WO2014203601A1 - Procédé de régénération du catalyseur pour une réaction d'hydrogénation, et procédé de production d'hydrure d'alcool polyhydrique - Google Patents

Procédé de régénération du catalyseur pour une réaction d'hydrogénation, et procédé de production d'hydrure d'alcool polyhydrique Download PDF

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WO2014203601A1
WO2014203601A1 PCT/JP2014/060393 JP2014060393W WO2014203601A1 WO 2014203601 A1 WO2014203601 A1 WO 2014203601A1 JP 2014060393 W JP2014060393 W JP 2014060393W WO 2014203601 A1 WO2014203601 A1 WO 2014203601A1
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catalyst
hydrogenation reaction
polyhydric alcohol
reaction
regenerating
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PCT/JP2014/060393
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English (en)
Japanese (ja)
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平井雄一郎
梶川泰照
内田敬之
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株式会社ダイセル
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Priority to JP2015522616A priority Critical patent/JP6351589B2/ja
Priority to CN201480031623.3A priority patent/CN105263625A/zh
Publication of WO2014203601A1 publication Critical patent/WO2014203601A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • 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
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/656—Manganese, technetium or rhenium
    • B01J23/6567—Rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B01J23/90—Regeneration or reactivation
    • B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B01J23/90—Regeneration or reactivation
    • B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/02—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
    • B01J38/52—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids oxygen-containing
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to a method for regenerating a hydrogenation catalyst for regenerating the catalytic activity of a poisoned catalyst, and a method for producing a hydride of a polyhydric alcohol including a step of regenerating the catalyst by the regeneration method.
  • biomass eg, cellulose, glucose, vegetable oil, etc.
  • biomass eg, cellulose, glucose, vegetable oil, etc.
  • the plant that is the source of biomass absorbs carbon dioxide by photosynthesis during its growth process, and the amount of carbon dioxide absorbed by the combustion of chemical products is offset by the amount of carbon dioxide absorbed.
  • a compound having 2 carbon atoms typified by ethylene among raw materials for chemical products can be produced by dehydration of bioethanol.
  • compounds having 3 carbon atoms such as propylene, 1,2-propanediol, 1,3-propanediol can be produced by hydrocracking and dehydrating glycerin produced as a by-product during biodiesel production.
  • biomass-derived raw materials for example, erythritol and the like
  • compounds having 4 carbon atoms for example, alcohols having 4 carbon atoms
  • the inventors of the present invention use glycerin or erythritol as a raw material and react with hydrogen in the presence of a hydrogenation reaction catalyst (a catalyst containing iridium supported on a support and rhenium supported on a support). It has been found that alcohols having a number 3 and alcohols having a carbon number 4 can be produced. However, there is a problem that the catalyst used in the above reaction is poisoned by a poisoning substance such as a sulfur component contained in the above raw material and deactivated, and the target product cannot be obtained after repeated use. It became clear that it would occur.
  • a hydrogenation reaction catalyst a catalyst containing iridium supported on a support and rhenium supported on a support.
  • the above-described method has a demerit that, by performing high-temperature firing of the catalyst, sublimable rhenium oxide in the catalyst is sublimated, and the metal in the catalyst is reduced.
  • selectivity for example, selectivity of 1,3-propanediol when glycerin is used
  • an object of the present invention is a method for regenerating a poisoned hydrogenation reaction catalyst used in the reaction of a polyhydric alcohol and hydrogen, which increases the complicated steps and reduces the metal in the catalyst.
  • An object of the present invention is to provide a method for regenerating a catalyst for a hydrogenation reaction that can restore catalyst activity to a high level while maintaining high selectivity without causing it.
  • Another object of the present invention is to regenerate the hydrogenation reaction catalyst by the regeneration method, and to produce a polyhydric alcohol hydride with excellent productivity using the regenerated hydrogenation reaction catalyst. It is to provide a method.
  • the present inventors have developed a poisoned hydrogenation reaction catalyst used in the production of a hydride of a polyhydric alcohol by reacting a polyhydric alcohol with hydrogen. It was found that the catalyst activity can be recovered to a high level while maintaining high selectivity without causing complicated process increase and reduction of metal in the catalyst by applying specific regeneration treatment. . Further, it has been found that when a reaction between a polyhydric alcohol and hydrogen is carried out in the presence of a hydrogenation reaction catalyst regenerated by the above method, a hydride of a polyhydric alcohol can be produced with excellent productivity. The present invention has been completed based on these findings.
  • the present invention is a method for regenerating a hydrogenation reaction catalyst poisoned by a poisoning substance, which is used when a polyhydric alcohol hydride is produced by reacting a polyhydric alcohol with hydrogen.
  • a method for regenerating a hydrogenation reaction catalyst is provided, wherein the catalyst for hydrogenation reaction is subjected to one or both of the following regeneration processes (1) and (2).
  • the hydrogenation reaction catalyst comprises at least one metal selected from the group consisting of cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, iridium, and platinum, and molybdenum, tungsten, and rhenium.
  • a method for regenerating the hydrogenation reaction catalyst which is a solid catalyst containing at least one of at least one metal selected from the group.
  • the poisoning substance is an inorganic compound containing at least one metal selected from the group consisting of sodium, potassium, iron, nickel, cobalt, manganese, chromium, and molybdenum, or nitrogen, sulfur, oxygen, and phosphorus
  • a method for regenerating the hydrogenation reaction catalyst which is an organic compound containing at least one atom selected from the group consisting of:
  • the present invention regenerates the hydrogenation reaction catalyst by the hydrogenation reaction catalyst regeneration method, and reacts the polyhydric alcohol with hydrogen in the presence of the regenerated hydrogenation reaction catalyst.
  • a method for producing a hydride of a polyhydric alcohol characterized by producing a hydride of a polyhydric alcohol.
  • a method for regenerating a hydrogenation reaction catalyst poisoned by a poisoning substance, which is used when a polyhydric alcohol and hydrogen are reacted to produce a hydride of the polyhydric alcohol A method for regenerating a hydrogenation reaction catalyst, comprising subjecting the hydrogenation reaction catalyst to one or both of the following regeneration treatment (1) and regeneration treatment (2).
