JPWO2014203601A1 - Method for regenerating catalyst for hydrogenation reaction and method for producing hydride of polyhydric alcohol - Google Patents

Abstract

A method for regenerating a poisoned hydrogenation reaction catalyst used in the reaction of a polyhydric alcohol and hydrogen, with high selectivity without causing an increase in complicated steps and a reduction in metal in the catalyst. A method for regenerating a catalyst for a hydrogenation reaction capable of recovering the catalyst activity to a high level while maintaining the above is provided. A method for regenerating a hydrogenation reaction catalyst poisoned by a poisoning substance, which was used in producing a hydride of the polyhydric alcohol by reacting a polyhydric alcohol with hydrogen, the hydrogenation A method for regenerating a hydrogenation reaction catalyst, characterized in that the reaction catalyst is subjected to either or both of the following regeneration treatment (1) and regeneration treatment (2). Regeneration treatment (1): Treatment regeneration treatment for washing the hydrogenation reaction catalyst with one or both of water and organic solvent (2): The hydrogenation reaction catalyst is 80 to 300 ° C. under the flow of a gas containing nitrogen. Heat treatment

Description

  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 a catalyst by the regeneration method. This application claims the priority of Japanese Patent Application No. 2013-127769 for which it applied to Japan on June 18, 2013, and uses the content here.

  Currently, crude oil is the starting material for chemical products. And a chemical product uses a carbon atom as a main structural component. Looking at the flow of carbon on a global scale, the carbon that was sleeping in the ground as crude oil is brought to the ground as a chemical product and used for various purposes. At that time, carbon becomes carbon dioxide and accumulates in the atmosphere. In addition, there are many chemical products whose purpose of use is combustion, such as gasoline and light oil. Carbon dioxide accumulated in the atmosphere by such a carbon flow causes global warming and is said to cause various harmful effects such as abnormal climate and sea level rise, and reduction of carbon dioxide emissions is screamed. .

  As one of the solutions, it has been proposed to use biomass (for example, cellulose, glucose, vegetable oil, etc.), which is a plant-derived resource, as a starting material for chemical products. This is because 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.

  For example, it is known that compounds having 2 carbon atoms typified by ethylene among raw materials for chemical products can be produced by dehydration of bioethanol. In addition, it is known that 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. (See, for example, Non-Patent Document 1). Furthermore, the induction of biomass-derived raw materials (for example, erythritol and the like) into compounds having 4 carbon atoms (for example, alcohols having 4 carbon atoms) has not yet been put into practical use, but has been studied energetically. It is being advanced.

Yoshinao Nakagawa, et al. "Direct hydrogenolysis of glycerol into 1,3-propanediol over rhenium-modified iridium catalyst", Journal of Catalysis, 2010, 272, p.191-194.

  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.

  As a result of repeated investigations by the present inventors with respect to the above problems, it is possible to recover the catalytic activity of the catalyst and regenerate the catalyst by firing the deactivated catalyst at a high temperature in a firing furnace. I found it. However, this method still has room for improvement mainly in the following two points. That is, in the above method, in addition to the step of firing the catalyst, complicated steps such as a step of removing the catalyst from the reactor, a step of refilling the reactor with the catalyst after the firing, and a step of reducing the catalyst before the hydrogenation reaction Is required, and the number of processes increases. Furthermore, 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. Thus, when the metal in the catalyst is reduced, the active sites are reduced, so that the performance of the catalyst is not completely recovered, and it cannot be reused over and over again. Furthermore, it became clear that the problem that selectivity (for example, selectivity of 1,3-propanediol when glycerin is used) slightly decreases after firing.

Therefore, 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.

  As a result of intensive investigations to solve the above problems, 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.

That is, 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. There,
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).
Regeneration treatment (1): Treatment for washing the hydrogenation reaction catalyst with one or both of water and organic solvent Regeneration treatment (2): The hydrogenation reaction catalyst is heated to 80 to 300 ° C. under the flow of a gas containing nitrogen. Heat treatment

  Further, 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. Provided is 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.

