TW201503956A - Method for regenerating catalyst for hydrogenation reaction, and method for producing hydride of polyhydric alcohol - Google Patents

Abstract

Provided is a method for regenerating a catalyst for hydrogenation reactions, said catalyst being poisoned during use in a reaction between a polyhydric alcohol and hydrogen, which is capable of restoring the catalytic activity of the catalyst to a high level without increasing the number of cumbersome processes nor decreasing a metal in the catalyst, while maintaining high selectivity. A method for regenerating a catalyst for hydrogenation reactions, said catalyst being used in the production of a hydride of a polyhydric alcohol by a reaction between the polyhydric alcohol and hydrogen and being poisoned by a poisoning substance. This method is characterized in that the catalyst for hydrogenation reactions is subjected to the following regeneration treatment (1) and/or regeneration treatment (2). Regeneration treatment (1): a treatment wherein the catalyst for hydrogenation reactions is cleaned by water and/or an organic solvent Regeneration treatment (2): a treatment wherein the catalyst for hydrogenation reactions is heated to 80-300 DEG C in a flow of a gas that contains nitrogen.

Description

Method for regenerating catalyst for hydrogenation reaction and method for producing hydride of polyol

The present invention relates to a method for regenerating a catalyst for hydrogenation reaction for regenerating a catalytic activity of a poisonous catalyst, and a method for producing a hydrogenated product of a polyol comprising a step of regenerating a catalyst by the regeneration method. The priority of Japanese Patent Application No. 2013-127769, which is filed on June 18, 2013 in Japan, is hereby incorporated by reference.

At present, the chemical system mainly uses crude oil as a starting material. Moreover, chemical products are mainly composed of carbon atoms. When the flow of the carbon is viewed on the scale of the earth, the carbon which is contained in the underground as a crude oil is taken out of the chemical, and it is used in various applications, and the waste is burned after the use is completed. At that time, the carbon system became carbon dioxide and accumulated in the atmosphere. Furthermore, among them, such as gasoline, light oil, etc., the chemical itself which burns itself for the purpose of use is also mostly present. Due to the flow of carbon, the carbon dioxide accumulated in the atmosphere causes global warming, causing various hazards such as abnormal weather or rising sea surface, and calls for reduction in the amount of carbon dioxide emissions.

As one of the countermeasures, it is proposed to use biomass derived from plants (for example, cellulose, glucose, vegetable oil, etc.) as a starting material for chemicals. The origin of the plant, the plant has grown In the process, carbon dioxide is absorbed by photo synthesis, so that the amount of carbon dioxide emitted by the combustion of the chemical is offset by the amount of carbon dioxide absorbed.

For example, it is known that a compound having a carbon number of 2 represented by ethylene in a raw material of a chemical product can be produced by dehydration of raw ethanol. Further, it is known that a compound having a carbon number of 3 such as propylene, 1,2-propanediol or 1,3-propanediol can be produced by hydrogenating decomposition and dehydration of glycerin which is produced by the production of biodiesel (for example, reference to non- Patent Document 1, etc.). Further, the induction of a compound having a carbon number of 4 (for example, an alcohol having 4 carbon atoms) using a raw material (for example, erythritol or the like) from a raw material has not yet been put into practical use, but is being fully reviewed.

Prior technical literature Non-patent literature

Non-Patent Document 1 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 present inventors have found that glycerin or erythritol is used as a raw material in the presence of a catalyst for hydrogenation reaction (including a catalyst supported by a support and a catalyst supported by a support). The hydrogen reaction can produce a carbon number 3 alcohol or a carbon number 4 alcohol. However, it was found that the catalyst used in the above reaction is a poisonous substance such as a sulfur component contained in the above raw material. It is poisoned and passivated. If it is used repeatedly, there is a problem that the product of the target cannot be obtained.

The inventors of the present invention repeated the review and found that the catalyst can be regenerated by recovering the catalytic activity of the catalyst by calcining the passivated catalyst in a calciner at a high temperature. However, in this method, there is still room for improvement in the following two points. That is, in the above method, in addition to the step of calcining the catalyst, the step of taking out the catalyst from the reactor, the step of refilling the catalyst in the reactor after calcination, and the step of reducing the catalyst before the hydrogenation reaction are carried out. Waiting for complicated steps, there are disadvantages of increasing the number of steps. Further, in the above method, since the high-temperature calcination of the catalyst is carried out, the sublimation cerium oxide in the catalyst is sublimated, and the metal in the catalyst is reduced. As described above, if the amount of metal in the catalyst is reduced, the performance of the catalyst cannot be completely recovered due to the decrease in the active point, and the reuse cannot be repeated many times. Further, the problem of a certain decrease in the selectivity (for example, the selectivity of 1,3-propanediol when glycerin is used) after calcination is also found.

Accordingly, an object of the present invention is to provide a method for regenerating a catalyst for hydrogenation reaction, which is a method for regenerating a poisoning hydrogenation reaction catalyst which is used in a reaction between a polyol and hydrogen, without cumbersome steps. Increasing or reducing the amount of metal in the catalyst while maintaining high selectivity while restoring catalytic activity to a high level.

Further, another object of the present invention is to provide a method for producing a hydrogenated product of a polyhydric alcohol by excellent productivity, which comprises regenerating the catalyst for hydrogenation reaction by the above-described regeneration method, and using a catalyst for hydrogenation reaction after regeneration.

In order to solve the above problems, the inventors of the present invention have intensively reviewed and found that a specific catalyst is delivered by a catalytic hydrogenation reaction catalyst used for producing a hydrogenated product of a polyol by reacting a polyol with hydrogen. The treatment can restore the catalytic activity to a high level while maintaining high selectivity without an increase in complicated steps or a decrease in metal in the catalyst. Further, it has been found that when a reaction between a polyol and hydrogen is carried out in the presence of a catalyst for hydrogenation reaction regenerated by the above method, a hydrogenated product of a polyol can be produced with excellent productivity. The present invention has been completed on the basis of such knowledge and knowledge.

That is, the present invention provides a method for regenerating a catalyst for hydrogenation reaction, which is a catalyst for hydrogenation which is poisoned by a poisonous substance used for reacting a polyol with hydrogen to produce a hydrogenated substance of the above-mentioned polyol, and is regenerated by a catalyst. In the method, the catalyst for hydrogenation reaction is supplied to a regeneration treatment of either or both of the following regeneration treatment (1) and regeneration treatment (2); regeneration treatment (1): by water and an organic solvent Either or both of the catalysts for the hydrogenation reaction are washed, and the regeneration treatment (2) is carried out by heating the catalyst for hydrogenation to 80 to 300 ° C under the flow of a nitrogen-containing gas.

Furthermore, the method for regenerating a catalyst for hydrogenation reaction is provided, wherein the catalyst for hydrogenation reaction comprises at least one selected from the group consisting of cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, iridium and platinum. A metal, and a solid catalyst of either or both of at least one selected from the group consisting of molybdenum, tungsten, and rhenium.

Furthermore, the present invention provides a method for regenerating a catalyst for hydrogenation reaction, wherein the poisonous substance comprises an inorganic substance of at least one metal selected from the group consisting of sodium, potassium, iron, nickel, cobalt, manganese, chromium, and molybdenum. a compound, or an organic compound of at least one atom selected from the group consisting of nitrogen, sulfur, oxygen, and phosphorus.