  • the hydrogenation reaction catalyst is at least one metal selected from the group consisting of cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, iridium and platinum, and molybdenum and tungsten.
  • the hydrogenation reaction catalyst is a catalyst containing at least a carrier, iridium supported on the carrier, and rhenium supported on the carrier.
  • the carrier is silica (SiO 2 ), titania (TiO 2 ), zirconia (ZrO 2 ), alumina (Al 2 O 3 ), magnesia (MgO), or a composite of two or more of these inorganic oxides.
  • the poisonous substance is an inorganic compound containing at least one metal selected from the group consisting of sodium, potassium, iron, nickel, cobalt, manganese, chromium, and molybdenum, or nitrogen, sulfur, oxygen, and
  • the organic solvent in the regeneration treatment (1) is benzene, toluene, xylene, ethylbenzene, diethyl ether, dimethoxyethane, tetrahydrofuran, dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, isopropyl acetate, acetic acid.
  • At least one organic solvent selected from the group consisting of butyl, N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, propionitrile, benzonitrile, methanol, ethanol, isopropyl alcohol (isopropanol), and butanol A method for regenerating a hydrogenation reaction catalyst according to any one of [1] to [10]. [12] Any one of [1] to [11], wherein the organic solvent in the regeneration treatment (1) is at least one organic solvent selected from the group consisting of methanol, ethanol, isopropyl alcohol (isopropanol), and butanol. A method for regenerating a catalyst for a hydrogenation reaction as described in 1.
  • the method of cleaning the hydrogenation reaction catalyst in the regeneration process (1) is a method of cleaning without removing the hydrogenation reaction catalyst from the reactor. Of regenerating a catalyst for hydrogenation reaction.
  • a flow rate when flowing one or both of water and an organic solvent (referred to as a cleaning solution) in the regeneration treatment (1) is 0.5 to 5.0 hr ⁇ as a liquid space velocity (LHSV). 1.
  • the cleaning temperature is 0 to 250 ° C.
  • the total cleaning time is 1 to 12 hours
  • the cleaning is performed in an air atmosphere or a nitrogen atmosphere
  • the number of cleanings is 1 to 10 [1] to [13 ]
  • the regeneration method of the catalyst for hydrogenation reaction in any one of.
  • the flow rate of the gas containing nitrogen in the regeneration process (2) is 200 to 600 hr ⁇ 1 as the space velocity (SV), the total heating time of the hydrogenation reaction catalyst is 0.5 to 48 hours, The method for regenerating a hydrogenation reaction catalyst according to any one of [1] to [16], wherein the number of times is 1 to 10.
  • the polyhydric alcohol is ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, pentanediol, 1,6-hexane.
  • the hydride of the polyhydric alcohol includes a monovalent alcohol having 3 carbon atoms, a divalent alcohol having 3 carbon atoms, a monovalent alcohol having 4 carbon atoms, a divalent alcohol having 4 carbon atoms, and carbon.
  • the reaction between the polyhydric alcohol and hydrogen in the method for producing a hydride of the polyhydric alcohol reacts with the liquid polyhydric alcohol and hydrogen in the presence of a catalyst for the hydrogenation reaction after regeneration, which is a solid.
  • the concentration of polyhydric alcohol is 5 to 100% by weight.
  • the hydrogenation reaction catalyst is regenerated by the method for regenerating a hydrogenation reaction catalyst according to any one of [1] to [23], and a polyhydric alcohol is obtained in the presence of the regenerated hydrogenation reaction catalyst.
  • a method for producing a hydride of a polyhydric alcohol comprising reacting hydrogen with hydrogen to produce a hydride of the polyhydric alcohol.
  • the method for regenerating a hydrogenation reaction catalyst according to the present invention has the above-described configuration, the catalyst activity can be recovered to a high level while maintaining high selectivity of the catalyst. Moreover, the increase of a complicated process is not required. Furthermore, since it is not necessary to heat at a very high temperature as in the case of calcination, no chemical reaction such as oxidation / reduction is involved, and no change or reduction of the metal in the catalyst occurs. As a result, the problem of catalyst poisoning due to poisoning substances such as sulfur compounds can be solved, and the catalyst can be used continuously for 1000 hours or more.
  • the method for regenerating a catalyst for a hydrogenation reaction of the present invention (sometimes simply referred to as “the method for regenerating a catalyst of the present invention”) reacts a polyhydric alcohol and hydrogen to produce a hydride of the polyhydric alcohol.
  • a method for regenerating a hydrogenation reaction catalyst (polyhydric alcohol hydrogenation reaction catalyst) poisoned by a poisoning substance, which is used at the time, wherein the hydrogenation reaction catalyst is subjected to the following regeneration treatment ( It is a method characterized by being attached to one or both of the reproduction processing 1) and the reproduction processing (2).
  • the catalyst for hydrogenation reaction to be regenerated in the catalyst regeneration method of the present invention is poisoned by a poisoning substance used when a hydride of the polyhydric alcohol is produced by reacting a polyhydric alcohol with hydrogen. It is a catalyst for hydrogenation reaction.
  • the hydrogenation reaction catalyst include known or conventional hydrogenation reaction catalysts that can be used for the reaction (hydrogenation reaction) between the above-described polyhydric alcohol and hydrogen, and are not particularly limited. At least one metal selected from the group consisting of nickel, copper, zinc, ruthenium, rhodium, palladium, iridium, and platinum (sometimes referred to as “metal (1)”), and molybdenum, tungsten, and rhenium.
  • a solid catalyst containing one or both of at least one metal selected from the group (sometimes referred to as “metal (2)”).
  • the metal (1) usually exhibits a function of activating hydrogen
  • the metal (2) exhibits a function of activating a substrate (polyhydric alcohol).
  • the solid catalyst is particularly preferably a solid catalyst containing metal (1) and metal (2).
  • a solid catalyst containing at least iridium as the metal (1) and rhenium as the metal (2) is particularly preferable in that the reactivity and selectivity in the hydrogenation reaction are excellent. More preferably, it is a catalyst (solid catalyst) containing at least a carrier, iridium supported on the carrier, and rhenium supported on the carrier.
