite metal oxide.
  • composite metal oxides include spinel type, perovskite type, magnetoplumbite type, garnet type, etc., but spinel type is preferred.
  • the catalyst used in step (1) preferably contains iron from the viewpoint of catalytic activity. More preferably, in addition to iron (Fe), it contains one or more metals (Me) selected from the group consisting of magnesium (Mg), calcium (Ca), manganese (Mn) and zinc (Zn).
  • Fe iron
  • Mg magnesium
  • Ca calcium
  • Mn manganese
  • Zn zinc
  • the catalyst containing one or more metals (Me) selected from the group consisting of magnesium (Mg), calcium (Ca), manganese (Mn) and zinc (Zn) has the following general formula: (1): MeO.nFe2O3 ( 1) (In formula (1), Me represents one or more metals selected from the group consisting of Mg, Ca, Mn and Zn, and n represents a number of 1 to 6), an iron composite oxide ( ferrite) is preferred. Specific examples of iron composite oxides include MgO.Fe 2 O 3 and ZnO.Fe 2 O 3 .
  • the catalyst containing one or more metals (Me) selected from the group consisting of magnesium (Mg), calcium (Ca), manganese (Mn) and zinc (Zn) is on the other hand, one or more metals (Me) selected from the group consisting of magnesium, calcium, manganese and zinc are preferably 0.4 to 0.7 mol, more preferably 0.4 to 0.6 mol. Yes, more preferably 0.45 to 0.55 mol. That is, n in the above formula (1) is preferably 1.43 to 2.5, more preferably 1.67 to 2.5, still more preferably 2 to 2.22. Good catalytic activity is obtained by setting it as the said range.
  • the catalyst used in step (1) is a metal element or metal oxide supported on a carrier
  • the carrier include activated carbon, silica, alumina, silica-alumina, zeolite, silica-calcia, ceria, magnesia, Diatomaceous earth etc. are mentioned.
  • the weight ratio of the carrier is preferably 20 to 70% by mass with respect to 100% by mass of the entire catalyst. . With such a ratio, the catalyst can be effectively dispersed and supported, and the catalyst can exhibit high activity.
  • the mass ratio of the carrier is more preferably 25-67% by mass, more preferably 30-60% by mass, relative to 100% by mass of the entire catalyst.
  • the catalyst used in step (1) contains aluminum (Al) as the metal element.
  • Al aluminum
  • the aluminum-containing catalyst is a compound containing aluminum singly, for example, aluminum oxide can be mentioned.
  • the aluminum-containing catalyst is a composite metal oxide containing other metal elements, examples thereof include composite metal oxides of aluminum and Sn, Pb, Zn, Fe, In, and the like.
  • the catalyst used in step (1) contains aluminum in the carrier, alumina (Al 2 O 3 ), silica-alumina and the like can be mentioned. From the viewpoint of catalytic performance, Al 2 O 3 is more preferable.
  • the amount of aluminum is preferably 0.01 to 0.5 mol, more preferably 0.05 to 0.5, per 1 mol of iron. mol, more preferably 0.1 to 0.4 mol. By setting it as the said range, a catalyst can express favorable durability.
  • the catalyst used in step (1) contains zirconium (Zr) as the metal element.
  • zirconium-containing catalyst is a compound containing only zirconium, for example, zirconium oxide can be mentioned.
  • zirconium is preferably 0.2 to 2.0 mol, more preferably 0.3 to 1.8 mol, per 1 mol of iron. mol, more preferably 0.4 to 1.5 mol. By setting it as the said range, a catalyst can express favorable durability.
  • the total amount of one or more metals (Me) selected from the group consisting of magnesium, calcium, manganese and zinc, iron, aluminum, and zirconium contained in the catalyst is 100 mass of the catalyst. %, preferably 50 to 100% by mass, more preferably 80 to 100% by mass.
  • the catalyst used in step (1) is not particularly limited in its manufacturing method, and can be manufactured, for example, by an impregnation method, a precipitation method, a coprecipitation method, or the like. More preferred is the coprecipitation method.
  • a coprecipitate sometimes referred to as a catalyst precursor
  • the metal elements which are the catalyst constituents, are uniformly and highly dispersed, resulting in a catalyst with excellent performance. can be manufactured.
  • a catalyst in the coprecipitation method, can be produced by mixing aqueous solutions of compounds of metal elements contained in the catalyst and then adding a basic aqueous solution to these metal elements to simultaneously precipitate sparingly soluble salts.
  • the compound of the metal element is not particularly limited as long as it is soluble in water. For example, it may be selected from chlorides, hydrochlorides, sulfates, nitrates, etc. according to the type of the metal element.
  • the alkali added to precipitate the sparingly soluble salt of the metal element is not particularly limited, and sodium hydroxide, aqueous ammonia, potassium hydroxide, and the like can be used.
  • a step of baking may be included.
  • the amount of metal elements in the solution can be changed as appropriate.
  • an impregnation method can be used.
  • a catalyst in which a metal element is supported on a support can be produced by mixing a solution of a compound of a metal element with a support and then drying the mixture.