  Further, 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:

  Further, 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. Provided is a method for producing a hydride of a polyhydric alcohol, characterized by producing a hydride of a polyhydric alcohol.

That is, the present invention relates to the following.
[1] 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).
Regeneration treatment (1): Treatment for washing the hydrogenation reaction catalyst with one or both of water and organic solvent Regeneration treatment (2): The hydrogenation reaction catalyst is heated to 80 to 300 ° C. under the flow of a gas containing nitrogen. [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. And a method for regenerating a hydrogenation reaction catalyst according to [1], which is a solid catalyst containing at least one of at least one metal selected from the group consisting of rhenium.
[3] The method for regenerating a hydrogenation reaction catalyst according to [1] or [2], wherein the hydrogenation reaction catalyst is a catalyst containing at least iridium and rhenium.
[4] The hydrogenation reaction according to any one of [1] to [3], wherein the hydrogenation reaction catalyst is a catalyst containing at least a carrier, iridium supported on the carrier, and rhenium supported on the carrier. Of regenerating catalyst for use.
[5] 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 method for regenerating a hydrogenation reaction catalyst according to [4].
[6] The method for regenerating a hydrogenation reaction catalyst according to [4] or [5], wherein the carrier is silica (SiO ₂ ) or zeolite.
[7] The hydrogenation reaction catalyst according to any one of [4] to [6], wherein the support has a specific surface area of 50 m ² / g or more, a pore size of 1 to 100 nm, and an average particle size of 100 to 10,000 μm. Playback method.
[8] The amount of iridium supported on the carrier in the hydrogenation reaction catalyst is 0.01 to 50% by weight relative to the total amount of iridium and the carrier (100% by weight), and the ratio of iridium and rhenium (mol) Ratio, metal conversion) [iridium / rhenium] is 50/1 to 1/6, [4] to [7] The method for regenerating a hydrogenation reaction catalyst according to any one of [4] to [7].
[9] In the hydrogenation reaction catalyst, the method in which rhenium is supported on the same carrier as iridium is impregnated with a solution containing iridium and dried, and the carrier containing rhenium is further impregnated with the solution. The method for regenerating a catalyst for a hydrogenation reaction according to any one of [4] to [8], wherein the catalyst is dried and then calcined.
[10] 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 method for regenerating a hydrogenation reaction catalyst according to any one of [1] to [9], which is an organic compound containing at least one atom selected from the group consisting of phosphorus.
[11] 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.
[13] The method according to any one of [1] to [12], wherein the method for washing the hydrogenation reaction catalyst in the regeneration treatment (1) is a method for washing without removing the hydrogenation reaction catalyst from the reactor. Of regenerating a catalyst for hydrogenation reaction.
[14] 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 in an air atmosphere or a nitrogen atmosphere, and the number of cleanings is 1 to 10 [1] to [13 ] The regeneration method of the catalyst for hydrogenation reaction in any one of.
[15] The hydrogenation according to any one of [1] to [14], wherein the regeneration treatment (2) is a treatment in which the hydrogenation reaction catalyst is heated to 80 to 300 ° C. under the flow of a gas containing nitrogen. A method for regenerating a catalyst for reaction.
[16] The method for regenerating a hydrogenation reaction catalyst according to any one of [1] to [15], wherein the gas containing nitrogen in the regeneration process (2) is nitrogen.
[17] 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, and the heating process. 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.
[18] 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. From diol, neopentyl glycol, cyclohexanedimethanol, glycerin, diglycerin, polyglycerin, trimethylolpropane, erythritol, pentaerythritol, dipentaerythritol, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol S, and sugar alcohol The method for regenerating a hydrogenation reaction catalyst according to any one of [1] to [17], which is at least one selected from the group consisting of:
[19] The method for regenerating a hydrogenation reaction catalyst according to any one of [1] to [18], wherein the polyhydric alcohol is glycerin and / or erythritol.
[20] 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 method for regenerating a hydrogenation reaction catalyst according to any one of [1] to [19], which is at least one selected from the group consisting of trivalent alcohols of formula 4.
[21] The hydrogenation reaction according to any one of [1] to [20], wherein the polyhydric alcohol hydride is at least one selected from the group consisting of propanediol, butanediol, and butanetriol. Catalyst regeneration method.
[22] 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 method for regenerating a hydrogenation reaction catalyst according to any one of [1] to [21], which is a gas-liquid solid three-phase reaction.
[23] In the reaction of polyhydric alcohol and hydrogen in the method for producing a hydride of polyhydric alcohol, the concentration of polyhydric alcohol (polyhydric alcohol content with respect to 100% by weight of the raw material liquid) is 5 to 100% by weight. The method for regenerating a hydrogenation reaction catalyst according to any one of [1] to [22], wherein the reaction temperature is 50 to 200 ° C., and the reaction pressure is 1 to 50 MPa.
[24] The hydrogenation reaction catalyst is regenerated by the hydrogenation reaction catalyst regeneration method according to any one of [1] to [23], and the polyhydric alcohol is present 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.