Moreover, the present invention provides a method for producing a hydrogenated product of a polyhydric alcohol, which is characterized in that the catalyst for hydrogenation reaction is regenerated by the above-described catalyst regeneration method for hydrogenation reaction, and the catalyst for hydrogenation reaction after regeneration is used. In the presence of the polyol, the polyol is reacted with hydrogen to form a hydride of the aforementioned polyol.

That is, the present invention relates to the following.

[1] A method for regenerating a catalyst for hydrogenation reaction, which is a method for regenerating a hydrogenation reaction catalyst which is poisoned by a poisonous substance used for reacting a polyhydric alcohol with hydrogen to produce a hydrogenated product of the above-mentioned polyol, It is characterized in that the catalyst for hydrogenation reaction is supplied to a regeneration treatment of either or both of the following regeneration treatment (1) and regeneration treatment (2); regeneration treatment (1): by water and organic solvent One or both of them wash the catalyst for hydrogenation reaction, and the regeneration treatment (2): the hydrogenation reaction is heated to 80 to 300 ° C under the flow of a nitrogen-containing gas.

[2] The method for regenerating a catalyst for hydrogenation according to [1], wherein the catalyst for hydrogenation reaction comprises a group consisting of cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, iridium, and platinum. A solid catalyst of at least one of a metal and at least one of the selected ones selected from the group consisting of molybdenum, tungsten, and rhenium is selected.

[3] The method for regenerating a catalyst for hydrogenation according to [1] or [2], wherein the catalyst for hydrogenation reaction contains at least ruthenium and osmium.

The method for regenerating a catalyst for hydrogenation reaction according to any one of the above aspects, wherein the catalyst for hydrogenation reaction contains at least a support and a support and a support on the support. On the support.

[5] The method for regenerating a catalyst for hydrogenation according to [4], wherein the supporting system is cerium oxide (SiO ₂ ), titanium oxide (TiO ₂ ), zirconium oxide (ZrO ₂ ), or aluminum oxide (Al ₂ O _{3 ).} ), magnesium oxide (MgO), or a composite of two or more of these inorganic oxides.

[6] The method for regenerating a catalyst for hydrogenation according to [4] or [5], wherein the above-mentioned system is cerium oxide (SiO ₂ ) or zeolite.

[7] The method for regenerating a catalyst for hydrogenation according to any one of [4], wherein the carrier has a specific surface area of 50 m ² /g or more, a pore diameter of 1 to 100 nm, and an average particle diameter. It is 100~10000μm.

[8] The method for regenerating a catalyst for hydrogenation according to any one of [4] to [7], wherein the total amount of the ruthenium and the support (100% by weight) is in the catalyst for hydrogenation reaction.担 The amount of support for the support is 0.01 to 50% by weight, and the ratio of 铱 to 铼 (mol ratio, metal conversion) [铱/铼] is 50/1~1/6.

[9] The method for regenerating a catalyst for hydrogenation according to any one of [4] to [8], wherein a method of supporting ruthenium on the same support as ruthenium in the catalyst for hydrogenation reaction The method of impregnating the cerium-containing solution, and impregnating the cerium-containing solution with the cerium-containing solution after drying, and then calcining the mixture.

[10] The method for regenerating a catalyst for hydrogenation according to any one of [1] to [9] wherein the toxic substance comprises sodium, potassium, iron, nickel, An inorganic compound of at least one metal selected from the group consisting of cobalt, manganese, chromium, and molybdenum, or an organic compound containing at least one atom selected from the group consisting of nitrogen, sulfur, oxygen, and phosphorus.

[11] The method for regenerating a catalyst for hydrogenation according to any one of [1] to [10] wherein the organic solvent in the regeneration treatment (1) is benzene, toluene, xylene, ethylbenzene, Diethyl ether, dimethoxyethane, tetrahydrofuran, two Alkane, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, N,N-dimethylformamide, N,N-di At least one organic solvent selected from the group consisting of methyl acetamide, acetonitrile, propionitrile, benzonitrile, methanol, ethanol, isopropanol, and butanol.

[12] The method for regenerating a catalyst for hydrogenation according to any one of [1] to [11] wherein the organic solvent in the regeneration treatment (1) is methanol, ethanol, isopropanol, and At least one organic solvent selected from the group consisting of butanol.

[13] The method for regenerating a catalyst for hydrogenation according to any one of [1] to [12] wherein the method for washing the catalyst for hydrogenation in the regeneration treatment (1) is not self-reactive The method of washing the hydrogenation reaction with a catalyst is taken out.

[14] The method for regenerating a catalyst for hydrogenation reaction according to any one of [1] to [13], wherein one or both of water and an organic solvent in the regeneration treatment (1) are referred to as The flow rate during the circulation of the cleaning solution is 0.5 to 5.0 hr ^-1 at the liquid space velocity (LHSV), the cleaning temperature is 0 to 250 ° C, and the total cleaning time is 1 to 12 hours, and the air is washed. Under the nitrogen or nitrogen environment, the number of washings is 1 to 10 times.

[15] The method for regenerating a catalyst for hydrogenation according to any one of [1] to [14] wherein the regeneration treatment (2) is carried out by heating a catalyst for hydrogenation under a flow of a nitrogen-containing gas. Processing to 80~300 °C.

[16] The method for regenerating a catalyst for hydrogenation according to any one of [1] to [15] wherein the nitrogen-containing gas system nitrogen in the regeneration treatment (2).

[17] The method for regenerating a catalyst for hydrogenation according to any one of [1] to [16] wherein the flow rate of the nitrogen-containing gas in the regeneration treatment (2) is measured by a space velocity (SV) of 200 ~ 600hr ^-1, the hydrogenation reaction catalyst with a total heating time is 0.5 to 48 hours, the number of heat treatment is 1 to 10 times.

[18] The method for regenerating a catalyst for hydrogenation according to any one of [1] to [17] wherein the polyol is ethylene glycol, diethylene glycol, triethylene glycol or polyethylene glycol. , propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, pentanediol, 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol, glycerin, diglycerin oil At least one selected from the group consisting of polyglycerol, trimethylolpropane, erythritol, pentaerythritol, dipentaerythritol, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol S, and sugar alcohol.

[19] The method for regenerating a catalyst for hydrogenation according to any one of [1] to [18] wherein the polyol is glycerin and/or erythritol.

[20] The method for regenerating a catalyst for hydrogenation according to any one of [1] to [19] wherein the hydride of the polyol is a monohydric alcohol having 3 carbon atoms or a diol having 3 carbon atoms. At least one selected from the group consisting of a carbon number 4 monohydric alcohol, a carbon number 4 diol, and a carbon number 4 triol.

[21] The method for regenerating a catalyst for hydrogenation according to any one of [1] to [20] wherein the hydride of the polyol is in the group consisting of propylene glycol, butylene glycol and butyl triol. At least one of the selected ones.

[22] The method for regenerating a catalyst for hydrogenation according to any one of [1] to [21] wherein the reaction of the polyol and the hydrogen in the method for producing a hydride of the polyol is carried out in the regeneration of a solid. The reaction of the gas-liquid-solid three-phase system in which the liquid polyol reacts with hydrogen in the presence of a catalyst for hydrogenation after the treatment.