  • a catalyst containing at least the above-mentioned carrier, iridium supported on the carrier, and rhenium supported on the carrier may be particularly referred to as “the catalyst of the present invention”.
  • the catalyst of the present invention will be specifically described.
  • the hydrogenation reaction catalyst in the catalyst regeneration method of the present invention is not limited to the catalyst of the present invention.
  • the iridium and rhenium in the catalyst of the present invention only have to be supported on the carrier, and the form (state) is not particularly limited. Although it does not specifically limit as a form of iridium and rhenium, For example, forms, such as a simple substance, a salt, an oxide, a hydroxide, a complex, are mentioned, respectively.
  • a known or conventional carrier used as a catalyst carrier can be used, and is not particularly limited.
  • an inorganic carrier such as an inorganic oxide or activated carbon; an ion exchange resin or the like
  • An organic substance carrier etc. are mentioned.
  • an inorganic oxide is preferable from the viewpoint of excellent catalytic activity.
  • the inorganic oxide include silica (SiO 2 ), titania (TiO 2 ), zirconia (ZrO 2 ), alumina (Al 2 O 3 ), magnesia (MgO), and a composite of two or more of these inorganic oxides.
  • Body for example, zeolite etc.
  • zeolite etc. are mentioned.
  • silica (SiO 2 ) and zeolite are particularly preferable in terms of excellent catalytic activity.
  • one type of carrier can be used alone, or two or more types can be used in combination.
  • iridium and rhenium may be supported on the same carrier or may be supported on different carriers. Among these, iridium and rhenium are preferably supported on the same carrier.
  • the specific surface area of the carrier is not particularly limited, but metals such as iridium and rhenium can be arranged in a highly dispersed state, aggregation of the metal can be suppressed, and catalytic activity per unit weight can be improved.
  • metals such as iridium and rhenium can be arranged in a highly dispersed state, aggregation of the metal can be suppressed, and catalytic activity per unit weight can be improved.
  • 50 m 2 / g or more for example, 50 to 1500 m 2 / g, preferably 100 to 1000 m 2 / g
  • the specific surface area of the carrier is less than the above range, the catalytic activity per unit weight tends to decrease.
  • the pore diameter of the carrier is not particularly limited, but metals such as iridium and rhenium can be arranged in a highly dispersed manner, and aggregation of the metal can be suppressed, and the catalytic activity per unit weight can be improved. In this respect, 1 to 100 nm is preferable, and 5 to 70 nm is more preferable.
  • the average particle size of the carrier is not particularly limited, but is preferably from 100 to 10,000 ⁇ m, more preferably from 1000 to 10,000 ⁇ m, in view of reactivity and not accompanied by excessive pressure loss when the reaction is carried out in a continuous flow mode. 10,000 ⁇ m.
  • the shape of the carrier may be any of powder, granule, molding (molded body) and the like, and is not particularly limited.
  • the amount of iridium supported on the carrier is not particularly limited, but is preferably about 0.01 to 50% by weight, more preferably about 0.01 to 20% by weight, based on the total amount of iridium and the carrier (100% by weight). More preferably, it is about 0.5 to 15% by weight, particularly preferably about 1.0 to 10% by weight.
  • the amount of iridium supported is 0.01% by weight or more, the conversion of polyhydric alcohol tends to be further improved.
  • the amount of iridium supported is 50% by weight or less, it tends to be economically advantageous.
  • the method for supporting iridium on the carrier is not particularly limited, and iridium can be supported on the carrier by a known or conventional supporting method.
  • the carrier can be supported by a method of impregnating a carrier with an iridium-containing solution (for example, an aqueous solution of chloroiridic acid), and then drying and then firing.
  • the amount of iridium supported can be controlled by adjusting the concentration of the iridium-containing solution, the impregnation of the carrier, and the number of times the drying treatment is applied.
  • the temperature at which the solution containing iridium is impregnated and the temperature at which the carrier impregnated with the solution is dried are not particularly limited.
  • the method for supporting rhenium on the carrier is not particularly limited, and rhenium can be supported on the carrier by a known or conventional supporting method. Specifically, for example, it can be supported by a method of impregnating a carrier with a solution containing rhenium (for example, an aqueous solution of ammonium perrhenate), then drying and then firing.
  • a solution containing rhenium for example, an aqueous solution of ammonium perrhenate
  • rhenium for example, an aqueous solution of ammonium perrhenate
  • the method of baking etc. are mentioned.
  • the temperature at which the solution containing rhenium is impregnated and the temperature at which the carrier impregnated with the solution is dried are not particularly limited.
  • a method of supporting iridium and rhenium on the carrier for example, a method of impregnating the carrier with a solution containing iridium and rhenium, drying, and then firing is also included.
  • the temperature (firing temperature) at which the support after impregnating and drying the solution containing iridium and the solution containing rhenium (or the solution containing iridium and rhenium) is not particularly limited.
  • 300 to 750 ° C. is preferable, more preferably 380 to 650 ° C., still more preferably 400 to 600 ° C., and particularly preferably 450 to 550 ° C.
  • the atmosphere at the time of baking is not limited to air
  • the ratio of iridium and rhenium (molar ratio, metal conversion) [iridium / rhenium] in the catalyst of the present invention is not particularly limited, but is preferably 50/1 to 1/6 from the viewpoint of the conversion of polyhydric alcohol, more The ratio is preferably 4/1 to 1/4, and more preferably 3/1 to 1/3.
  • the catalyst of this invention may contain platinum, rhodium, cobalt, palladium, nickel, molybdenum, tungsten, manganese etc. other than iridium and rhenium as a metal component, for example.
  • the average particle size of the hydrogenation reaction catalyst is not particularly limited, but is not reactive and does not involve excessive pressure loss when the reaction is carried out in a continuous flow mode. 100 to 10000 ⁇ m, more preferably 1000 to 10000 ⁇ m.
  • the shape of the hydrogenation reaction catalyst is not particularly limited, and examples thereof include powder, granular, and molded (molded body).
  • the method for regenerating a catalyst of the present invention comprises a catalyst used for producing a hydride of a polyhydric alcohol by reacting the hydrogenation reaction catalyst (particularly the catalyst of the present invention) with a polyhydric alcohol and hydrogen.