  • the compound of the metal element is not particularly limited as long as it is soluble in a solvent such as water.
  • the impregnation method may include a step of mixing the solution of the compound of the metal element and the carrier, a step of drying the mixture, and a step of firing the dried product.
  • the amount of metal elements in the solution can be changed as appropriate.
  • the dispersion state of each catalyst component in the produced catalyst can be evaluated using, for example, an electron microprobe analyzer (EPMA).
  • EPMA electron microprobe analyzer
  • the dispersibility of the metal component contained in the catalyst, such as aluminum is measured by measuring the X-ray dose in each 900 ⁇ m plane in the X-axis and Y-axis directions on the catalyst surface, and calculating the average value from arbitrary points measured. (S) and its standard deviation ( ⁇ ) are obtained.
  • the dispersibility of aluminum contained in the catalyst can be evaluated by the ratio ( ⁇ /S) of the standard deviation ( ⁇ ) to the average value (S).
  • the value of the ratio ( ⁇ /S) is preferably less than 0.25, more preferably less than 0.2, and even more preferably less than 0.15.
  • reaction product containing acetone, hydrogen and carbon dioxide can be obtained by bringing ethanol and water, which are raw materials, into contact with a catalyst.
  • a step of removing components adhering to the catalyst Before bringing ethanol and water, which are raw materials, into contact with the catalyst in step (1), a step of removing components adhering to the catalyst may be performed. Thereby, the function of the catalyst can be exhibited more sufficiently.
  • the method for removing the components adhering to the catalyst is not particularly limited, but a method such as passing an inert gas through the catalyst under heating can be used.
  • the reaction in step (1) is not particularly limited, and may be either a batch system or a continuous system, but a continuous system is preferred from the viewpoint of productivity.
  • the reaction in step (1) is preferably a gas phase reaction.
  • As the reaction format by gas phase reaction fixed bed, moving bed, fluidized bed and the like can be mentioned, but simpler fixed bed format is preferable.
  • a mixture of gaseous ethanol and gaseous water (sometimes referred to as water vapor) is supplied as a raw material gas to the reactor and brought into contact with the catalyst.
  • gaseous ethanol and water vapor may be separately supplied to the reactor as raw material gases and brought into contact with the catalyst.
  • Gaseous ethanol is obtained, for example, by heating liquid ethanol in a vaporizer.
  • Gaseous water is obtained, for example, by heating water in a vaporizer.
  • the raw material gas may contain an inert gas such as nitrogen or helium.
  • the raw material gas includes all gases supplied to the reactor.
  • the concentration of ethanol contained in the raw material gas is preferably 3 to 66 mol %. With such a ratio, isopropyl alcohol can be produced with high productivity.
  • the concentration of ethanol contained in the raw material gas is more preferably 5 to 50 mol %.
  • the molar ratio of water to ethanol contained in the source gas is preferably 0.5-10. With such a ratio, the reaction between ethanol and water is carried out more efficiently. More preferably, the molar ratio of water to ethanol contained in the source gas is 1-5.
  • Ethanol used for the raw material gas is not particularly limited, and may be obtained by any method. Examples include ethanol obtained by a hydration reaction of ethylene, and bioethanol made from biomass raw materials such as carbohydrates such as sugarcane, starches such as grains, and celluloses such as plants.
  • the ethanol used for the gas preferably contains bioethanol.
  • the content of bioethanol contained in 100% by mass of ethanol is preferably 50% by mass or more. More preferably, it is 75% by mass or more, and still more preferably 90% by mass or more.
  • the reaction in step (1) can be carried out under reduced pressure, normal pressure, or increased pressure.
  • the reaction pressure is preferably 0.07 MPa to 0.2 MPa, more preferably 0.1 MPa to 0.15 MPa. be.
  • the reaction temperature in step (1) is preferably 250-600°C, more preferably 300-550°C, and even more preferably 330-500°C.
  • the space velocity of the raw material gas is preferably 300 to 10000 (1/h), more preferably 400 to 8000 (1/h), and further Preferably, it is 500 to 6000 (1/h).
  • the method for producing isopropyl alcohol of the present disclosure includes a step of separating acetone from a mixture containing acetone (hereinafter also referred to as an acetone-containing mixture) and/or purifying acetone (hereinafter referred to as step (2)).
  • the acetone-containing mixture used in step (2) contains at least the acetone obtained in step (1).
  • the acetone-containing mixture used in step (2) may be the product obtained in step (1) as it is, or the product obtained in step (1) may be used in step (3). ) may be the product obtained by performing. Moreover, both of these may be included. That is, in the method for producing isopropyl alcohol of the present disclosure, step (2) may be performed between step (1) and step (3), or may be performed after step (1) and step (3). may be performed both before and after step (3).
  • the ratio of the acetone-containing mixture obtained in the step (1) to the acetone-containing mixture used in the step (2) is arbitrary, but for example, relative to 100% by mass of the acetone-containing mixture used in the step (2) , is preferably 25% by mass or more, more preferably 50% by mass or more, and even more preferably 80% by mass or more.