[23] The method for regenerating a catalyst for hydrogenation according to any one of [1] to [22] wherein, in the reaction of the polyol and the hydrogen in the method for producing a hydride of the polyol, the polyol The concentration (content of the polyol relative to 100% by weight of the raw material liquid) is 5 to 100% by weight, the reaction temperature is 50 to 200 ° C, and the reaction pressure is 1 to 50 MPa.

[24] A method for producing a hydride of a polyhydric alcohol, which is characterized in that the catalyst for hydrogenation reaction is regenerated by a method for regenerating a catalyst for hydrogenation according to any one of [1] to [23]. In the presence of a catalytic hydrogenation reaction after regeneration, the polyol is reacted with hydrogen to form a hydrogenated product of the above polyol.

According to the method for regenerating the catalyst for hydrogenation reaction of the present invention, the catalytic activity can be restored to a high level while maintaining high selectivity of the catalyst. Again, there is no need for an increase in the number of complicated steps. Further, since it is not necessary to heat at a very high temperature as in calcination, without a chemical reaction such as oxidation, reduction, or the like, no change or decrease in metal in the catalyst occurs. Thereby, the problem of catalytic toxicity caused by a poisonous substance such as a sulfur compound can be solved, and continuous use of the catalyst for 1,000 hours or more is possible. Further, the catalyst for hydrogenation reaction is regenerated by the above-described regeneration method, and the reaction of the polyol with hydrogen is carried out in the presence of the catalyst after regeneration (multiple The method of hydrogenation of a primary alcohol is advantageous in terms of cost because it can produce a hydrogenated product of a polyol with excellent productivity.

Form of implementing the invention <Regeneration method of catalyst for hydrogenation reaction>

The method for regenerating a catalyst for hydrogenation reaction of the present invention (also referred to as "the method for regenerating a catalyst of the present invention") is a toxic substance used when a polyol is reacted with hydrogen to produce a hydrogenated product of the above polyol. A method for regenerating a poisoning hydrogenation reaction catalyst (catalyst for hydrogenation reaction of a polyhydric alcohol), which is characterized in that the catalyst for hydrogenation reaction is supplied to the following regeneration treatment (1) and regeneration treatment (2) Regeneration treatment of one or both; regeneration treatment (1): washing of the catalyst for hydrogenation reaction by either or both of water and an organic solvent, regeneration treatment (2): gas containing nitrogen Under the circulation, the hydrogenation reaction is heated to 80 to 300 ° C with a catalyst.

[catalyst for hydrogenation reaction]

The catalyst for hydrogenation reaction which is regenerated in the catalyst regeneration method of the present invention is a catalyst for hydrogenation which is poisoned by a poisonous substance used for producing a hydrogenated product of the above polyol by reacting a polyol with hydrogen. The catalyst for the hydrogenation reaction is not particularly limited as long as it is a known or conventional hydrogenation reaction catalyst which can be used in the above-described reaction (hydrogenation reaction) of a polyol with hydrogen, but is not particularly limited, and examples thereof include cobalt, At least one metal selected from the group consisting of nickel, copper, zinc, antimony, bismuth, palladium, iridium and platinum (also referred to as "metal (1)"), and a group consisting of molybdenum, tungsten and rhenium A solid catalyst of any one or both of the selected metals (also referred to as "metal (2)"). In the above solid catalyst, the metal (1) usually functions to activate hydrogen, and the metal (2) functions to activate a matrix (polyol). From such a viewpoint, as the above solid catalyst, a solid catalyst containing the metal (1) and the metal (2) is particularly preferable.

As the catalyst for the above hydrogenation reaction, particularly the above hydrogen In terms of excellent reactivity and selectivity in the chemical reaction, it is preferred to contain at least a solid catalyst of ruthenium as the metal (1) and ruthenium as the metal (2), and more preferably at least a support and a support The crucible on the body and the catalyst (solid catalyst) supported on the support. Furthermore, in the present specification, the above-mentioned at least the support and the crucible supported on the support and the catalyst supported on the support are also referred to as "the catalyst of the present invention". . Hereinafter, the catalyst of the present invention is specifically described, and the catalyst for hydrogenation reaction in the method for regenerating the catalyst of the present invention is not limited to the catalyst of the present invention.

The enthalpy and enthalpy in the catalyst of the present invention are as long as they are The shape (state) is not particularly limited as long as it is held on the support. The form of ruthenium and osmium is not particularly limited, and examples thereof include a simple substance, a salt, an oxide, a hydroxide, a complex, and the like.

The carrier in the catalyst of the present invention is not particularly limited as long as it is a well-known or conventional carrier used as a support for the catalyst, and examples thereof include inorganic carriers such as inorganic oxides and activated carbon. An organic carrier such as an ion exchange resin. As the above-mentioned support, among the points which are excellent in catalytic activity, an inorganic oxide is preferable. Examples of the inorganic oxide include cerium oxide (SiO ₂ ), titanium oxide (TiO ₂ ), zirconium oxide (ZrO ₂ ), aluminum oxide (Al ₂ O ₃ ), magnesium oxide (MgO), and the like. Two or more complexes of the substance (for example, zeolite or the like). Among the above inorganic oxides, in particular, those having excellent catalytic activity are preferably cerium oxide (SiO ₂ ) or zeolite. Further, in the catalyst of the present invention, the carrier may be used singly or in combination of two or more.

Further, in the catalyst of the present invention, the ruthenium and the ruthenium are supported on the same support, and may be supported on the respective supports. Among them, 铱 and 铼 are preferably supported on the same support.

The specific surface area of the above-mentioned support is not particularly limited, but it is preferable that the metal such as ruthenium and osmium is highly dispersed, and the aggregation of the metal can be suppressed, and the catalytic activity per unit weight is increased. 50 m ² /g or more (for example, 50 to 1500 m ² /g, preferably 100 to 1000 m ² /g). When the specific surface area of the above-mentioned support is less than the above range, the catalytic activity per unit weight tends to be lowered.

The pore diameter of the above-mentioned support is not particularly limited, but it is preferable that the metal such as ruthenium and osmium is highly dispersed, and the aggregation of the metal can be suppressed, and the catalytic activity per unit weight is increased. 1 to 100 nm, more preferably 5 to 70 nm.

The average particle diameter of the above-mentioned support is not particularly limited, but it is preferably 100 to 10000 μm, more preferably 1,000 to 10,000 μm, in the case where the reaction is carried out in a continuous flow at the point of reactivity without excessive pressure loss. . Further, the shape of the above-mentioned support may be any of powder, granule, and molded (molded body), and is not particularly limited.

铱The amount of support for the support is not particularly limited, but the phase The total amount (100% by weight) of the crucible and the support is preferably about 0.01 to 50% by weight, more preferably about 0.01 to 20% by weight, particularly preferably about 0.5 to 15% by weight, particularly preferably 1.0 to 10%. About weight%. When the amount of rhodium supported is 0.01% by weight or more, the conversion ratio of the polyol tends to be further increased. On the other hand, it is economically advantageous to make the amount of ruthenium to be 50% by weight or less.