  Since the method for regenerating a hydrogenation reaction catalyst of the present invention has the above-described configuration, the catalyst activity can be recovered to a high level while maintaining high catalyst selectivity. 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. Furthermore, according to the method of regenerating the hydrogenation reaction catalyst by the above regeneration method and proceeding the reaction between the polyhydric alcohol and hydrogen (polyhydric alcohol hydrogenation reaction) in the presence of the regenerated catalyst, excellent production is achieved. Since a hydride of a polyhydric alcohol can be produced, it is advantageous in terms of cost.

<Method for regenerating catalyst for hydrogenation reaction>
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).
Regeneration treatment (1): Treatment for washing the hydrogenation reaction catalyst with one or both of water and organic solvent Regeneration treatment (2): The hydrogenation reaction catalyst is heated to 80 to 300 ° C. under the flow of a gas containing nitrogen. Heat treatment

[Hydrogenation catalyst]
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. Examples of 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. And a solid catalyst containing one or both of at least one metal selected from the group (sometimes referred to as “metal (2)”). In the solid catalyst, the metal (1) usually exhibits a function of activating hydrogen, and the metal (2) exhibits a function of activating a substrate (polyhydric alcohol). From this point of view, the solid catalyst is particularly preferably a solid catalyst containing metal (1) and metal (2).

  As the catalyst for the hydrogenation reaction, 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. In the present specification, 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”. Hereinafter, the catalyst of the present invention will be specifically described. However, 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 are only required 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.

As the carrier in the catalyst of the present invention, a known or conventional carrier used as a catalyst carrier can be used, and is not particularly limited. For example, 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. As the carrier, an inorganic oxide is preferable from the viewpoint of excellent catalytic activity. Examples of 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.) etc. are mentioned. Among the inorganic oxides, silica (SiO ₂ ) and zeolite are particularly preferable in terms of excellent catalytic activity. In the catalyst of the present invention, one type of carrier can be used alone, or two or more types can be used in combination.

  In the catalyst of the present invention, 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. at point, 50 m ² / g or more (e.g., 50~1500m ² / g, preferably 100~1000m ² / g) are preferable. When 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 100 to 10,000 μm, more preferably 1000 to 1000 μm in terms of reactivity and no excessive pressure loss when the reaction is carried out in a continuous flow mode. 10,000 μm. 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. When the amount of iridium supported is 0.01% by weight or more, the conversion of polyhydric alcohol tends to be further improved. On the other hand, when 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. Specifically, for example, 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. Further, 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 loading 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. In the case where rhenium is supported on the same carrier as iridium, for example, after impregnating the solution containing iridium and drying the carrier, further impregnating the solution containing rhenium and drying, 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.

  Examples of other methods for supporting iridium and rhenium on the carrier include a method of impregnating the carrier with a solution containing iridium and rhenium, drying, and then firing.

