JP2023016704A - Hydrogenation catalyst and method for producing hydrogenated compound - Google Patents

Abstract

To provide a platinum group-based hydrogenation catalyst having excellent durability and reactivity for a base compound having a functional group containing a catalyst poisoning atom such as a sulfur atom.SOLUTION: A hydrogenation catalyst contains at least one catalyst particle selected from the group consisting of ruthenium phosphide, rhodium phosphide, palladium phosphide, iridium phosphide, and platinum phosphide.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a hydrogenation catalyst containing alloy particles of phosphorus and a platinum group element as a catalyst component, and a method for producing a hydrogenated compound using the same.

Hydrogenation reactions are used for nuclear hydrogenation, hydrogenation of unsaturated bonds, hydrodeoxygenation reactions, etc. in hydrocarbon compounds, and are required when producing various chemical products from raw material compounds. It is an extremely important technology with many

A platinum group element is a catalyst component commonly used as a catalyst for hydrogenation reactions. A platinum group element is usually supported on a carrier such as carbon to form a heterogeneous catalyst and used in various hydrogenation reactions.

However, heterogeneous catalysts containing platinum group elements are susceptible to catalyst poisoning from sulfur and the like due to their high reactivity. For example, nitrogen compounds such as amines, sulfur compounds, phosphorus compounds such as phosphines, and various halides react When present in the liquid, there is a problem that the active sites of the catalyst are deactivated. Therefore, heterogeneous catalysts containing platinum group elements could not be used for some sulfur compounds and raw materials containing sulfur.

In view of the above problems, various improvements have been studied for the hydrogenation reaction of compounds containing catalyst poisoning components. For example, US Pat. No. 6,200,001 discloses a selective hydrogenation catalyst composition that exhibits improved recovery from sulfur poisoning, such as by contacting a palladium-supported composition with an organophosphorus compound and a weak acid. Further, Patent Document 2 discloses a hydrogenation catalyst in which nanoparticles of cobalt phosphide are used as an active ingredient and supported on a specific carrier. However, Patent Literature 2 neither describes nor suggests the use of a platinum group element for the hydrogenation catalyst, which is a nanoparticle.

Japanese Patent Publication No. 2018-501085 JP 2021-013923 A

As a result of studies by the present inventors, the catalyst composition produced by contacting the palladium-supported composition described in Patent Document 1 with an organic phosphorus compound and a weak acid is resistant to ppm-order petroleum-derived residual sulfur components. It just improved. Therefore, development of a catalyst that can be used under reaction conditions with a large amount of poisoning components, such as in the presence of sulfur compounds, has not been achieved.

In view of the above sulfur poisoning problem peculiar to platinum group catalysts, the present invention provides a raw material compound having a functional group containing an atom that acts as a catalyst poisoning such as a sulfur atom, and has excellent durability and reactivity. An object of the present invention is to provide a platinum group-based hydrogenation catalyst having
Another object of the present invention is to provide a platinum group hydrogenation catalyst that is not deactivated even if a poisoning substance such as sulfur is present in the reaction solution, and that has excellent durability and reactivity. .

As a result of intensive studies, the inventors of the present invention found that the commonly used metal-metal nanoalloy catalysts could not provide sufficient poisoning resistance, and started to study metal-nonmetal nanoalloys. As a result of examining various combinations of metal-nonmetal nanoalloys, it was surprisingly found that a hydrogenation catalyst containing a platinum group phosphide as a catalyst component was functionalized with atoms such as sulfur atoms that act as catalyst poisoning. It was found that the hydrogenation reaction proceeds stably for a long period of time without deactivating the raw material compound having the group. That is, the gist of the present invention is as follows.

[1] A hydrogenation catalyst comprising at least one catalyst particle selected from the group consisting of ruthenium phosphide, rhodium phosphide, palladium phosphide, iridium phosphide, and platinum phosphide.
[2] The hydrogenation catalyst according to [1], further comprising a catalyst carrier that is an inorganic carrier or a carbon carrier, wherein the catalyst particles are supported on the catalyst carrier.
[3] The hydrogenation catalyst according to [1] or [2], wherein the catalyst particles have an average particle size of 0.1 to 1000 nm.
[4] A platinum group element (hereinafter referred to as " The hydrogenation catalyst according to any one of [1] to [3], wherein the content of PGM is 10 to 90% by mass.
[5] The hydrogen according to any one of [1] to [4] in the presence of a poisoning substance having at least one atom selected from the group consisting of a sulfur atom, a nitrogen atom, a phosphorus atom, and a halogen atom. A method for producing a hydrogenated compound, comprising a hydrogenation step of reacting a raw material compound with a hydrogen molecule using a hydrogenation catalyst.
[6] The production method according to [5], wherein the poisoning substance is a sulfur molecule or a sulfur compound.
[7] The production method according to [6], wherein the sulfur compound is thioanisole.
[8] A hydrogenation step of reacting a raw material compound with a hydrogen molecule using the hydrogenation catalyst according to any one of [1] to [4], wherein the raw material compound contains a sulfur atom, a nitrogen atom, and a phosphorus atom. , and a halogen atom.
[9] The production method according to [8], wherein the functional group is a functional group containing a sulfur atom.
[10] The production method according to [9], wherein the functional group containing a sulfur atom is at least one selected from the group consisting of a sulfinyl group, a sulfide group, a thiol group, and a thienyl group.
[11] The production method according to [8], wherein the functional group is a functional group containing a nitrogen atom.
[12] The production method according to [11], wherein the functional group containing a nitrogen atom is at least one selected from the group consisting of a nitro group, an optionally substituted amino group, and a cyano group. .