  • the acetone-containing mixture used contains gas, it is separated into a gas mainly composed of hydrogen or carbon dioxide and a liquid mixture mainly composed of acetone by a known gas-liquid separation method (gas-liquid (sometimes referred to as separation).
  • gas means a substance that exists as a gas under pressurized and cooled conditions in the gas-liquid separation operation.
  • the pressure in the gas-liquid separation operation is preferably 0.1 MPa to 2 MPa, more preferably 0.2 MPa to 1 MPa.
  • the temperature in the gas-liquid separation operation is preferably 0°C to 50°C, more preferably 5°C to 40°C.
  • step (2) an operation of absorbing acetone from a gas mainly composed of hydrogen, carbon dioxide, etc. may be performed.
  • the method of absorbing acetone is not particularly limited, but gas may be introduced into an absorption tower, the acetone in the gas may be absorbed by the absorbent supplied from the top of the tower, and recovered as an acetone-containing liquid from the bottom of the tower.
  • the absorbent supplied from the top of the column any liquid can be used as long as it can effectively absorb acetone, but water is particularly preferred.
  • the acetone-containing absorbent obtained from the bottom of the absorption tower may be combined with the acetone-based liquid mixture obtained by gas-liquid separation. Thereby, the recovery rate of acetone can be improved.
  • step (2) purified acetone can be obtained by distilling the acetone-containing mixture, which is a liquid mixture mainly composed of acetone.
  • Distillation can be performed by a known method. Known distillation methods include, for example, thin film distillation and rectification. Distillation may be continuous or batchwise.
  • step (2) only gas-liquid separation may be performed, gas-liquid separation and distillation may be performed, or only distillation may be performed. in that order.
  • purified acetone is obtained as a distillate by distillation, while the bottom liquid is a liquid mainly composed of water.
  • Step (2) may be performed only once, or may be performed twice or more.
  • step (2) The purified acetone obtained in step (2) can be used as an introduction material in step (3) below. As described above, step (2) may be performed between steps (1) and (3), or may be performed after steps (1) and (3) are performed. When step (2) is performed after step (3), the purified acetone obtained in step (2) can be returned to the reactor in which step (3) is performed and used as a raw material for step (3).
  • the content of acetone contained in the purified acetone obtained in step (2) is preferably 90% by mass or more, more preferably 95% by mass or more, more preferably 98% by mass with respect to 100% by mass of purified acetone. It is more preferable that it is above.
  • the acetone reduction reaction in the following step (3) is performed, and the isopropyl alcohol and gas contained in the obtained product are separated from the gas and liquid, thereby easily obtaining high-purity Isopropyl alcohol is obtained.
  • the method for producing isopropyl alcohol of the present disclosure includes a step of reducing acetone to obtain isopropyl alcohol (hereinafter referred to as step (3)).
  • At least part of the acetone used in step (3) is the acetone obtained in step (1) above.
  • the product (acetone-containing mixture) of step (1) may be used as it is, but purified acetone in step (2) is preferably used.
  • purified high-purity acetone is used as a raw material for the acetone reduction reaction, high-purity isopropyl alcohol can be easily obtained by gas-liquid separation of the isopropyl alcohol contained in the product in step (3) and the gas. . Therefore, performing step (2) before step (3) is one of the preferred embodiments of the method for producing isopropyl alcohol of the present disclosure.
  • the substance for reduction (sometimes referred to as a reducing agent) includes hydrogen, lithium aluminum hydride, sodium borohydride, and the like. Hydrogen is preferred.
  • step (3) the hydrogen used as the reducing agent is not particularly limited, and industrially produced hydrogen may be used. It is preferred to use the hydrogen obtained in step (1).
  • the hydrogenation may also be carried out using the product of step (1) as is.
  • the hydrogen used for reduction in step (3) may contain hydrogen obtained by separation from the acetone-containing mixture in step (2).
  • step (3) hydrogen separated from the acetone-containing mixture in step (2) is brought into contact with purified acetone as a reducing agent, whereby isopropyl alcohol of high purity can be easily obtained.
  • step (3) it is preferable that the content of carbon dioxide contained in all the components to be introduced is small.
  • the content of carbon dioxide in all components introduced in step (3) is preferably less than 10 mol%, more preferably less than 5 mol%, and even more preferably less than 2 mol%.
  • step (2) is performed before step (3), and carbon dioxide is separated from the acetone-containing mixture obtained in step (1) and then introduced into the reactor in which step (3) is performed.
  • step (3) is one of the preferred embodiments of the method for producing isopropyl alcohol of the present disclosure.
  • the catalyst used in step (3) is not particularly limited, and examples thereof include Raney catalysts.
  • Other catalysts include, for example, solid catalysts containing metal elements such as Ba, Co, Cr, Cu, Fe, Mn, Ni, Pd, Pt, Zn, Zr, Ru, and Rh.
  • a solid catalyst containing at least one metal element selected from the group consisting of Pt, Ru, Ni, Fe and Co is preferable, and the group consisting of Ru catalyst, Ni—Pt catalyst, Ru—Pt catalyst, and Ni—Ru catalyst. It is more preferable to use at least one or more solid catalysts selected from.