  • a catalyst used for producing a hydride of a polyhydric alcohol by reacting the hydrogenation reaction catalyst (particularly the catalyst of the present invention) with a polyhydric alcohol and hydrogen.
  • the catalyst for hydrogenation reaction poisoned by a toxic substance has its catalytic activity significantly reduced or deactivated.
  • the poisoning substance include various known or commonly used poisoning substances that poison the hydrogenation reaction catalyst, and are not particularly limited.
  • sodium, potassium, iron, nickel, cobalt, manganese, chromium, and Inorganic compounds containing at least one metal selected from the group consisting of molybdenum; organic compounds containing at least one atom selected from the group consisting of nitrogen, sulfur, oxygen, and phosphorus are generally used.
  • the hydrogenation reaction catalyst is the catalyst of the present invention, in particular, long-chain fatty acids; metal salts; sulfur-containing compounds such as thiols, thioethers, sulfur-containing aromatic compounds (for example, thiophene); amines It is easily poisoned by poisoning substances such as nitrogen-containing compounds.
  • the poisoning substance that poisons the hydrogenation reaction catalyst is regenerated (1) or It is surmised that the regeneration process (2) surprisingly and efficiently desorbs from the hydrogenation reaction catalyst.
  • the used hydrogenation reaction catalyst is subjected to either or both of regeneration treatment (1) and regeneration treatment (2).
  • the regeneration treatment includes reacting polyhydric alcohol and hydrogen in a reactor, and then components other than the hydrogenation reaction catalyst (after use) (polyhydric alcohol, polyhydric alcohol hydride, solvent, etc.) Is preferably taken out from the reactor and then performed in this reactor in terms of preventing an increase in complicated steps, but is not particularly limited.
  • the regeneration treatment (1) is a treatment for washing the hydrogenation reaction catalyst with one or both of water and an organic solvent (hereinafter sometimes collectively referred to as “cleaning liquid”).
  • the organic solvent organic solvent
  • organic solvent may be a known or commonly used organic solvent, and is not particularly limited.
  • aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; diethyl ether, dimethoxyethane, Ethers such as tetrahydrofuran and dioxane; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate, isopropyl acetate, and butyl acetate; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; Nitriles such as acetonitrile, propionitrile, and benzonitrile; alcohols such as methanol, ethanol, isopropyl alcohol (isopropanol), butanol, and the like.
  • aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene
  • alcohol is preferable as the organic solvent.
  • cleaning liquid only any one of water and an organic solvent can also be used, and both can also be used.
  • water and an organic solvent it can also use in the form of the mixed solution which mixed both, and can also use both separately.
  • the organic solvent can also be used individually by 1 type, and can also be used in combination of 2 or more type.
  • the method for washing the hydrogenation reaction catalyst in the regeneration treatment (1) is not particularly limited.
  • the washing solution is continuously or intermittently passed through the reactor containing the hydrogenation reaction catalyst;
  • Various methods such as a method in which the hydrogenation reaction catalyst and the cleaning liquid are put in and stirred; a method in which the hydrogenation reaction catalyst taken out from the reactor is immersed in a container containing the cleaning liquid are included.
  • the amount of the cleaning liquid used in the regeneration process (1) can be appropriately selected according to the cleaning method and the like, and is not particularly limited.
  • the flow rate when the cleaning liquid is circulated in the reactor can be set as appropriate and is not particularly limited.
  • the liquid space velocity (LHSV) is preferably 0.5 to 5.0 hr ⁇ 1 , more Preferably, it is 1.2 to 3.0 hr ⁇ 1 .
  • the washing temperature in the regeneration treatment (1) (for example, the temperature of the washing liquid to be circulated, the temperature for stirring the hydrogenation reaction catalyst and the washing liquid) is not particularly limited, but is preferably 0 to 250 ° C., more preferably 20 to 200 ° C., more preferably 50 to 160 ° C. By controlling the washing temperature within the above range, there is a tendency that the catalytic activity of the hydrogenation reaction catalyst can be recovered more efficiently.
  • the cleaning temperature can be controlled so as to be always constant (substantially constant) during the cleaning, or can be controlled to change stepwise or continuously.
  • the cleaning time in the regeneration treatment (1) (for example, the time for circulating the cleaning liquid, the time for adding the hydrogenation reaction catalyst and the cleaning liquid and stirring) is not particularly limited, and can be set as appropriate.
  • the total washing time in the regeneration treatment (1) of the catalyst regeneration method of the present invention can be appropriately selected from the range of 1 to 12 hours. By controlling the total washing time within the above range, there is a tendency that the catalytic activity of the hydrogenation reaction catalyst can be recovered more efficiently. In particular, the longer the total cleaning time, the greater the catalyst regeneration effect.
  • the pressure at the time of washing in the regeneration treatment (1) is not particularly limited, and the washing can be performed at normal pressure, or under pressure or under reduced pressure.
  • washing is preferably performed under pressure.
  • the cleaning in the regeneration treatment (1) can be performed in various atmospheres such as an air atmosphere and a nitrogen atmosphere, and is not particularly limited.
  • the number of washings in the regeneration process (1) when regeneration is performed in a batch reactor can be appropriately set and is not particularly limited, but is preferably 1 to 10 times, more preferably 1 to 3 times.
  • cleaning may be the same and may differ.
  • the hydrogenation reaction catalyst after washing in the regeneration treatment (1) can be dried by a known or conventional method (for example, a heating method or the like).
  • the regeneration process (2) is a process in which the hydrogenation reaction catalyst is heated to 80 to 300 ° C. under the flow of a gas containing nitrogen (sometimes referred to as “nitrogen-containing gas”).
  • the nitrogen-containing gas is not particularly limited, and examples thereof include nitrogen and a mixed gas containing nitrogen (for example, air). Of these, nitrogen is preferable.
  • Velocity of the nitrogen-containing gas is not particularly limited, for example, as a space velocity (SV), preferably 200 ⁇ 600hr -1, more preferably 300 ⁇ 500 hr -1.