  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. In the atmosphere, 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. Moreover, the atmosphere at the time of baking is not limited to air | atmosphere as mentioned above, For example, it can also bake in inert gas atmosphere etc., such as nitrogen and argon.

  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 rate of polyhydric alcohol. Preferably it is 4/1-1/4, More preferably, it is 3/1-1/3.

  In addition, the catalyst of this invention may contain platinum, rhodium, cobalt, palladium, nickel, molybdenum, tungsten, manganese etc. as a metal component other than iridium and rhenium, for example.

  The average particle size of the hydrogenation reaction catalyst (especially the catalyst of the present invention) 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 10,000 μm is preferable, and 1000 to 10,000 μm is more preferable. The shape of the hydrogenation reaction catalyst (particularly, the catalyst of the present invention) 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. Particularly effective when the catalyst for hydrogenation reaction (catalyst for the reduction reaction of polyhydric alcohol) poisoned by a toxic substance has its catalytic activity significantly reduced or deactivated. Is. Examples of the poisoning substance include various known or commonly used poisoning substances that poison the hydrogenation reaction catalyst, and are not particularly limited. For example, 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. In particular, when 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. Although the reason why the catalytic activity of the hydrogenation reaction catalyst is efficiently recovered by the catalyst regeneration method of the present invention is not clear, 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.

[Playback method]
As described above, in the catalyst regeneration method of the present invention, the used hydrogenation reaction catalyst is subjected to either or both of regeneration treatment (1) and regeneration treatment (2). For example, 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.

(Reproduction process (1))
As described above, 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) may be a known or commonly used organic solvent, and is not particularly limited. For example, 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. Among these, alcohol is preferable as the organic solvent. In addition, as said washing | cleaning liquid, only any one of water and an organic solvent can also be used, and both can also be used. Moreover, when using both 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. Moreover, 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. For example, 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. Among these, it is preferable to employ a method of washing without removing the hydrogenation reaction catalyst from the reactor.

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. In addition, the flow rate when the cleaning liquid is circulated in the reactor can be appropriately set and is not particularly limited. For example, the liquid space velocity (LHSV) is preferably 0.5 to 5.0 hr ⁻¹ , more Preferably it is 1.2-3.0 hr < ^-1 >. By controlling the liquid space velocity of the cleaning liquid in the above range, there is a tendency that the catalytic activity of the hydrogenation reaction catalyst can be recovered more efficiently.

  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 degreeC, More preferably, it is 50-160 degreeC. 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 process (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. For example, the total washing time in the regeneration process (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 can be performed under pressure or reduced pressure. For example, when washing is performed at a temperature equal to or higher than the boiling point of the washing liquid, washing is preferably performed under pressure.

  The cleaning in the regeneration process (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 treatment (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. In addition, when performing 2 times or more of washing | cleaning, the conditions of each washing | cleaning may be the same and may differ.

  In the regeneration treatment (1), the hydrogenation reaction catalyst after washing can be dried by a known or conventional method (for example, a heating method or the like).

(Reproduction process (2))
As described above, the regeneration process (2) is a process of heating the hydrogenation reaction catalyst 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.

The flow rate of the nitrogen-containing gas is not particularly limited. For example, the space velocity (SV) is preferably 200 to 600 hr ⁻¹ , more preferably 300 to 500 hr ⁻¹ . By controlling the space velocity of the nitrogen-containing gas within the above range, there is a tendency that the catalytic activity of the hydrogenation reaction catalyst can be recovered more efficiently.

  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 time (heating time) for the heat treatment 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. For example, the total heating time in the regeneration process (2) of the catalyst regeneration method of the present invention can be appropriately selected from the 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 treatment (2) can be performed in one stage, or can be performed in two or more stages.

  The frequency | count of the heat processing of the catalyst for hydrogenation reaction in a regeneration process (2) is not specifically limited, It can set suitably, 1-10 times are preferable, More preferably, it is 1-3 times. Note that when two or more heat treatments are performed, the conditions of each heat treatment may be the same or different.