  • the catalyst it is possible to use one in the form of a single metal element, an alloy, an oxide, or the like. It may also be a mixture of a single metal, a mixture of a single metal and a metal oxide, a mixture of metal oxides, or a mixed metal oxide.
  • the metal elements are activated carbon, silica (SiO 2 ), alumina (Al 2 O 3 ), titania (TiO 2 ), zirconia (ZrO 2 ), ceria (CeO 2 ), magnesia (MgO), diatomaceous earth. You may use the thing carried
  • the shape of these catalysts is not particularly limited, and may be ring-shaped, spherical, or the like.
  • one type of catalyst may be used alone, or two or more types may be used.
  • a known catalyst that reduces acetone to produce isopropyl alcohol may be used.
  • the introduction containing acetone used in step (3) may be liquid or gas.
  • a reaction solvent may be used in step (3).
  • Examples include alcohols, ethers, hydrocarbons and the like. Water may be used.
  • the reaction in step (3) is not particularly limited, and may be carried out either batchwise or continuously, but from the viewpoint of productivity, it is preferably carried out continuously.
  • the reaction in step (3) is preferably a gas phase reaction.
  • the reaction form of the gas phase reaction is not particularly limited, and fixed bed, fluidized bed and the like can be mentioned, but the simpler fixed bed form is preferred.
  • the reaction pressure for the reaction in step (3) is preferably 0.1 MPa to 2 MPa, more preferably 0.1 MPa to 1 MPa.
  • the reaction temperature of the reaction in step (3) is preferably 20°C to 200°C, more preferably 25°C to 150°C.
  • a lower reaction temperature is advantageous in terms of equilibrium, but the hydrogenation is less likely to proceed. is concomitant with hydrocracking, and the yield tends to decrease.
  • the space velocity of the introduced material containing acetone is preferably 200 to 50000 (1/h), more preferably 1000 to 20000 (1/h). Yes, more preferably 2000 to 10000 (1/h).
  • the method for producing isopropyl alcohol of the present disclosure includes a step of recovering isopropyl alcohol.
  • the isopropyl alcohol to be subjected to this recovery step may be the product obtained in the above step (3), and the product obtained by performing the step (3) may be used as it is in the recovery step. After subjecting the product obtained in step (3) to step (2) to separate acetone, the product may be used in the recovery step. Also, both of these products may be used in the recovery process.
  • the isopropyl alcohol to be subjected to the present recovery step is a gas-liquid mixture containing isopropyl alcohol and gas
  • a known method of gas-liquid separation can be used to obtain a gas containing mainly gas such as hydrogen and isopropyl alcohol.
  • the isopropyl alcohol may be recovered after separation into the liquid mixture.
  • gas means a substance that exists as a gas under pressurized and cooled conditions in the gas-liquid separation operation.
  • the pressure in the gas-liquid separation operation is preferably 0.1 MPa to 2 MPa, more preferably 0.2 MPa to 1 MPa.
  • the temperature in the gas-liquid separation operation is preferably 0°C to 50°C, more preferably 5°C to 40°C.
  • Purified isopropyl alcohol can be obtained by distilling the liquid mixture containing isopropyl alcohol obtained by the gas-liquid separation operation in this recovery process.
  • Distillation of the liquid mixture containing isopropyl alcohol can be performed by a known distillation method.
  • Known distillation methods include, for example, thin film distillation and rectification.
  • the distillation operation may be performed continuously or batchwise.
  • azeotropic distillation may be performed as a distillation operation. Since isopropyl alcohol forms an azeotropic mixture with water, high-purity isopropyl alcohol can also be obtained by azeotropic distillation when the liquid mixture containing isopropyl alcohol contains water.
  • the method of producing isopropyl alcohol of the present disclosure may include the step of separating the gas.
  • the step of separating the gas includes, for example, a step of purifying hydrogen contained in the gas phase component obtained in the step (2) of purifying acetone (gas-liquid separation step).
  • the step of purifying the hydrogen contained in the gas phase component obtained in step (2) is also referred to as step (4).
  • the hydrogen-rich composition obtained in step (4) may be recovered as is, or part or all of it may be used for the reduction of acetone in step (3).
  • the hydrogen/carbon dioxide molar ratio in the hydrogen-rich composition obtained in step (4) is preferably at least 90:10, more preferably at least 95:5, and at least 98:2. is more preferred.
  • Examples of methods for separating gas (methods for refining hydrogen) in step (4) include known methods such as physical absorption, chemical absorption, membrane separation, cryogenic separation, and compression liquefaction.
  • the physical absorption method is a method of separating and recovering carbon dioxide from a mixed gas by physical actions such as adsorption and dissolution without performing a chemical reaction, and particularly preferred is the PSA (Pressure Swing Adsorption) method.
  • PSA Pressure Swing Adsorption
  • the chemical absorption method mainly involves reacting carbon dioxide with basic substances such as amines and alkalis, converting them into forms such as hydrogen carbonates and absorbing them.