  • SV space velocity
  • the temperature of the heat treatment of the hydrogenation reaction catalyst in the regeneration treatment (2) may be 80 to 300 ° C., and is not particularly limited, but is preferably 120 to 200 ° C. By setting the temperature of the heat treatment to 80 ° C. or higher, the catalytic activity of the hydrogenation reaction catalyst tends to be more efficiently recovered. On the other hand, by setting the temperature of the heat treatment to 300 ° C. or less, sublimation of metal components such as rhenium oxide is suppressed, and a decrease in catalyst activity tends to be further suppressed. Note that the temperature of the heat treatment can be controlled to be constant (substantially constant) during the heat treatment, or can be controlled to change stepwise or continuously.
  • the heat treatment means in the regeneration process (2) can be appropriately selected from known or conventional heating means.
  • the heat treatment time (heating time) of the hydrogenation reaction catalyst in the regeneration treatment (2) is not particularly limited, and can be appropriately set according to, for example, the degree of decrease in the catalyst activity of the hydrogenation reaction catalyst.
  • the total heating time in the regeneration process (2) of the catalyst regeneration method of the present invention can be appropriately selected from a range of 0.5 to 48 hours, for example. By controlling the total heating time within the above range, the catalytic activity of the hydrogenation reaction catalyst tends to be more efficiently recovered.
  • the heat treatment of the hydrogenation reaction catalyst in the regeneration process (2) can be carried out in one stage, or can be carried out in two or more stages.
  • the number of times of the heat treatment of the hydrogenation reaction catalyst in the regeneration treatment (2) is not particularly limited and can be set as appropriate, preferably 1 to 10 times, more preferably 1 to 3 times. Note that when two or more heat treatments are performed, the conditions of each heat treatment may be the same or different.
  • either the regeneration process (1) or the regeneration process (2) may be performed, or both the regeneration process (1) and the regeneration process (2) may be performed. it can.
  • both the reproduction process (1) and the reproduction process (2) are performed, the time sequence of both reproduction processes is not particularly limited, and can be implemented in combination as appropriate.
  • the hydrogenation reaction catalyst (regenerated catalyst) regenerated by the catalyst regeneration method of the present invention is not particularly limited, but the production of the hydride that generates a hydride of a polyhydric alcohol by the reaction of the polyhydric alcohol and hydrogen. Preferably used in the process. Since the regenerated catalyst has been recovered to a sufficiently high catalytic activity level, according to the above production method, a hydride of a polyhydric alcohol can be produced with excellent productivity.
  • the method for producing a hydride of a polyhydric alcohol of the present invention comprises regenerating a hydrogenation reaction catalyst by the above-described catalyst regeneration method of the present invention, and regenerating the hydrogenation reaction catalyst (particularly, the catalyst of the present invention).
  • a polyhydric alcohol hydride is produced by reacting a polyhydric alcohol with hydrogen in the presence. That is, the method for producing a hydride of a polyhydric alcohol of the present invention comprises a step of regenerating a catalyst (hereinafter sometimes referred to as “regeneration step”) and a step of reacting a polyhydric alcohol and hydrogen (hereinafter referred to as “reaction”).
  • the step of regenerating the hydrogenation reaction catalyst can be performed according to the method described in the above section ⁇ Method for Regenerating Hydrogenation Reaction Catalyst>.
  • the process (reaction process) of reacting polyhydric alcohol and hydrogen will be described.
  • the hydrogenation reaction catalyst used in the reaction step in the method for producing a hydride of a polyhydric alcohol of the present invention is a hydrogenation reaction catalyst regenerated in the regeneration step (particularly, the catalyst of the present invention). .
  • the hydrogenation reaction catalyst may be reduced as necessary.
  • the reduction treatment of the hydrogenation reaction catalyst can be carried out by a known or conventional method, and is not particularly limited, and examples thereof include a method of heating in a reducing gas atmosphere such as hydrogen. Conditions such as the heating temperature, heating time, and pressure for the reduction treatment can be appropriately selected and are not particularly limited.
  • Polyhydric alcohol As the polyhydric alcohol used as a raw material (reactant) in the reaction step of the method for producing a hydride of polyhydric alcohol of the present invention, a known or conventional organic compound having two or more hydroxyl groups in the molecule is used.
  • ethylene glycol diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, pentanediol, 1,6 -Hexanediol, neopentyl glycol, cyclohexanedimethanol, glycerin, diglycerin, polyglycerin, trimethylolpropane, erythritol, pentaerythritol, dipentaerythritol, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol S, sugar alcohol and the like.
  • the polyhydric alcohol is preferably a polyhydric alcohol having 3 to 6 carbon atoms (particularly a polyhydric alcohol having 3 to 6 carbon atoms having 3 to 6 hydroxyl groups in the molecule), and particularly derived from biomass. Glycerin and erythritol are preferable from the viewpoint of being possible.
  • a hydride of a polyhydric alcohol obtained by reacting a polyhydric alcohol with hydrogen is a compound in which at least one hydroxyl group of the polyhydric alcohol is substituted with a hydrogen atom.
  • a hydride of a polyhydric alcohol obtained by reacting a polyhydric alcohol with hydrogen is a compound in which at least one hydroxyl group of the polyhydric alcohol is substituted with a hydrogen atom.
  • glycerin glycerol
  • hydrides thereof include monovalent alcohols having 3 carbon atoms (propanol; 1-propanol, 2-propanol) and divalent alcohols having 3 carbon atoms. (Propanediol; 1,3-propanediol, 1,2-propanediol) and the like.
  • propanediol in particular, 1,3-propanediol used as a raw material for polyurethane, polyester, etc.
  • propanediol in particular, 1,3-propanediol used as a raw material for polyurethane, polyester, etc.
  • the hydride thereof has a monohydric alcohol having 4 carbon atoms (butanol; 1-butanol, 2-butanol), a dihydric alcohol having 4 carbon atoms (butane).
  • 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol), and trivalent alcohols having 4 carbon atoms butanetriol; 4-butanetriol, 1,2,3-butanetriol) and the like.
  • butanediol for example, used as a solvent, antifreeze, pharmaceutical, fuel, etc., or a raw material thereof
  • butanetriol for example, a pharmaceutical, explosive, etc., or a raw material thereof
  • the number of carbon atoms is smaller than the number of carbon atoms of polyhydric alcohol produced by the cleavage of the carbon-carbon bond of polyhydric alcohol. This compound is not included.