  In the catalyst regeneration method of the present invention, 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. When 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.

<Method for Producing Polyhydric Alcohol Hydride of the Present Invention>
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”). In some cases, it may be referred to as a “process”. Among these, the step of regenerating the hydrogenation reaction catalyst (regeneration step) can be performed according to the method described in the above section <Method for Regenerating Hydrogenation Reaction Catalyst>. Hereinafter, the process (reaction process) of reacting polyhydric alcohol and hydrogen will be described.

[Hydrogenation catalyst]
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). . Before the reaction between the polyhydric alcohol and hydrogen, 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. For example, 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. Among these, 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.

[Hydride of polyhydric alcohol]
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. For example, when glycerin (glycerol) is used as the polyhydric alcohol, as its hydride, a monovalent alcohol having 3 carbon atoms (propanol; 1-propanol, 2-propanol) and a divalent alcohol having 3 carbon atoms are used. (Propanediol; 1,3-propanediol, 1,2-propanediol) and the like. In particular, by using the catalyst of the present invention, propanediol (in particular, 1,3-propanediol used as a raw material for polyurethane, polyester, etc.) tends to be generated with high selectivity. On the other hand, for example, by using erythritol as a polyhydric alcohol, as its hydride, a monovalent alcohol having 4 carbon atoms (butanol; 1-butanol, 2-butanol), a divalent 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. In particular, when the catalyst of the present invention is used, butanediol (for example, used as a solvent, antifreeze, pharmaceutical, fuel, etc. or a raw material thereof) and butanetriol (for example, a pharmaceutical, explosive, etc., or a raw material thereof) Can be generated with high selectivity. In the present specification, in general, in the case of “hydration product of polyhydric alcohol”, the number of carbon atoms is smaller than the number of carbon atoms of polyhydric alcohol generated by the cleavage of the carbon-carbon bond of polyhydric alcohol. This compound is not included.

[hydrogen]
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. In addition, hydrogen (unreacted hydrogen) recovered from the reaction mixture obtained as a result of the above reaction (reaction of polyhydric alcohol and hydrogen) 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 of the polyhydric alcohol, it is preferable to proceed with the above reaction in a gas-liquid solid three-phase system.

  More specifically, 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.

  In addition to the polyhydric alcohol, 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 polyhydric alcohol in the raw material liquid (polyhydric alcohol content with respect to 100% by weight of 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. By setting the concentration of the polyhydric alcohol to 5% by weight or more, the reaction rate (conversion rate) of the polyhydric alcohol tends to be further improved.

  In the above reaction (reaction of polyhydric alcohol and hydrogen), other components may be allowed to coexist within a range not impairing the effects of the present invention. That is, 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.). However, since such impurities may poison the hydrogenation reaction catalyst, it is possible to use raw materials as much as possible by known or conventional methods (for example, distillation, adsorption, ion exchange, crystallization, extraction, etc.). It is preferable to remove from the liquid.

  Although the said raw material liquid is not specifically limited, It is obtained by mixing a polyhydric alcohol, a solvent, and another component uniformly as needed. A known or conventional stirrer can be used for mixing.

  The ratio of hydrogen to polyhydric alcohol to be subjected to the above reaction (reaction between polyhydric alcohol and hydrogen) is not particularly limited, and can be appropriately set according to the reaction type to be employed.

  The reaction temperature in the above reaction (reaction of polyhydric alcohol and hydrogen) is not particularly limited, but is preferably 50 to 200 ° C, more preferably 60 to 150 ° C, and further preferably 70 to 130 ° C. By setting the reaction temperature to 50 ° C. or higher, the reaction rate (conversion rate) of the polyhydric alcohol tends to be further improved. On the other hand, by setting the reaction temperature to 200 ° C. or lower, the decomposition of the polyhydric alcohol (for example, 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). In some cases, 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. Note that 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.

  The reaction time in the above reaction (reaction between a polyhydric alcohol and hydrogen) is not particularly limited, and can be appropriately set according to the reaction format to be employed.