  • carbon dioxide can be separated and recovered from the absorption liquid by heating or reducing the pressure.
  • the membrane separation method is preferably a method using a separation membrane that selectively allows hydrogen or carbon dioxide to permeate.
  • the membrane used at this time is not particularly limited, but examples include polymer material membranes, dendrimer membranes, amine group-containing membranes, inorganic material membranes such as zeolite membranes, and the like.
  • the separation membrane may contain metal atoms. Although the metal atom is not particularly limited, examples thereof include Pd and the like.
  • the step (4) preferably includes at least one step selected from a membrane separation step, an absorption step with a basic substance or an organic solvent, and an adsorption step with an adsorbent such as PSA or activated carbon.
  • FIGS. 1 and 3 An example of a preferred embodiment of the process for producing isopropyl alcohol of the present disclosure is shown.
  • the process of FIGS. 1 and 3 is an example of a process having an isopropyl alcohol recovery step after the steps (1) ⁇ (2) ⁇ (3) are performed in this order.
  • the process of FIG. 2 is an example of a process having an isopropyl alcohol recovery step after the steps (1) ⁇ (3) ⁇ (2) are performed in this order.
  • the process of FIG. 1 is an example including a gas separation step. If high purity isopropyl alcohol is to be obtained, the process of FIG. 2 would involve performing an azeotropic distillation step of isopropyl alcohol in the isopropyl alcohol recovery step.
  • the processes shown in FIGS. 1 to 3 are more preferable from the viewpoint of simplicity in manufacturing. Furthermore, from the standpoint of catalytic activity, the process of FIG. 1 is more preferred, with a lower content of carbon dioxide being introduced into step (3).
  • the method for producing isopropyl alcohol of the present disclosure may include a step of regenerating the catalyst when a change in activity of the catalyst is observed.
  • the method of regeneration is not particularly limited, but a method of contacting with an oxidizing gas such as oxygen at a high temperature can be used.
  • an oxidizing gas such as oxygen at a high temperature
  • the raw material gas may be changed to an oxidizing gas to regenerate the catalyst. regeneration of the catalyst may be performed.
  • a production apparatus used for producing isopropyl alcohol of the present disclosure may be of a batch type or a continuous type, but a continuous type is preferable from the viewpoint of productivity.
  • a continuous reactor for carrying out step (1) known reactors such as fixed bed reactors, fluidized bed reactors and moving bed reactors can be used. Among these, it is preferable to use a fixed bed reactor, which is easier in terms of equipment and operation.
  • the gas-liquid separation apparatus is not particularly limited, and an ordinary gas-liquid separation apparatus having a pressurization/cooling mechanism can be used.
  • the distillation apparatus is not particularly limited, but a distillation apparatus using a distillation column having 4 to 40 theoretical plates is preferable.
  • step (3) known reactors such as fixed bed reactors, fluidized bed reactors and moving bed reactors can be used. Among these, it is preferable to use a fixed bed reactor, which is easier in terms of equipment and operation.
  • the isopropyl alcohol obtained by the production method of the present disclosure preferably has concentrations of ethanol, water, and acetone as impurities of 10000 ppm or less. Such a low concentration of impurities makes it suitable for various industrial uses. Concentrations of ethanol, water, and acetone as impurities are more preferably 10000 ppm or less, and still more preferably 5000 ppm or less. From the viewpoint of reducing impurities, the processes shown in FIGS. 1 and 3 are more preferable. From the viewpoint of the number of steps, the process of FIG. 1 is more preferable.
  • isopropyl alcohol obtained by the production method of the present disclosure The use of isopropyl alcohol obtained by the production method of the present disclosure is not particularly limited, but it can be suitably used as a raw material for the production of propylene.
  • Propylene can be produced from isopropyl alcohol of the present disclosure, for example, by dehydration by a known method.
  • Catalyst Preparation B1/Catalyst for Acetone Hydrogenation 0.4 mL of dinitrodiammineplatinum nitric acid solution (Tanaka Kikinzoku Kogyo Co., Ltd., platinum content: 100 g/L) was added to 4.0 g of pure water to prepare a platinum-containing aqueous solution.
  • the platinum-containing aqueous solution was added to 4.0 g of cerium oxide powder (manufactured by Rhodia, 3CO) weighed in a magnetic dish and mixed uniformly with a glass rod. Then, after drying at 120° C. for 10 hours, it was calcined at 400° C. for 1 hour to obtain catalyst B1.
  • Step (1) Acetone synthesis reaction
  • Acetone synthesis reaction was carried out using a SUS316 tubular reactor (outer diameter: 10 mm, inner diameter: 8 mm).
  • Catalyst A1 powder uniformly pulverized in an agate mortar is filled in a vinyl chloride disk, compressed at 30 MPaG with a compression molding machine to form a disk, crushed and classified into 0.71 to 1.18 mm, and the granules are obtained.
  • 2.0 g of the catalyst was packed in a SUS tubular reaction tube.