铱 There is no particular limitation on the method of supporting the carrier. The cockroaches are carried on the support by well-known or conventional methods of support. Specifically, for example, a solution containing ruthenium (for example, an aqueous solution of ruthenic acid or the like) may be impregnated into a support, followed by drying, followed by calcination or the like. Further, the amount of ruthenium supported can be controlled by adjusting the concentration of the ruthenium-containing solution, the impregnation of the support, and the number of application times of the drying treatment. Further, the temperature at which the cerium-containing solution is impregnated and the temperature at which the carrier impregnated with the solution are dried are not particularly limited.

铼 There is no particular limitation on the method of supporting the carrier. The cockroaches are carried on the support by well-known or conventional methods of support. Specifically, for example, a solution containing ruthenium (for example, an aqueous solution of ammonium perruthenate or the like) may be impregnated into a support, followed by drying, a method of secondary calcination, and the like. In addition, when the crucible is supported on the same crucible as the crucible, for example, a solution containing impregnation is added, and the dried support is further impregnated with a solution containing rhodium, and after drying, calcination is carried out. . Further, the temperature at which the solution containing cerium is impregnated and the temperature at which the support impregnated with the solution are dried are not particularly limited.

Also, as other parties that hold 铱 and 铼 on the support The method may, for example, be a method in which a solution containing cerium and lanthanum is impregnated into a support, followed by drying, followed by calcination.

Impregnated cerium-containing solution and cerium-containing solution (or containing cerium) The temperature at which the dried support is calcined (calcination temperature) is not particularly limited, and is, for example, preferably 300 to 750 ° C in the atmosphere, more preferably 380 to 650 ° C. It is 400~600°C, especially 450~550°C. Moreover, the environment at the time of calcination is not limited to the atmosphere as described above, and for example, it may be calcined in an inert gas atmosphere such as nitrogen or argon.

Ratio of bismuth to bismuth in the catalyst of the present invention (Moerby, Gold The conversion method [铱/铼] is not particularly limited, but from the viewpoint of the conversion ratio of the polyol, it is preferably 50/1 to 1/6, more preferably 4/1 to 1/4, and particularly preferably 3 /1~1/3.

Furthermore, the catalyst of the present invention is in the metal component except The ruthenium and osmium may further contain, for example, platinum, rhodium, cobalt, palladium, nickel, molybdenum, tungsten, manganese, or the like.

The average particle diameter of the catalyst for hydrogenation reaction (especially the catalyst of the present invention) is not particularly limited, but when the reaction is carried out at a point of reactivity or in a continuous flow, the pressure loss is not accompanied by an excessive pressure loss. Preferably, it is 100 to 10000 μm, more preferably 1000 to 10000 μm. In addition, the shape of the catalyst for hydrogenation reaction (especially the catalyst of the present invention) is not particularly limited, and examples thereof include powder form, granular form, and molding (molded form).

The catalyst regeneration method of the present invention is based on the catalyst for hydrogenation reaction (especially the catalyst of the present invention) for reacting a polyol with hydrogen. The catalyst for hydrogenation reaction (catalyst for reduction reaction of a polyhydric alcohol) which is poisoned by a toxic substance used in the formation of a hydride of a polyhydric alcohol is particularly effective in the case where the catalytic activity is remarkably lowered or the passivation is carried out. Examples of the toxic substance include various toxic substances which are well known or conventionally used for the catalyst for poisoning hydrogenation reaction, and are not particularly limited, but generally include, for example, sodium, potassium, iron, nickel, cobalt, manganese, chromium, and molybdenum. The inorganic compound of at least one metal selected from the group consisting of an organic compound of at least one atom selected from the group consisting of nitrogen, sulfur, oxygen, and phosphorus. Among them, when the catalyst for hydrogenation reaction is the catalyst of the present invention, it is particularly susceptible to a sulfur compound such as a long-chain fatty acid, a metal salt, a thiol, a thioether or a sulfur-containing aromatic compound (for example, thiophene), and an amine. It is poisoned by toxic substances such as nitrogen-containing compounds. In addition, although the reason why the catalytic activity of the catalyst for hydrogenation reaction is efficiently recovered by the method for regenerating the catalyst of the present invention is not known, it is presumed that the poisonous substance of the catalyst for poisoning hydrogenation reaction is regenerated (1). Or regenerating treatment (2) and unexpectedly and efficiently desorbing from the hydrogenation reaction catalyst.

[Regeneration method]

As described above, in the catalyst regeneration method of the present invention, the catalyst for hydrogenation reaction after use is subjected to regeneration treatment of either or both of the regeneration treatment (1) and the regeneration treatment (2). In the above-described regeneration treatment, for example, after the polyol is reacted with hydrogen in the reactor, components other than the catalyst for hydrogenation reaction (after use) (hydrocarbons, hydrides of polyols, solvents, etc.) are taken out from the reactor, and then This is carried out in the reactor, which is preferable in terms of preventing the increase of the complicated steps, but is not particularly limited.

(regeneration treatment (1))

The regeneration treatment (1) is a process of washing the catalyst for hydrogenation reaction by any one or both of water and an organic solvent (hereinafter also referred to as "cleaning liquid" as described above. As the organic solvent (organic solvent), a known or customary organic solvent can be used, and it is not particularly limited, and examples thereof include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, and diethyl ether and Methoxyethane, tetrahydrofuran, two An ether such as an alkane, a ketone such as acetone, methyl ethyl ketone or methyl isobutyl ketone, an ester of methyl acetate, ethyl acetate, isopropyl acetate or butyl acetate, N,N-dimethyl A guanamine such as formamide or N,N-dimethylacetamide; a nitrile such as acetonitrile, propionitrile or benzonitrile; an alcohol such as methanol, ethanol, isopropanol or butanol; and the like. Among them, as the organic solvent, an alcohol is preferred. Further, as the cleaning liquid, either water or an organic solvent may be used, or both may be used. Further, when both water and an organic solvent are used, they may be used in the form of a mixed solution of the two, or they may be used separately. Further, the organic solvent may be used singly or in combination of two or more.

The method of washing the catalyst for hydrogenation reaction in the regeneration treatment (1) is not particularly limited, and for example, in the reactor equipped with the catalyst for hydrogenation reaction, the cleaning liquid is continuously or intermittently distributed. A method of adding a catalyst for hydrogenation reaction and a cleaning solution to a reactor, stirring, and a method of immersing a catalyst for hydrogenation reaction taken out from the reactor in a vessel containing the cleaning solution. Among them, a method in which the catalyst for hydrogenation reaction is not taken out from the reactor and is washed is preferably used.

The amount of the cleaning liquid used in the regeneration treatment (1) can be appropriately selected according to the washing method or the like, and is not particularly limited. Further, the flow rate when the cleaning liquid is passed through 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 1.2 to 3.0 hr ^{-1 .} . By controlling the liquid space velocity of the cleaning liquid to the above range, the catalytic activity of the catalyst for hydrogenation reaction tends to be more efficiently recovered.

Washing temperature in regeneration treatment (1) (for example, cleaning in circulation) The temperature of the liquid and the temperature at which the catalyst for the hydrogenation reaction and the washing liquid are stirred are not particularly limited, but are preferably 0 to 250 ° C, more preferably 20 to 200 ° C, and particularly preferably 50 to 160 ° C. By controlling the washing temperature to the above range, the catalytic activity of the catalyst for hydrogenation reaction tends to be more efficiently recovered. Further, the washing temperature may be frequently controlled to be fixed (substantially fixed) between washings, or may be controlled to be changed stepwise or continuously.