  • Hydrogen (hydrogen gas) used in the reaction step of the method for producing a hydride of a polyhydric alcohol of the present invention can be used in a state of substantially only hydrogen, or inert such as nitrogen, argon, helium, etc. It can also be used in a state diluted with gas or the like.
  • hydrogen (unreacted hydrogen) recovered from the reaction mixture obtained as a result of the above reaction can be reused.
  • reaction conditions, etc. In the method for producing a hydride of polyhydric alcohol of the present invention, the reaction between polyhydric alcohol and hydrogen is carried out in the presence of a hydrogenation reaction catalyst (particularly, the catalyst of the present invention) after regeneration, which is a solid. It may be a gas-solid two-phase reaction in which a (vaporized) polyhydric alcohol and hydrogen are reacted, or the presence of a catalyst for hydrogenation reaction (particularly, the catalyst of the present invention) after regeneration that is a solid. Below, it may be a gas-liquid solid three-phase reaction in which a liquid polyhydric alcohol and hydrogen are reacted. In particular, from the viewpoint of suppressing the formation of by-products due to the cleavage of the carbon-carbon bond possessed by the polyhydric alcohol, the above reaction is preferably allowed to proceed in a gas-liquid solid three-phase system.
  • the reaction proceeds, for example, by enclosing a raw material liquid containing polyhydric alcohol as an essential component and hydrogen in a reactor and heating in the presence of the hydrogenation reaction catalyst. be able to.
  • the raw material liquid may contain, for example, a solvent such as water or an organic solvent, or may contain substantially no solvent.
  • the organic solvent is not particularly limited, and examples thereof include alcohols such as methanol, ethanol, isopropanol, n-butanol and 2-butanol, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMAc) and the like. Examples include polar organic solvents.
  • the raw material liquid preferably contains at least water as a solvent from the viewpoint of excellent reactivity and easy handling and disposal.
  • the concentration of the polyhydric alcohol in the raw material liquid is not particularly limited, but is preferably 5 to 100% by weight, more preferably 8 to 90% by weight, and still more preferably. It is 10 to 90% by weight, particularly preferably 15 to 80% by weight.
  • the raw material liquid may contain other components (for example, alcohols and the like) as long as the effects of the present invention are not impaired.
  • the raw material liquid contains, for example, impurities derived from the raw material of polyhydric alcohol (for example, long-chain fatty acids, metal salts, sulfur-containing compounds such as thiols and thioethers, nitrogen-containing compounds such as amines, etc.).
  • the above raw material liquid is not particularly limited, but can be obtained by uniformly mixing a polyhydric alcohol with a solvent and other components as necessary.
  • a known or conventional stirrer can be used for mixing.
  • the ratio of hydrogen and polyhydric alcohol to be subjected to the above reaction is not particularly limited, and can be appropriately set according to the type of reaction employed.
  • the reaction temperature in the above reaction is not particularly limited, but is preferably 50 to 200 ° C, more preferably 60 to 150 ° C, and further preferably 70 to 130 ° C.
  • the reaction temperature By setting the reaction temperature to 50 ° C. or higher, the reaction rate (conversion rate) of the polyhydric alcohol tends to be further improved.
  • the reaction temperature by setting the reaction temperature to 200 ° C. or lower, the decomposition of the polyhydric alcohol (for example, the cleavage of the carbon-carbon bond) is suppressed, and the hydride of the polyhydric alcohol that is the target compound (for example, glycerin is used).
  • the selectivity of alcohols having 3 carbon atoms for example, when erythritol is used, the selectivity for alcohols having 4 carbon atoms tends to be improved.
  • the reaction temperature may be controlled to be always constant (substantially constant) in the above reaction, or may be controlled to change stepwise or continuously.
  • reaction time in the above reaction is not particularly limited, and can be set as appropriate according to the reaction format employed.
  • the reaction pressure (hydrogen pressure in the above reaction) in the above reaction is not particularly limited, but is preferably 1 to 50 MPa, more preferably 3 to 30 MPa, and further preferably 5 to 15 MPa. .
  • the reaction pressure is preferably 1 to 50 MPa, more preferably 3 to 30 MPa, and further preferably 5 to 15 MPa.
  • the reaction rate (conversion rate) of the polyhydric alcohol tends to be further improved.
  • the reaction pressure exceeds 50 MPa, the reactor needs to have a high pressure resistance, and thus the production cost tends to increase.
  • reaction between polyhydric alcohol and hydrogen can be carried out in any format such as a batch format, a semi-batch format, or a continuous flow format.
  • a process of separating and recovering and recycling unreacted polyhydric alcohol after the above reaction is employed. May be. If this recycling process is employed, the amount of polyhydric alcohol hydride produced when a predetermined amount of polyhydric alcohol is used can be increased.
  • a known or conventional reactor can be used as a reactor, for example, a batch reactor, a fluidized bed reactor, a fixed bed reactor or the like is used. it can.
  • a trickle bed reactor can be used as the fixed bed reactor.
  • a trickle bed reactor has a catalyst packed bed filled with a solid catalyst inside, and a liquid (raw material liquid in the above reaction) and a gas (hydrogen in the above reaction) together with the catalyst packed bed.
  • the reactor (fixed bed continuous reaction device) is of a type that circulates in a downward flow (gas-liquid downward parallel flow) from above the reactor.
  • the regeneration step and the reaction step can be performed in separate lines, or can be performed as a series of steps (in-line).
  • the method for producing a hydride of a polyhydric alcohol of the present invention may include other steps as necessary in addition to the regeneration step and the reaction step.
  • Other steps include, for example, a step of preparing and purifying the raw material liquid before supplying the raw material liquid and hydrogen to the reactor, and a reaction mixture discharged (outflowed) from the reactor (for example, polyhydric alcohol, hydrogen, And a mixture containing a hydride of a polyhydric alcohol) and the like.
  • these processes may be implemented in a line different from the above reaction process, or may be implemented as a series of processes (in-line).