  • a reaction tube filled with catalyst A1 was placed in a circular electric furnace, and nitrogen was supplied at a rate of 50.0 mL/min. (0° C., converted to 1 atm) and heated to 400° C. by heating in an electric furnace for 30 min. held. After that, nitrogen was stopped, and 0.08 g/min. and the reaction was carried out at normal pressure.
  • the ethanol aqueous solution was supplied into the reaction system by the feeder to the ethanol aqueous solution vaporizer provided on the inlet side of the reaction tube.
  • the ethanol aqueous solution vaporization section was heated to 100° C. by external heating.
  • the ethanol aqueous solution supplied to the ethanol aqueous solution vaporization section in a liquid state by the feeder was immediately vaporized and introduced into the SUS316 tubular reactor.
  • the ethanol conversion rate was 100% and the acetone selectivity was 69%.
  • Acetone yield 100 x reactor outlet acetone flow rate x 3/(reactor inlet ethanol flow rate x 2) (2)
  • the acetone yield in formula (2) is evaluated by the amount of carbon in the produced acetone with respect to the total carbon contained in the ethanol supplied from the inlet of the reactor. Therefore, the maximum acetone yield is 75%.
  • Step (2) Acetone purification step
  • the reactor outlet gas obtained in step (1) was introduced into a glass absorption bottle cooled to ice temperature. Pure water was contained in the glass absorption bottle, and condensed components consisting of acetone and water in the reactor outlet gas were collected by bubbling the ice-temperature pure water. When the collected liquid was analyzed by gas chromatography, most of the collected components other than water were acetone, and only a very small amount of components with unknown structures were present.
  • Acetone can be separated and purified from the aqueous acetone solution by a normal distillation operation. Therefore, by distilling the aqueous acetone solution obtained here under appropriate conditions, high-purity acetone can be obtained from the top of the distillation apparatus.
  • gaseous components Components that were not condensed and collected in the absorption bottle were discharged as gaseous components from the absorption bottle.
  • the gaseous components mainly consisted of hydrogen and carbon dioxide, and a small amount of hydrocarbons such as methane, ethylene, and ethane, which were by-products of the reaction, were detected as other components. It was found that the amount of acetone in the gaseous component was extremely small, and that almost all of the acetone produced in the reaction process was collected in the previous absorption operation.
  • This gas component was passed through an absorption bottle containing a 10% by weight sodium hydroxide aqueous solution at room temperature to absorb carbon dioxide in the gas. Hydrocarbons such as methane, ethylene, and ethane were then removed by adsorption through a column packed with activated carbon to obtain hydrogen gas with increased purity.
  • Step (3) Acetone hydrogenation reaction
  • acetone hydrogenation reaction Purified acetone obtained by distilling the acetone aqueous solution obtained by the absorption operation of the acetone synthesis reactor outlet gas is replaced with reagent acetone (manufactured by Nacalai Tesque, purity 99.5% or more), and hydrogen is also used in the acetone synthesis reaction.
  • the acetone hydrogenation reaction was carried out by supplying hydrogen from a cylinder (manufactured by Nippon Steel Chemical & Materials Co., Ltd., purity 99.999% or higher) instead of hydrogen purified by treating the outlet gas.
  • the acetone hydrogenation reaction was carried out using a SUS316 tubular reactor (outer diameter 10 mm, inner diameter 8 mm).
  • Catalyst B1 powder uniformly pulverized in an agate mortar is filled in a vinyl chloride disk, compressed at 30 MPaG with a compression molding machine to form a disk, crushed and classified into 0.71 to 1.18 mm, and the granular form is obtained.
  • 1.4 g of the catalyst was packed in a SUS tubular reaction tube.
  • a reaction tube filled with catalyst B1 was placed in an annular electric furnace, and hydrogen was supplied at a rate of 10.0 mL/min. (0° C., converted to 1 atm), nitrogen at 40.0 mL/min.
  • Acetone conversion 100-100 x (reactor outlet acetone flow rate/reactor inlet acetone flow rate) (4)
  • Isopropyl alcohol selectivity 100 x reactor outlet isopropyl alcohol flow rate / (reactor inlet acetone flow rate - reactor outlet acetone flow rate) (5)
  • acetone hydrogenation reactor outlet gas consists of hydrogen, isopropyl alcohol, and a trace amount of acetone, isopropyl alcohol and hydrogen can be easily separated by normal gas-liquid separation under pressure and cooling.
  • Step (3): Acetone hydrogenation reaction Acetone hydrogenation reaction was carried out under conditions corresponding to the case where the hydrogen used in (Acetone hydrogenation reaction) in Example 1 was changed to a gas mainly composed of hydrogen and carbon dioxide discharged from the absorption bottle after acetone collection. carried out.
  • the composition of the gas discharged from the absorption bottle after acetone collection is mainly composed of hydrogen and carbon dioxide. Cylinders (Nippon Steel Chemical & Materials, purity 99.999% or more) and liquefied carbon dioxide cylinders (Sumitomo Seika, purity 99.9% or more) are used to create a simulated gas and acetone hydrogenation reaction. used for
  • Example 1 In the acetone hydrogenation reaction, the hydrogen in Example 1 was 60 mL/min. (0° C., converted to 1 atm), hydrogen 48 mL/min. (0° C., converted to 1 atm) and carbon dioxide 12 mL/min. (0°C, converted to 1 atmospheric pressure) total 60mL/min. It was carried out in the same manner as in Example 1, except that it was changed to (0° C., converted to 1 atm).