  The reaction pressure (hydrogen pressure in the above reaction) in the above reaction (reaction between polyhydric alcohol and hydrogen) is not particularly limited, but is preferably 1 to 50 MPa, more preferably 3 to 30 MPa, and still more preferably 5 to 15 MPa. . By setting the reaction pressure to 1 MPa or more, the reaction rate (conversion rate) of the polyhydric alcohol tends to be further improved. On the other hand, when the reaction pressure exceeds 50 MPa, the reactor needs to have a high pressure resistance, and thus the production cost tends to increase.

  The above reaction (reaction of polyhydric alcohol and hydrogen) can be carried out in any format such as a batch format, a semi-batch format, a continuous flow format, and the like. In addition, when it is desired to increase the amount of polyhydric alcohol hydride obtained from a predetermined amount of polyhydric alcohol, 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.

  In the above reaction (reaction of polyhydric alcohol and hydrogen), 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. As the fixed bed reactor, for example, a trickle bed reactor can be used. 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.

  In the method for producing a hydride of a polyhydric alcohol of the present invention, the regeneration step and the reaction step can be carried out in separate lines, or can be carried out as a series of steps (in-line).

  The method for producing a hydride of a polyhydric alcohol according to 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. In addition, 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 (hydride of a polyhydric alcohol) is obtained by a known or conventional method (for example, distillation, adsorption, ion exchange, crystallization, extraction, etc.). Can be purified.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by these Examples.

Production Example 1
[Preparation of Ir-Re catalyst]
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. To the carrier, 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 .
Next, an aqueous solution of ammonium perrhenate (NH ₄ ReO ₄ ) prepared so as to have a rhenium (Re) concentration of 3% by weight on the above carrier (a carrier on which iridium is supported) is dropped 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. Thereafter, 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 a glycerol aqueous solution (glycerol concentration: 80 wt%) containing 6.4 ppm of sulfur on an element weight basis, and the temperature was 120 ° C. The mixture was stirred at a hydrogen pressure of 12 MPa for 6 hours to carry out a hydrogenation reaction of glycerin. Then, the whole 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). Next, 500 g of ultrapure water (sulfur content 0.012 ppm) was placed in the reactor and stirred at room temperature for 10 minutes. The water after washing was taken out from the reactor and the sulfur content in the water was measured to be 0.072 ppm, which was increased compared to before washing. Next, 500 g of ultrapure water (sulfur content 0.012 ppm) was again put into the reactor and stirred at 120 ° C. for 60 minutes while being pressurized with nitrogen. Thereafter, the water after washing was taken out from the reactor, and the sulfur content in the water was measured to be 0.391 ppm, and the sulfur removal amount was further increased as compared with the case of washing at room temperature. Thus, it was suggested that the amount of sulfur adsorbed on the Ir-Re catalyst after use can be reduced by washing with water.

  In addition, the reaction rate (conversion rate) of glycerol 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
The 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 (0.8% by weight of glycerin concentration) containing 0.8 ppm of sulfur on an element weight basis, and the temperature was 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). Then, the whole 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). Next, 500 g of an aqueous glycerin solution having a sulfur content of 0.08 ppm or less (glycerin concentration: 80% by weight) was charged and stirred at a temperature of 120 ° C. and a hydrogen pressure of 12 MPa for 6 hours to produce a hydrogenation reaction of glycerin (second hydrogenation reaction). ) From the reaction rate (conversion rate) of glycerin in the first hydrogenation reaction and the reaction rate (conversion rate) of glycerin in the second hydrogenation reaction, the catalyst activity in the first hydrogenation reaction is 100%. As a result of calculating the catalyst activity in the second hydrogenation reaction, the catalyst activity was reduced to about 51% in the second hydrogenation reaction.
A regeneration treatment for washing the Ir-Re catalyst after the second hydrogenation reaction with ultrapure water was performed. Specifically, after removing 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 total 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.
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). When 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. 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). When 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 85%.