  • the hydride obtained by the method for producing a hydride of a polyhydric alcohol of the present invention is obtained by a known or conventional method (for example, distillation, adsorption, ion exchange, crystallization, extraction, etc.). Can be purified.
  • SiO 2 Silicon dioxide (SiO 2 ) (trade name “CARBECT Q-15”, manufactured by Fuji Silysia Chemical Ltd., pore size: 15 nm) was used as a catalyst support.
  • an aqueous solution of chloroiridate (H 2 IrCl 6 ) prepared so that the iridium (Ir) concentration is 4.47% by weight is added dropwise to wet the entire carrier, and then the carrier is cooled to 110 ° C. And dried for 3 hours. Then, the dropping and drying of the chloroiridium acid aqueous solution were repeated and the iridium was supported so as to be 4% by weight with respect to SiO 2 .
  • the ammonium perrhenate (NH 4 ReO 4 ) aqueous solution prepared so as to have a rhenium (Re) concentration of 3% by weight is dropped onto the above carrier (a carrier on which iridium is supported) and dried.
  • Rhenium was supported so that the molar ratio of iridium and rhenium was 1/2 [iridium / rhenium] by repeating in the same manner as dropping and drying of the iridium acid aqueous solution.
  • the dried support was calcined under an air atmosphere (in the air) at 500 ° C. for 3 hours to prepare an Ir—Re catalyst [Ir—ReO x / SiO 2 ].
  • Example 1 An autoclave (reactor) was charged with 14.5 g of the Ir—Re catalyst obtained in Production Example 1 and 500 g of an aqueous glycerin solution containing 6.4 ppm of sulfur on an element weight basis (glycerin concentration: 80 wt%) at a temperature of 120 ° C. The mixture was stirred at a hydrogen pressure of 12 MPa for 6 hours to carry out a hydrogenation reaction of glycerin. Thereafter, the entire amount of the aqueous solution containing glycerin and hydride of glycerin was withdrawn from the reactor (the Ir-Re catalyst after use is in the reactor).
  • reaction rate conversion rate of glycerin in the following examples and comparative examples is gas chromatography (gas chromatograph apparatus: “GC-2014” (manufactured by Shimadzu Corporation), GC column: TC-WAX, DB. -FFAP, detector: FID).
  • Example 2 An autoclave (reactor) was charged with 14.5 g of the Ir—Re catalyst obtained in Production Example 1 and 500 g of an aqueous glycerin solution (glycerin concentration: 80 wt%) containing 0.8 ppm of sulfur on an element weight basis, at a temperature of 120 ° C. Then, the mixture was stirred at a hydrogen pressure of 12 MPa for 6 hours to perform a hydrogenation reaction of glycerin (first hydrogenation reaction). Thereafter, the entire amount of the aqueous solution containing glycerin and hydride of glycerin was withdrawn from the reactor (the Ir-Re catalyst after use is in the reactor).
  • a regeneration treatment was performed in which the Ir-Re catalyst after the second hydrogenation reaction was washed with ultrapure water. Specifically, after removing all components other than the Ir-Re catalyst from the reactor, 500 g of washing water (ultra pure water) was added to the reactor and stirred for 10 minutes at room temperature, and then the entire amount of water was removed. Subsequently, 500 g of washing water (ultra pure water) was put into the reactor and stirred at 200 ° C. for 60 minutes, and then the whole amount of water was extracted three times.
  • washing water ultra pure water
  • a glycerin aqueous solution (glycerin concentration: 80% by weight) having a sulfur content of 0.08 ppm or less was charged into the reactor containing the regenerated (washed) Ir-Re catalyst at a temperature of 120 ° C. and a hydrogen pressure of 12 MPa.
  • the mixture was stirred for 6 hours to carry out a hydrogenation reaction of glycerin (third hydrogenation reaction).
  • the catalytic activity in the third hydrogenation reaction was calculated from the reaction rate (conversion rate) of glycerin in the third hydrogenation reaction, the third time when the catalyst activity in the first hydrogenation reaction was 100% was calculated.
  • the catalytic activity in the hydrogenation reaction was recovered to 69%.
  • Example 3 As in Example 2, after performing the first hydrogenation reaction and the second hydrogenation reaction, the same procedure as in Example 2 was performed except that isopropyl alcohol (IPA) was used instead of water as the cleaning liquid.
  • IPA isopropyl alcohol
  • the catalyst was regenerated. Thereafter, 500 g of a glycerin aqueous solution (glycerin concentration: 80% by weight) having a sulfur content of 0.08 ppm or less was charged into the reactor containing the regenerated (washed) Ir-Re catalyst at a temperature of 120 ° C. and a hydrogen pressure of 12 MPa. The mixture was stirred for 6 hours to carry out a hydrogenation reaction of glycerin (third hydrogenation reaction).
  • a glycerin aqueous solution glycerin concentration: 80% by weight
  • the mixture was stirred for 6 hours to carry out a hydrogenation reaction of glycerin (third hydrogenation reaction).
  • Example 4 The same operation as in Example 3 was performed except that the temperature of the washing treatment at 200 ° C. using isopropyl alcohol was changed to 50 ° C.
  • the catalytic activity in the third hydrogenation reaction was calculated from the reaction rate (conversion rate) of glycerin in the third hydrogenation reaction, the third time when the catalytic activity in the first hydrogenation reaction was 100% was calculated. The catalytic activity in the hydrogenation reaction exceeded 100%, and the catalytic activity was completely recovered.
  • Example 5 In the same manner as in Example 2, the first hydrogenation reaction and the second hydrogenation reaction were performed. Thereafter, a regeneration treatment was performed on the Ir-Re catalyst after the second hydrogenation reaction by heating (drying) under a nitrogen flow. Specifically, the internal temperature of the reactor was set to 160 ° C., and nitrogen was continuously circulated at a flow rate of 160 NL / hour for 12 hours. Thereafter, 500 g of a glycerin aqueous solution (glycerin concentration: 80% by weight) having a sulfur content of 0.08 ppm or less was charged into the reactor containing the regenerated (heated) Ir-Re catalyst at a temperature of 120 ° C. and a hydrogen pressure of 12 MPa.