Washing time in regeneration treatment (1) (for example, circulating cleaning liquid) The time, the time during which the catalyst for hydrogenation reaction and the washing liquid are added and stirred, are not particularly limited, and can be appropriately set. For example, the total washing time in the regeneration treatment (1) of the catalyst regeneration method of the present invention can be suitably selected from the range of 1 to 12 hours. By controlling the total washing time to the above range, there is a tendency to more efficiently recover the catalytic activity of the catalyst for hydrogenation reaction. In particular, the more the total cleaning time is, the greater the tendency of the catalyst to regenerate.

The pressure during the washing in the regeneration treatment (1) is not special. In addition, the above washing may be carried out under normal pressure, or may be carried out under pressure or under reduced pressure. For example, when washing at a temperature equal to or higher than the boiling point of the cleaning liquid, it is preferred to wash it under pressure.

The washing in the regeneration treatment (1) can be carried out, for example, in various environments such as an air atmosphere or a nitrogen atmosphere, and is not particularly limited.

The number of times of washing in the regeneration treatment (1) at the time of regeneration in the batch reactor is not particularly limited, but is preferably 1 to 10 times, more preferably 1 to 3 times. Further, when the cleaning is performed twice or more, the conditions of the respective washing may be the same or different.

The catalyst for hydrogenation reaction after washing in the regeneration treatment (1) may be dried by a well-known or conventional method (for example, a heating method).

(regeneration treatment (2))

The regeneration treatment (2) is carried out by heating the catalyst for hydrogenation to 80 to 300 ° C under the flow of a gas containing nitrogen (also referred to as "nitrogen-containing gas") as described above. The nitrogen-containing gas is not particularly limited, and examples thereof include nitrogen and a nitrogen-containing mixed gas (for example, air). Among them, nitrogen is preferred.

Velocity of the nitrogen gas system is not particularly limited, for example, at a space velocity (SV) basis, is preferably 200 ~ 600hr ^-1, more preferably 300 ~ 500hr ^-1. By controlling the space velocity of the nitrogen-containing gas to the above range, the catalytic activity of the catalyst for hydrogenation reaction can be more efficiently recovered.

The heat treatment temperature of the hydrogenation reaction catalyst in the regeneration treatment (2) is not particularly limited as long as it is 80 to 300 ° C, but is preferably 120 to 200 ° C. When the temperature of the heat treatment is 80 ° C or higher, the catalytic activity of the catalyst for hydrogenation reaction tends to be more efficiently recovered. On the other hand, by setting the temperature of the heat treatment to 300 ° C or lower, There is a tendency to suppress sublimation of a metal component such as cerium oxide, and further suppress a decrease in catalytic activity. Further, the temperature of the heat treatment may be controlled to be fixed (substantially fixed) between the heat treatments, or may be controlled to be changed stepwise or continuously. Further, the means for heat treatment in the regeneration treatment (2) can be suitably selected from known or conventional heating means.

Heating of the catalyst for hydrogenation in the regeneration treatment (2) The conditioning time (heating time) is not particularly limited, and can be appropriately set, for example, according to the degree of reduction in the catalytic activity of the catalyst for hydrogenation reaction. For example, the total heating time in the regeneration treatment (2) of the catalyst regeneration method of the present invention can be suitably selected, for example, from the range of 0.5 to 48 hours. By controlling the total heating time to the above range, the catalytic activity of the catalyst for hydrogenation reaction tends to be more efficiently recovered.

Heating of the catalyst for hydrogenation in the regeneration treatment (2) It can also be implemented in one stage or in multiple stages of two or more stages.

Heating of the catalyst for hydrogenation in the regeneration treatment (2) The number of times is not particularly limited and may be appropriately set, and is preferably 1 to 10 times, more preferably 1 to 3 times. Further, when the heat treatment is performed twice or more, the conditions of the respective heat treatments may be the same or different.

In the regeneration method of the catalyst of the present invention, regeneration can be performed Only one of the processing (1) and the regeneration processing (2) may perform both the regeneration processing (1) and the regeneration processing (2). When both the regeneration treatment (1) and the regeneration treatment (2) are performed, the timing of the two regeneration treatments is not particularly limited, and may be carried out in a suitable combination.

Hydrogenation regenerated by the regeneration method of the catalyst of the present invention The catalyst for the reaction (regeneration catalyst) is not particularly limited, but it is preferably used in a method for producing the above-mentioned hydride in which a hydride of a polyol is formed by a reaction between a polyol and hydrogen. Since the above-mentioned regenerating catalyst has sufficiently restored the catalytic activity to a high level, a hydrogenated product of a polyol can be produced with excellent productivity in accordance with the above production method.

<Method for Producing Hydride of Polyol of the Present Invention>

The method for producing a hydride of a polyhydric alcohol according to the present invention is characterized in that the catalyst for hydrogenation reaction is regenerated by the catalyst regeneration method of the present invention, and the catalyst for hydrogenation reaction after regeneration (especially the catalyst of the present invention) In the presence of a polyol, the polyol is reacted with hydrogen to form a hydride of the polyol. That is, the method for producing a hydride of a polyhydric alcohol of the present invention includes a step of regenerating a catalyst (hereinafter also referred to as "regeneration step"), and a step of reacting a polyol with hydrogen (hereinafter also referred to as "reaction step") ) as a method of necessary steps. Here, the step of regenerating the catalyst for hydrogenation reaction (regeneration step) can be carried out in accordance with the method described in the item "Regeneration method of catalyst for hydrogenation reaction". Hereinafter, a step (reaction step) of reacting a polyol with hydrogen will be described.

[catalyst for hydrogenation reaction]

The catalyst for hydrogenation reaction used in the above-mentioned reaction step in the method for producing a hydride of a polyol of the present invention is a catalyst for hydrogenation reaction (especially the catalyst of the present invention) which is regenerated by the above-described regeneration step. The reduction treatment of the catalyst for hydrogenation may be carried out as needed before the reaction of the polyol with hydrogen. The reduction treatment of the catalyst for hydrogenation reaction can be carried out by a well-known or conventional method, and is not particularly limited. For example, a method of heating in a reducing gas atmosphere such as hydrogen or the like can be mentioned. The conditions of the heating temperature, the heating time, the pressure, and the like of the reduction treatment are appropriately selected, and are not particularly limited.

[Polyol]

In the reaction step of the method for producing a hydride of a polyol of the present invention, as the polyol used as the raw material (reactant), a well-known or conventional organic compound having two or more hydroxyl groups in the molecule can be used, and there is no particular Examples of the limitation include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,4-butanediol, and pentanediol. 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol, glycerin, diglycerin, polyglycerol, trimethylolpropane, erythritol, pentaerythritol, dipentaerythritol, hydrogenated bisphenol A, hydrogenation Bisphenol F, hydrogenated bisphenol S, sugar alcohol, and the like. Among them, the polyhydric alcohol is preferably a polyhydric alcohol having 3 to 6 carbon atoms (especially a polyhydric alcohol having 3 to 6 carbon atoms in the molecule and having 3 to 6 carbon atoms), particularly in the form of autogenous growth. Preferably, it is glycerin or erythritol.