  • catalyst B2 The composition of the resulting catalyst B2 was 1 wt% Pt/ZrO2 ( ie 99 wt% ZrO2 for 1 wt% Pt).
  • Catalyst preparation B3/acetone hydrogenation catalyst Catalyst B3 was prepared in the same manner as Catalyst Preparation B2, except that 0.49 g of the dinitrodiammineplatinum nitric acid solution in Catalyst Preparation B2 was changed to 1.03 g of a ruthenium nitrate solution (manufactured by Tanaka Kikinzoku Co., Ltd., Ru content: 3.92% by mass). did. The composition of the resulting catalyst B3 was 5 mass % Ru/ZrO2.
  • Catalyst preparation B4/acetone hydrogenation catalyst Catalyst B4 was prepared in the same manner as Catalyst Preparation B2, except that 0.49 g of the dinitrodiammineplatinum nitric acid solution in Catalyst Preparation B2 was changed to 11.3 g of a ruthenium nitrate solution (manufactured by Tanaka Kikinzoku Co., Ltd., Ru content: 3.92% by mass). did. The composition of the resulting catalyst B4 was 10 mass % Ru/ZrO2.
  • Catalyst preparation B5/acetone hydrogenation catalyst Catalyst B5 was prepared in the same manner as Catalyst Preparation B2, except that 0.49 g of the dinitrodiammineplatinum nitric acid solution in Catalyst Preparation B2 was changed to 1.24 g of nickel nitrate hexahydrate (manufactured by Nacalai Tesque, special grade). The composition of the resulting catalyst B5 was 5.9 mass % Ni/ZrO2.
  • Catalyst preparation B6/acetone hydrogenation catalyst 0.49 g of dinitrodiammine platinum nitric acid solution in catalyst preparation B2 was mixed with 0.36 g of nickel nitrate hexahydrate (manufactured by Nacalai Tesque, special grade) and dinitrodiammine platinum nitric acid solution (manufactured by Tanaka Kikinzoku Co., Ltd., Pt content 8.19 mass %)
  • Catalyst B6 was prepared in the same manner as Catalyst Preparation B2, except that it was changed to 0.49 g.
  • the composition of the resulting catalyst B6 was 1.8 mass % Ni-1 mass % Pt/ZrO 2 .
  • Catalyst preparation B7/acetone hydrogenation catalyst 1.10 g of nickel nitrate hexahydrate (manufactured by Nacalai Tesque, special grade) and 5.67 g of ruthenium nitrate solution (manufactured by Tanaka Kikinzoku, Ru content 3.92% by mass) were weighed, and pure water was added to make nickel and ruthenium were prepared. After adding the above mixed aqueous solution to 4 g of ZrO 2 powder (Daiichi Kigenso Kagaku Co., Ltd., EP-L, specific surface area: 102 m 2 /g) placed in a magnetic dish, the mixture was heated while stirring with a glass rod to evaporate water. let me The obtained powder was dried at 120° C. for 10 hours and then calcined at 400° C. for 1 hour to prepare catalyst B7. The composition of the obtained catalyst B7 was 5 mass % Ni-5 mass % Ru/ZrO 2 .
  • Catalyst preparation B8/acetone hydrogenation catalyst ZrO 2 powder (Daiichi Kigenso Kagaku Co., Ltd., EP-L, specific surface area 102 m 2 /g) in catalyst preparation B7 was changed to ZrO 2 powder (Daiichi Kigenso Kagaku Co., Ltd., RC-100, specific surface area 118 m 2 /g Catalyst B8 was prepared in the same manner as in Catalyst Preparation B7, except for changing to ).
  • the composition of the obtained catalyst B8 was 5 mass % Ni-5 mass % Ru/ZrO 2 .
  • Catalyst preparation B9/acetone hydrogenation catalyst ZrO 2 powder (Daiichi Kigenso Kagaku Co., Ltd., EP-L, specific surface area 102 m 2 /g) in catalyst preparation B7 was changed to CeO 2 powder (Rhodia Co., 3CO, specific surface area 171 m 2 /g).
  • Catalyst B9 was prepared analogously to Preparation B7.
  • the composition of the obtained catalyst B9 was 5% by weight Ni-5% by weight Ru/CeO 2 .
  • Catalyst preparation B10/acetone hydrogenation catalyst ZrO 2 powder (Daiichi Kigenso Kagaku Co., Ltd., EP-L, specific surface area 102 m 2 /g) in catalyst preparation B7 was added to SiO 2 powder (Fuji Silysia Chemical Co., Ltd. Cariact Q-6, specific surface area 113 m 2 /g).
  • Catalyst B10 was prepared in the same manner as Catalyst Preparation B7, except for the changes. The composition of the resulting catalyst B10 was 5 mass % Ni-5 mass % Ru/SiO 2 .