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.
When 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 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, the Ir-Re catalyst after the second hydrogenation reaction was regenerated by heating (drying) under 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. The mixture was stirred for 6 hours to carry out a hydrogenation reaction of glycerin (third hydrogenation reaction). When 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 a glycerol aqueous solution (glycerol concentration: 80 wt%) containing 6.4 ppm of sulfur on an element weight basis, and the temperature was 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). Then, the whole 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). Next, 500 g of an aqueous glycerin solution having a sulfur content of 0.08 ppm or less (glycerin concentration: 80% by weight) was charged and stirred at a temperature of 120 ° C. and a hydrogen pressure of 12 MPa for 6 hours to produce a hydrogenation reaction of glycerin (second hydrogenation reaction). ) From the reaction rate (conversion rate) of glycerin in the first hydrogenation reaction and the reaction rate (conversion rate) of glycerin in the second hydrogenation reaction, the catalyst activity in the first hydrogenation reaction is 100%. As a result of calculating the catalyst activity in the second hydrogenation reaction, the catalyst activity was reduced to about 34% in the second hydrogenation reaction.
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.
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 a reactor containing an Ir-Re catalyst after regeneration (washing and heating), 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). When 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 from 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. When 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 72%.

  The results obtained in Examples 2 to 6 and Comparative Example 1 are summarized in Table 1.

  As shown in Table 1, it was confirmed that the catalyst activity of the hydrogenation reaction catalyst can be efficiently recovered by the catalyst regeneration method of the present invention (Examples 1 to 6). In the catalyst regeneration method of the present invention, since it is possible to regenerate without removing the hydrogenation reaction catalyst from the reactor in which the hydrogenation reaction has been carried out, no complicated steps are required. Further, it is not necessary to heat at a very high temperature as in calcination, and no chemical reaction such as oxidation / reduction is involved, so there is no possibility that the catalyst metal changes or decreases. Further, in the catalyst regeneration method of the present invention, as shown in Table 1, high selectivity of 1,3-propanediol (1,3-PD) was maintained even when the regenerated catalyst was used. . On the other hand, when the catalyst regenerated by calcination was used (Comparative Example 1), a decrease in the selectivity of 1,3-propanediol was confirmed.

  The “activity index” in Table 1 represents the reaction rate (conversion rate) of glycerin (unit:%) at a reaction time of 6 hours.

  Since the method for regenerating a hydrogenation reaction catalyst of the present invention has the above-described configuration, the catalyst activity can be recovered to a high level while maintaining high catalyst selectivity. 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. Furthermore, according to the method of regenerating the hydrogenation reaction catalyst by the above regeneration method and proceeding the reaction between the polyhydric alcohol and hydrogen (polyhydric alcohol hydrogenation reaction) in the presence of the regenerated catalyst, excellent production is achieved. Since a hydride of a polyhydric alcohol can be produced, it is advantageous in terms of cost.

Claims (4)

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).
Regeneration treatment (1): Treatment for washing the hydrogenation reaction catalyst with one or both of water and organic solvent Regeneration treatment (2): The hydrogenation reaction catalyst is heated to 80 to 300 ° C. under the flow of a gas containing nitrogen. Heat treatment   The hydrogenation catalyst is at least one metal selected from the group consisting of cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, iridium, and platinum, and a group consisting of molybdenum, tungsten, and rhenium. The method for regenerating a catalyst for a hydrogenation reaction according to claim 1, wherein the catalyst is a solid catalyst containing one or both of at least one selected metal.   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 composed of nitrogen, sulfur, oxygen, and phosphorus. The method for regenerating a hydrogenation reaction catalyst according to claim 1 or 2, which is an organic compound containing at least one atom selected from the group.   The hydrogenation reaction catalyst is regenerated by the hydrogenation reaction catalyst regeneration method according to any one of claims 1 to 3, and in the presence of the regenerated hydrogenation reaction catalyst, a polyhydric alcohol, hydrogen, To produce a hydride of the polyhydric alcohol.