[Hydrogen of Polyol]

The hydrogenated product of the polyol obtained by the reaction of a polyhydric alcohol and 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 polyol, examples of the hydride thereof include a monohydric alcohol having 3 carbon atoms (propanol; 1-propanol, 2-propanol) and a diol having 3 carbon atoms. (propylene glycol; 1,3-propanediol, 1,2-propanediol) and the like. In particular, by using the catalyst of the present invention, there is a tendency that propylene glycol (especially 1,3-propanediol used as a raw material of a polyurethane or a polyester) can be produced at a high selectivity. On the other hand, for example by using The erythritol is a polyhydric alcohol, and examples of the hydride thereof include a carbon number 4 monohydric alcohol (butanol; 1-butanol, 2-butanol) and a carbon number 4 diol (butanediol; , 4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol), and a carbon number 3 triol (butanetriol; for example, 1,2 , 4-butanetriol, 1,2,3-butanetriol) and the like. In particular, when the catalyst of the present invention is used, butanediol can be produced at a high selectivity (for example, as a solvent, an antifreeze, a medicine, a fuel, or the like), and butyltriol (for example, as a medicine, a gunpowder, etc.) Or the tendency to use such raw materials. In the present specification, when it is generally referred to as "hydrogenated product of a polyhydric alcohol", a compound which is formed by cleaving a carbon-carbon bond of a polyhydric alcohol and having a carbon number smaller than a carbon number of the polyhydric alcohol is not included.

[hydrogen]

The hydrogen (hydrogen) used in the reaction step of the method for producing a hydride of a polyhydric alcohol of the present invention may be used in the form of substantially only hydrogen, or may be used in a state of being diluted with an inert gas such as nitrogen, argon or helium. Further, hydrogen (unreacted hydrogen) recovered from the reaction mixture obtained as a result of the above reaction (reaction of a polyol with hydrogen) may be reused.

[Reaction conditions, etc.]

The reaction of the polyol and the hydrogen in the method for producing a hydride of a polyol of the present invention may be carried out in the presence of a catalyst for hydrogenation after the regeneration treatment of the solid (especially the catalyst of the present invention). The gas-solid two-phase reaction of the (vaporized) polyol reacted with hydrogen may also be in the presence of a catalyst for hydrogenation after the regeneration of the solid (especially the catalyst of the present invention). The reaction of a gas-liquid-solid three-phase system in which a polyol reacts with hydrogen. In particular, from the viewpoint of suppressing the formation of by-products due to the cleavage of the carbon-carbon bond of the polyol, it is preferred to carry out the above reaction in a gas-liquid-solid three-phase system.

More specifically, the above reaction can be carried out, for example, by The raw material liquid in which the alcohol is an essential component is sealed with hydrogen in the reactor, and heated in the presence of the catalyst for the hydrogenation reaction.

The above raw material liquid may contain water in addition to a polyhydric alcohol. The solvent such as an organic solvent may not substantially contain a solvent. The organic solvent is not particularly limited, and examples thereof include alcohols such as methanol, ethanol, isopropanol, n-butanol, and 2-butanol, dimethyl hydrazine (DMSO), and dimethylformamide ( DMF), a highly polar organic solvent such as dimethylacetamide (DMAc), and the like. The raw material liquid preferably contains at least water as a solvent at a point where the reactivity is excellent and the handling or disposal is easy.

The concentration of the polyol in the above raw material liquid (relative to 100 The content of the raw material liquid and the content of the polyhydric alcohol are not particularly limited, but are preferably 5 to 100% by weight, more preferably 8 to 90% by weight, particularly preferably 10 to 90% by weight, particularly preferably 15 to 15% by weight. 80% by weight. When the concentration of the polyol is 5% by weight or more, the reaction rate (conversion ratio) of the polyol tends to be further increased.

In the above reaction (reaction of polyol with hydrogen), may wish Other components may be coexisted within the scope of the effects of the present invention. That is, the raw material liquid may contain other components (for example, alcohols, etc.) within a range that does not impair the effects of the present invention. Further, the raw material liquid may contain, for example, impurities derived from a raw material of a polyol (for example, a long-chain fatty acid, a metal salt, a sulfur-containing compound such as a thiol or a thioether, or a nitrogen-containing compound such as an amine). The impurities are preferably removed from the raw material liquid by a well-known or conventional method (for example, distillation, adsorption, ion exchange, crystallization, extraction, etc.) because of the poisoning of the catalytic catalyst for hydrogenation reaction.

The above raw material liquid system is not particularly limited, but by The alcohol is obtained by uniformly mixing the solvent and other components as needed. In the mixing, a well-known or conventional mixer or the like can be used.

Deliver the hydrogen of the above reaction (reaction of polyol with hydrogen) The ratio of the alcohol is not particularly limited and may be appropriately set depending on the reaction form to be employed and the like.

The reaction temperature of the above reaction (reaction of polyol with hydrogen) It is not particularly limited, but is preferably 50 to 200 ° C, more preferably 60 to 150 ° C, and particularly preferably 70 to 130 ° C. When the reaction temperature is 50 ° C or higher, the reaction rate (conversion ratio) of the polyol tends to be further increased. On the other hand, when the reaction temperature is 200° C. or lower, the decomposition of the polyol (for example, cracking of a carbon-carbon bond) is suppressed, and the hydride of the polyol of the target compound is further increased (for example, when glycerin is used, the carbon number is used). The tendency of the selectivity of the alcohol of 3; for example, when using erythritol, the alcohol having 4 carbon atoms). Further, the reaction temperature may be constantly controlled (fixedly fixed) in the above reaction, or may be controlled to be changed stepwise or continuously.

The reaction time of the above reaction (reaction of polyol with hydrogen) It is not particularly limited and may be appropriately set depending on the reaction form to be employed and the like.

Reaction pressure of the above reaction (reaction of polyol with hydrogen) The hydrogen pressure of the above reaction 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. When the reaction pressure is 1 MPa or more, the reaction rate (conversion ratio) of the polyol tends to be further increased. On the other hand, if the reaction pressure exceeds 50 MPa, the reactor needs to have a high pressure resistance, and the manufacturing cost tends to be high.

The above reaction (reaction of a polyol with hydrogen) can be carried out by any of a batch form, a semi-batch form, a continuous flow form or the like. Further, in order to increase the amount of the hydride of the polyol obtained from the specified amount of the polyol, the process of separating and recovering the unreacted polyol after the above reaction is carried out, and recycling is employed. When this cycle process is employed, the amount of hydride formation of the polyol when a specified amount of polyol is used can be increased.

In the above reaction (reaction of a polyol with hydrogen), a well-known or conventional reactor can be used as the reactor, and for example, a batch reactor, a fluidized bed reactor, a fixed bed reactor or the like can be used. As the above fixed bed reactor, for example, a trickle bed reactor can be used. The so-called trickle bed reactor has a catalyst packed bed filled with a solid catalyst inside, and for the catalyst packed bed, a liquid (in the above reaction, a raw material liquid) and a gas (hydrogen in the above reaction) are simultaneously Above the reactor, a reactor (fixed bed continuous reactor) in the form of a downward flow (gas-liquid down-flow).

In the method for producing a hydride of a polyol of the present invention, the above-described regeneration step and reaction step may be carried out in different production lines, or may be carried out as a series of steps (in-line).