  • a glycerin aqueous solution glycerin concentration: 80% by weight
  • the mixture was stirred for 6 hours to carry out a hydrogenation reaction of glycerin (third hydrogenation reaction).
  • the catalytic activity in the third hydrogenation reaction was calculated from the reaction rate (conversion rate) of glycerin in the third hydrogenation reaction, the third time when the catalyst activity in the first hydrogenation reaction was 100% was calculated. The catalytic activity in the hydrogenation reaction was recovered to 91%.
  • Example 6 An autoclave (reactor) was charged with 14.5 g of the Ir—Re catalyst obtained in Production Example 1 and 500 g of an aqueous glycerin solution containing 6.4 ppm of sulfur on an element weight basis (glycerin concentration: 80 wt%) at a temperature of 120 ° C. Then, the mixture was stirred at a hydrogen pressure of 12 MPa for 6 hours to perform a hydrogenation reaction of glycerin (first hydrogenation reaction). Thereafter, the entire amount of the aqueous solution containing glycerin and hydride of glycerin was withdrawn from the reactor (the Ir-Re catalyst after use is in the reactor).
  • the Ir-Re catalyst after the second hydrogenation reaction was subjected to a washing treatment with ultrapure water and a heat treatment under air circulation. Specifically, 500 g of washing water (ultra pure water) was put into the reactor and stirred at room temperature for 10 minutes, and the entire amount of water was extracted twice. Subsequently, the internal temperature of the reactor was set to 200 ° C. Then, air was circulated continuously at a flow rate of 150 NL / hour for 24 hours.
  • washing water ultrapure water
  • a glycerin aqueous solution (glycerin concentration: 80% by weight) having a sulfur content of 0.08 ppm or less was charged into the reactor containing the regenerated (washed and heated) Ir-Re catalyst, at a temperature of 120 ° C., and a hydrogen pressure.
  • the mixture was stirred at 12 MPa for 6 hours to carry out a glycerin hydrogenation reaction (third hydrogenation reaction).
  • the catalytic activity in the third hydrogenation reaction was calculated from the reaction rate (conversion rate) of glycerin in the third hydrogenation reaction, the third time when the catalyst activity in the first hydrogenation reaction was 100% was calculated.
  • the catalytic activity in the hydrogenation reaction was recovered to 69%.
  • Comparative Example 1 In the same manner as in Example 6, the first hydrogenation reaction and the second hydrogenation reaction were performed. Thereafter, the Ir—Re catalyst was taken out of the reactor, placed in a firing furnace, and fired (refired) at 500 ° C. for 3 hours. Next, the catalyst after calcination is charged again into the reactor, charged with 500 g of a glycerol aqueous solution (glycerol concentration: 80 wt%) having a sulfur content of 0.08 ppm or less, and stirred at a temperature of 120 ° C. and a hydrogen pressure of 12 MPa for 6 hours. Then, hydrogenation reaction of glycerin (third hydrogenation reaction) was performed.
  • glycerol aqueous solution glycerol concentration: 80 wt% having a sulfur content of 0.08 ppm or less
  • the “activity index” in Table 1 represents the reaction rate (conversion rate) (unit:%) of glycerin at a reaction time of 6 hours.
  • the method for regenerating a hydrogenation reaction catalyst according to the present invention has the above-described configuration, the catalyst activity can be recovered to a high level while maintaining high selectivity of the catalyst. Moreover, the increase of a complicated process is not required. Furthermore, since it is not necessary to heat at a very high temperature as in the case of calcination, no chemical reaction such as oxidation / reduction is involved, and no change or reduction of the metal in the catalyst occurs. As a result, the problem of catalyst poisoning due to poisoning substances such as sulfur compounds can be solved, and the catalyst can be used continuously for 1000 hours or more.

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Abstract

La présente invention concerne un procédé de régénération d'un catalyseur pour des réactions d'hydrogénation, ledit catalyseur étant empoisonné pendant l'utilisation au cours d'une réaction entre un alcool polyhydrique et de l'hydrogène, ledit procédé permettant de restaurer l'activité catalytique du catalyseur à un niveau élevé sans augmenter le nombre de procédés encombrants ni diminuer un métal dans le catalyseur, tout en maintenant une sélectivité élevée. La présente invention concerne aussi un procédé de régénération d'un catalyseur pour des réactions d'hydrogénation, ledit catalyseur étant utilisé dans la production d'un hydrure d'un alcool polyhydrique par une réaction entre l'alcool polyhydrique et l'hydrogène et étant empoisonné par une substance d'empoisonnement. Ce procédé est caractérisé en ce que le catalyseur pour les réactions d'hydrogénation est soumis au traitement de régénération (1) et/ou au traitement de régénération (2) suivant. Traitement de régénération (1): un traitement dans lequel le catalyseur pour les réactions d'hydrogénation est nettoyé par de l'eau et/ou un solvant organique Traitement de régénération (2): un traitement dans lequel le catalyseur pour les réactions d'hydrogénation est chauffé à 80-300°C dans un flux de gaz qui contient de l'azote
PCT/JP2014/060393 2013-06-18 2014-04-10 Procédé de régénération du catalyseur pour une réaction d'hydrogénation, et procédé de production d'hydrure d'alcool polyhydrique WO2014203601A1 (fr)

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JP2018108577A (ja) * 2016-12-28 2018-07-12 栗田工業株式会社 過酸化水素除去方法及び装置
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JP2020172455A (ja) * 2019-04-09 2020-10-22 出光興産株式会社 Ｃ５＋化合物の製造方法及びｃ５＋化合物
JP7253960B2 (ja) 2019-04-09 2023-04-07 出光興産株式会社 Ｃ５＋化合物の製造方法
CN116139879A (zh) * 2023-02-14 2023-05-23 安徽大学 二氧化硅负载铱镍催化剂IrNi/SiO2及其高选择性催化苯甲腈、巴豆醛和苄叉丙酮中的加氢方法和应用
CN116139879B (zh) * 2023-02-14 2024-01-26 安徽大学 二氧化硅负载铱镍催化剂IrNi/SiO2及其高选择性催化苯甲腈、巴豆醛和苄叉丙酮中的加氢方法和应用

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