  • the reactor outlet gas was introduced into a trap placed in an ice water bath, where unreacted raw materials and products were collected.
  • the liquid component collected by the trap was quantitatively analyzed by GC-FID (Agilent, 7890B/capillary column HP-plot Q). Gas products not collected by the trap were introduced directly into the GC-FID for analysis. From these analysis results, acetone conversion and isopropyl alcohol selectivity were calculated according to Equations 3 and 4. Table 1 shows the reaction results obtained at an electric furnace temperature of 100°C.
  • Example 8 An isopropyl alcohol production reaction was initiated by hydrogenation of acetone in the presence of carbon dioxide in the same manner as in Experimental Example 1, except that catalyst B2 was changed to catalyst B9. Table 1 shows the reaction results obtained at an electric furnace temperature of 100°C.
  • Catalyst B5 (5.9% by mass Ni/ZrO 2 ) containing 5.9% by mass of nickel only had a low acetone conversion rate of 14.7%.
  • a high acetone conversion rate was also obtained with catalysts B8, B9, and B10 in which the amounts of ruthenium and nickel supported were each fixed at 5% by mass, and the supports were ZrO 2 (RC-100), CeO 2 , and SiO 2 .
  • Catalyst A3 was obtained in the same manner as in Catalyst Preparation Example A2, except that 22.3 g of zirconium oxynitrate hydrate (manufactured by Aldrich, technical grade) in Catalyst Preparation Example A2 was changed to 3.32 g.
  • Catalyst A4 was obtained in the same manner as in Catalyst Preparation Example A2, except that 22.3 g of zirconium oxynitrate hydrate (manufactured by Aldrich, technical grade) in Catalyst Preparation Example A2 was changed to 11.1 g.
  • Acetone synthesis reaction was carried out using a SUS316 tubular reactor (outer diameter: 10 mm, inner diameter: 8 mm).
  • Catalyst A2 powder uniformly pulverized in an agate mortar is filled in a vinyl chloride disk, compressed at 30 MPaG with a compression molding machine to form a disk, crushed and classified to 0.71 to 1.18 mm, and the granules are obtained.
  • 1.4 g of the catalyst was packed in a SUS tubular reaction tube.
  • a reaction tube filled with catalyst A2 was placed in a circular electric furnace, and nitrogen was supplied at a rate of 11.0 mL/min. (0° C., converted to 1 atm) and heated to 375° C.
  • the ethanol aqueous solution was supplied into the reaction system by the feeder to the ethanol aqueous solution vaporizer provided on the inlet side of the reaction tube.
  • the ethanol aqueous solution vaporization section was heated to 100 degrees by external heating.
  • the ethanol aqueous solution supplied to the ethanol aqueous solution vaporization section in a liquid state by the feeder was immediately vaporized and introduced into the SUS316 tubular reactor together with nitrogen.
  • the reaction temperature was set at 375° C., it was confirmed that acetaldehyde, an intermediate product, was produced in addition to acetone.
  • Catalyst A3 had a low ZrO2 content, so that the catalytic activity decreased in a short period of time. However, it was found that catalysts A2 and A4 with a higher ZrO2 content suppressed the decrease in catalytic activity over time . With catalyst A4, the conversion rate decreased from 51.6% to 43.4% at the beginning of the reaction, but after that, the activity was observed to recover. This behavior was reproduced when tested again under the same conditions. From these, it was found that acetone can be stably synthesized from ethanol by using a Fe 2 O 3 /ZnO/ZrO 2 catalyst containing a predetermined amount of ZrO 2 .

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JP2000103751A (ja) * 1998-09-28 2000-04-11 Degussa Huels Ag アルコ―ルの製造方法
JP2002128716A (ja) * 2000-10-20 2002-05-09 Mitsui Chemicals Inc イソプロピルアルコールの製造方法
JP2004526686A (ja) * 2000-12-23 2004-09-02 デグサ アクチエンゲゼルシャフト カルボニル化合物の水素化によるアルコールの製法
JP2012240914A (ja) * 2011-05-13 2012-12-10 Tokyo Institute Of Technology プロピレンの製造方法
JP2012240913A (ja) * 2011-05-13 2012-12-10 Tokyo Institute Of Technology 炭素数３以上の含酸素化合物の製造方法

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JP2000103751A (ja) * 1998-09-28 2000-04-11 Degussa Huels Ag アルコ―ルの製造方法
JP2002128716A (ja) * 2000-10-20 2002-05-09 Mitsui Chemicals Inc イソプロピルアルコールの製造方法
JP2004526686A (ja) * 2000-12-23 2004-09-02 デグサ アクチエンゲゼルシャフト カルボニル化合物の水素化によるアルコールの製法
JP2012240914A (ja) * 2011-05-13 2012-12-10 Tokyo Institute Of Technology プロピレンの製造方法
JP2012240913A (ja) * 2011-05-13 2012-12-10 Tokyo Institute Of Technology 炭素数３以上の含酸素化合物の製造方法

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