The method for producing a hydride of a polyol of the present invention may contain other steps as needed in addition to the regeneration step and the reaction step. As another step, for example, a step of preparing a raw material liquid after supplying the raw material liquid and hydrogen to the reactor, and separating and purifying the reaction mixture discharged (flowed out from the reactor) (for example, containing a polyol, hydrogen, and the like) a step of a mixture of a hydride or the like of a polyhydric alcohol). Furthermore, these steps can also be carried out in a different production line than the above-described reaction steps, or as a series of steps (in-line).

The hydride (hydrogenated polyol) obtained by the method for producing a hydride of a polyol of the present invention can be purified by a well-known or conventional method (for example, distillation, adsorption, ion exchange, crystallization, extraction, etc.).

Example

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by the examples.

Manufacturing example 1 [Ir-Re Catalyst Modulation]

As a catalyst carrier, cerium oxide (SiO ₂ ) (trade name "Cariact Q-15", manufactured by Fuji SILYSIA Chemical Co., Ltd., pore size: 15 nm) was used. An aqueous solution of ruthenium chloride (H ₂ IrCl ₆ ) prepared so as to have a concentration of iridium (Ir) of 4.47% by weight was dropped on the above-mentioned support, and the support was dried at 110 ° C after the whole of the support was wetted. 3 hours. Then, the dropwise addition and drying of such an aqueous solution of citric acid were repeated, and the lanthanide was supported at 4% by weight on SiO ₂ .

In the same manner as in the case of dropping and drying of the previous aqueous solution of ruthenium citrate, the ruthenium (Re) concentration was adjusted to 3% by weight. The aqueous solution of ammonium acid (NH ₄ ReO ₄ ) was dropped and dried, and the enthalpy of lanthanum and cerium was carried as 1/2 [铱/铼]. Then, the dried support was calcined in an air atmosphere (atmosphere) at 500 ° C for 3 hours to prepare an Ir-Re catalyst [Ir-ReO _X /SiO ₂ ].

Example 1

In an autoclave (reactor), 14.5 g of Ir-Re catalyst obtained in Production Example 1 and 500 g of glycerin aqueous solution (glycerin concentration: 80% by weight) containing 6.4 ppm of sulfur on an element weight basis were added thereto at a temperature of 120 ° C. The mixture was stirred under a hydrogen pressure of 12 MPa for 6 hours to carry out a hydrogenation reaction of glycerin. Then, an aqueous solution containing a hydride of glycerin and glycerin (the Ir-Re catalyst after use was placed in the reactor) was completely extracted from the reactor. Next, 500 g (sulphur content: 0.012 ppm) of ultrapure water was placed in the reactor and stirred at normal temperature for 10 minutes. The washed water was taken out from the reactor, and the sulfur content in the water was measured and found to be 0.072 ppm, which was higher than that before washing. Next, 500 g of ultrapure water (sulfur content: 0.012 ppm) was again placed in the reactor, and stirred at 120 ° C for 60 minutes while being pressurized with nitrogen. Then, the washed water was taken out from the reactor, and the sulfur content in the water was measured and found to be 0.391 ppm. The amount of sulfur removal was further increased as compared with the case of washing at normal temperature. In this way, it is 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 ratio) of glycerol in the following examples and comparative examples was gas chromatography (gas chromatography apparatus: "GC-2014" (manufactured by Shimadzu Corporation), GC Column: TC-WAX, DB-FFAP, detector: FID).

Example 2

In an autoclave (reactor), 14.5 g of Ir-Re catalyst obtained in Production Example 1 and 500 g of glycerin aqueous solution (glycerin concentration: 80% by weight) containing 0.8 ppm of sulfur on an element weight basis were added thereto at a temperature of 120 ° C. Stirring under hydrogen pressure of 12 MPa for 6 hours to carry out hydrogenation of glycerol It should be (the first hydrogenation reaction). Then, an aqueous solution containing a hydride of glycerin and glycerin (the Ir-Re catalyst after use was placed in the reactor) was completely extracted from 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 added, and the mixture was stirred at a temperature of 120 ° C under a hydrogen pressure of 12 MPa for 6 hours to carry out hydrogenation reaction of glycerol (second hydrogenation reaction). . When the reaction rate (conversion ratio) of glycerin in the first hydrogenation reaction and the reaction rate (conversion ratio) of glycerol in the second hydrogenation reaction are calculated, when the catalytic activity in the first hydrogenation reaction is 100% The catalytic activity in the second hydrogenation reaction was such that the catalytic activity was lowered to about 51% in the second hydrogenation reaction.

The regeneration treatment of the Ir-Re catalyst after the second hydrogenation reaction was washed by ultrapure water. Specifically, after extracting Ir-Re catalyst from the reactor, 500 g of washing water (ultra-pure water) was placed in the reactor, stirred at room temperature for 10 minutes, and then the total amount of water extracted twice was performed twice. In the operation, 500 g of washing water (ultra-pure water) was continuously placed in the reactor, stirred at 200 ° C for 60 minutes, and then the entire operation of extracting water was performed three times.

Then, 500 g of an aqueous glycerin solution having a sulfur content of 0.08 ppm or less (glycerin concentration: 80% by weight) was added to a reactor equipped with Ir-Re catalyst after regeneration (washing) at a temperature of 120 ° C and a pressure of 12 MPa. The mixture was stirred under hydrogen pressure for 6 hours to carry out a hydrogenation reaction of glycerin (the third hydrogenation reaction). The catalytic activity in the third hydrogenation reaction was calculated from the reaction rate (conversion ratio) of glycerin in the third hydrogenation reaction, and the third time when the catalytic activity in the first hydrogenation reaction was 100% The catalytic activity in the hydrogenation reaction was restored to 69%.

Example 3

In the same manner as in Example 2, the first hydrogenation reaction and the second hydrogenation reaction were carried out, and then the catalyst was used in the same manner as in Example 2 except that isopropyl alcohol (IPA) was used instead of water as the cleaning liquid. Regeneration processing.

Then, 500 g of an aqueous glycerin solution having a sulfur content of 0.08 ppm or less (glycerin concentration: 80% by weight) was added to a reactor equipped with Ir-Re catalyst after regeneration (washing) at a temperature of 120 ° C and a pressure of 12 MPa. The mixture was stirred under hydrogen pressure for 6 hours to carry out a hydrogenation reaction of glycerin (the third hydrogenation reaction). The catalytic activity in the third hydrogenation reaction was calculated from the reaction rate (conversion ratio) of glycerin in the third hydrogenation reaction, and the third time when the catalytic activity in the first hydrogenation reaction was 100% The catalytic activity in the hydrogenation reaction was restored to 85%.

Example 4

The same operation as in Example 3 was carried out except that the temperature of the washing treatment at 200 ° C was changed to 50 ° C using isopropyl alcohol.

The catalytic activity in the third hydrogenation reaction was calculated from the reaction rate (conversion ratio) of glycerin in the third hydrogenation reaction, and the third time when the catalytic activity in the first hydrogenation reaction was 100% The catalytic activity in the hydrogenation reaction is more than 100%, and the catalytic activity is completely recovered.

Example 5

In the same manner as in Example 2, the first hydrogenation reaction and the second hydrogenation reaction were carried out. Then, the Ir-Re catalyst after the second hydrogenation reaction is subjected to regeneration treatment by heating (drying) under nitrogen flow. Specifically, the internal temperature of the reactor was set to 160 ° C, and nitrogen was continuously flowed at a flow rate of 160 NL per hour for 12 hours.

Then, 500 g of an aqueous glycerin solution having a sulfur content of 0.08 ppm or less (glycerin concentration: 80% by weight) was added to a reactor equipped with a regenerated (heated) Ir-Re catalyst, and hydrogen at a temperature of 120 ° C and 12 MPa was used. The mixture was stirred under pressure for 6 hours to carry out a hydrogenation reaction of glycerin (the third hydrogenation reaction). The catalytic activity in the third hydrogenation reaction was calculated from the reaction rate (conversion ratio) of glycerin in the third hydrogenation reaction, and the third time when the catalytic activity in the first hydrogenation reaction was 100% The catalytic activity in the hydrogenation reaction was restored to 91%.

Example 6

In an autoclave (reactor), 14.5 g of Ir-Re catalyst obtained in Production Example 1 and 500 g of glycerin aqueous solution (glycerin concentration: 80% by weight) containing 6.4 ppm of sulfur on an element weight basis were added thereto at a temperature of 120 ° C. The mixture was stirred under a hydrogen pressure of 12 MPa for 6 hours to carry out a hydrogenation reaction of glycerin (the first hydrogenation reaction). Then, an aqueous solution containing a hydride of glycerin and glycerin (the Ir-Re catalyst after use was placed in the reactor) was completely extracted from 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 added, and the mixture was stirred at a temperature of 120 ° C under a hydrogen pressure of 12 MPa for 6 hours to carry out hydrogenation reaction of glycerol (second hydrogenation reaction). . When the reaction rate (conversion ratio) of glycerin in the first hydrogenation reaction and the reaction rate (conversion ratio) of glycerol in the second hydrogenation reaction are calculated, when the catalytic activity in the first hydrogenation reaction is 100% The catalytic activity in the second hydrogenation reaction was such that the catalytic activity was lowered to about 34% in the second hydrogenation reaction.

The Ir-Re catalyst after the second hydrogenation reaction is subjected to a washing treatment of ultrapure water and a heat treatment under the circulation of air. Specifically, 500 g of washing water (ultra-pure water) was added to the reactor, and the mixture was stirred at normal temperature. In the minute, the entire operation of the extracted water was performed twice, and the internal temperature of the reactor was continued to be 200 ° C, and the air was continuously supplied at a flow rate of 150 NL per hour for 24 hours.

Then, 500 g of an aqueous glycerin solution having a sulfur content of 0.08 ppm or less (glycerin concentration: 80% by weight) was placed in a reactor equipped with Ir-Re catalyst after regeneration (washing and heating) at a temperature of 120 ° C. The mixture was stirred under a hydrogen pressure of 12 MPa for 6 hours to carry out a hydrogenation reaction of glycerin (the third hydrogenation reaction). The catalytic activity in the third hydrogenation reaction was calculated from the reaction rate (conversion ratio) of glycerin in the third hydrogenation reaction, and the third time when the catalytic activity in the first hydrogenation reaction was 100% The catalytic activity in the hydrogenation reaction was restored to 69%.

Comparative example 1

In the same manner as in Example 6, the first hydrogenation reaction and the second hydrogenation reaction were carried out. Then, the Ir-Re catalyst was taken out from the reactor, placed in a calciner, and calcined (recalcined) at 500 ° C for 3 hours. Next, the calcined catalyst was refilled in the reactor, and 500 g of an aqueous glycerin solution having a sulfur content of 0.08 ppm or less (glycerin concentration: 80% by weight) was added thereto, and the mixture was stirred at a temperature of 120 ° C under a hydrogen pressure of 12 MPa for 6 hours. The hydrogenation reaction of glycerol (the third hydrogenation reaction) was carried out. The catalytic activity in the third hydrogenation reaction was calculated from the reaction rate (conversion ratio) of glycerin in the third hydrogenation reaction, and the third time when the catalytic activity in the first hydrogenation reaction was 100% 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 by the catalyst of the present invention. The raw method (Examples 1 to 6) can efficiently recover the catalytic activity of the catalyst for hydrogenation reaction. In the method for regenerating the catalyst of the present invention, since the catalyst for hydrogenation reaction is not taken out from the reactor after the hydrogenation reaction, the regeneration is carried out, so that an increase in the number of complicated steps is not required. Further, since it is not required to be heated at a very high temperature as in calcination, without a chemical reaction such as oxidation, reduction, or the like, there is no change or reduction in the catalytic metal. Further, in the method for regenerating the catalyst of the present invention, as shown in Table 1, the high selectivity of 1,3-propanediol (1,3-PD) is maintained even in the case of using the regenerated catalyst. . On the other hand, in the case of using the catalyst regenerated by calcination (Comparative Example 1), the decrease in the selectivity of 1,3-propanediol was confirmed.

Further, the "activity index" in Table 1 indicates the reaction rate (conversion ratio) (unit: %) of glycerin at a reaction time of 6 hours.

Industrial utilization possibility

According to the method for regenerating the catalyst for hydrogenation reaction of the present invention, the catalytic activity can be restored to a high level while maintaining high selectivity of the catalyst. Again, there is no need for an increase in the number of complicated steps. Further, since it is not necessary to heat at a very high temperature as in calcination, without a chemical reaction such as oxidation, reduction, or the like, no change or decrease in metal in the catalyst occurs. Thereby, the problem of catalytic toxicity caused by a poisonous substance such as a sulfur compound can be solved, and continuous use of the catalyst for 1,000 hours or more is possible. Further, the catalyst for hydrogenation reaction is regenerated by the above-described regeneration method, and a reaction between a polyol and hydrogen (hydrogenation of a polyol) is carried out in the presence of a catalyst after regeneration, and the product can be produced with excellent productivity. A hydride of alcohol, which is advantageous in terms of cost.

Claims (4)

A method for regenerating a catalyst for hydrogenation reaction, which is a method for regenerating a hydrogenation reaction poisoned by a poisonous substance used for reacting a polyol with hydrogen to produce a hydrogenated product of the polyol, characterized by : The hydrogenation reaction catalyst is supplied to any of the following regeneration treatment (1) and regeneration treatment (2) or both; regeneration treatment (1): by either water or organic solvent or Both of them wash the catalyst for hydrogenation reaction, and the regeneration treatment (2): the hydrogenation reaction is heated to 80 to 300 ° C under the flow of a nitrogen-containing gas. The method for regenerating a catalyst for hydrogenation according to claim 1, wherein the catalyst for hydrogenation comprises at least one selected from the group consisting of cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, iridium and platinum. A solid catalyst of either or both of a metal and at least one metal selected from the group consisting of molybdenum, tungsten, and rhenium. The method for regenerating a catalyst for hydrogenation according to claim 1 or 2, wherein the toxic substance comprises at least one metal selected from the group consisting of sodium, potassium, iron, nickel, cobalt, manganese, chromium, and molybdenum. An inorganic compound or an organic compound containing at least one atom selected from the group consisting of nitrogen, sulfur, oxygen, and phosphorus. A method for producing a hydride of a polyhydric alcohol, which is characterized in that the catalyst for hydrogenation is regenerated by a regeneration method for a catalyst for hydrogenation according to any one of claims 1 to 3, and is used for hydrogenation after regeneration. In the presence of a catalyst, the polyol is reacted with hydrogen to form a hydride of the polyol.