The hydrogenation catalyst of the present invention has excellent durability and reactivity with respect to a raw material compound having a functional group containing an atom such as a sulfur atom that acts as catalyst poisoning.
Further, the hydrogenation catalyst of the present invention is not deactivated even if poisoning substances such as sulfur are present in the reaction liquid, and has excellent durability and reactivity.

FIG. 1 is a chart of XRD measurements of the Ru—P/SiO ₂ catalyst, Rh—P/SiO ₂ catalyst, Pd—P/SiO ₂ catalyst, and Pt—P/SiO ₂ catalyst produced in Production Examples 1 to 4. indicates FIG. 2 shows the Ru--P/SiO.sub.2, Rh--P/ _SiO.sub.2 , Pd--P/ _SiO.sub.2 , and Pt--P/ _SiO.sub.2 catalysts produced in Production Examples 1 to ₄ with a transmission electron microscope. A photograph of measurements is shown.

An example of a preferred mode for carrying out the present invention will be described below. However, the following embodiments are examples for explaining the present invention, and the present invention is not limited to the following embodiments.

[Hydrogenation catalyst]
The hydrogenation catalyst of the present invention contains at least one catalyst particle selected from the group consisting of ruthenium phosphide, rhodium phosphide, palladium phosphide, iridium phosphide, and platinum phosphide.
The reason why the hydrogenation catalyst of the present invention has improved catalytic activity and improved poisoning resistance against atoms acting as catalyst poisoning such as sulfur atoms, compared to conventional platinum group element-supported catalysts, can be explained by various spectroscopic methods. and density functional theory calculations, it is presumed that this is due to the ``ligand effect'' caused by charge transfer from the platinum group atom to phosphorus and the ``ensemble effect'' that prevents strong coordination of the sulfide product. be.

The phosphorus element content of the catalyst particles is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 25 to 75% by mass. Also, the content of the platinum group element in the catalyst particles is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 25 to 75% by mass. That is, the ratio of the platinum group element and the phosphorus element in the catalyst particles is preferably 10:90 to 90:10, more preferably 20:80 to 80:20, and 75:25 to 25:75. It is even more preferable to have
The catalyst particles (PGMxPy) include PGM ₁ P _0.86 , PGM ₁ P ₃ and the like, but may be a mixture of catalyst particles with different molar ratios.

Catalyst particles can be obtained as a precipitate from a known method, for example, a mixed solution of a platinum group compound solution and a phosphorus compound solution.
A method for obtaining such a precipitate includes the method described in the literature (Junfeng Liu and Andreu Cabot et al, J. Mater. Chem. A, 2018, 6, 11453-11462). More specifically, a platinum group compound salt, a component that suppresses particle growth (that is, an increase in particle size) during reduction of the platinum group compound salt (hereinafter also referred to as a "particle growth suppressing component"), A method of heating and holding a solvent and a phosphorus compound that is easily soluble in the solvent in an inert gas atmosphere can be used.

Although the platinum group compound salt is not particularly limited, it is preferably easy to handle. Examples of such platinum group compound salts include ruthenium chloride, hexaammineruthenium chloride, rhodium chloride, palladium chloride, dichlorotetraamminepalladium, dichlorodiamminepalladium, platinum chloride, chloroplatinic acid, tetraamminedichloroplatinum, and iridium chloride. .

Examples of the particle growth suppressing component include components described in Japanese Patent Application Laid-Open No. 2014-514451. More specifically, one or two or more capping components selected from the group consisting of compounds having an amino group such as propylamine, butylamine, octylamine, decylamine, dodecylamine, hexadecylamine, and oleylamine.

Examples of the solvent include, but are not limited to, aliphatic saturated hydrocarbons such as water, hexane, toluene, n-decane, n-dodecane, n-hexadecane, and n-octadecane; 1-undecene, 1- Aliphatic unsaturated hydrocarbons such as dodecene, 1-hexadecene and 1-octadecene can be mentioned, and hexane, toluene and n-dodecane are preferably used.

Although the phosphorus compound that is easily soluble in the solvent is not particularly limited, it is preferably one that is easy to handle. Examples of such phosphorus compounds include tertiary phosphites such as triphenylphosphite and tertiary phosphines such as triphenylphosphine. The term "easily soluble in a solvent" means that the phosphorus compound can be completely dissolved in the solvent at a temperature lower than the heating temperature at which the precipitate of the catalyst particles is generated, and at 100 ° C., 14 g / L or more of the phosphorus compound can be dissolved. Preferably possible. A person skilled in the art can select one corresponding to such properties by appropriately changing the types of solvents and phosphorus compounds.

The amount of the platinum group compound salt, the grain growth inhibiting component, and the phosphorus compound easily soluble in the solvent is usually 0.1 to 10 mol, preferably 1 to 5 mol, of the platinum group compound salt, and the grain growth inhibiting The component is generally 1-100 mol, preferably 10-50 mol, and the phosphorus compound is generally 1-100 mol, preferably 10-50 mol.

The following conditions can be mentioned as heating and holding in an inert gas atmosphere. Argon, nitrogen, etc. are mentioned as an inert gas. The heating temperature is usually 250 to 350° C., preferably 280 to 320° C., and the holding time is about 2 to 6 hours, and a precipitate can be obtained by heating and holding. The precipitate may be washed and filtered. After washing and filtering, further drying and the like may be performed.

For the purpose of promoting the action of the hydrogenation catalyst according to the present invention, salts of metal components such as nickel, manganese, copper, iron, chromium and molybdenum may be added instead of part of the platinum group compound salts.

In the hydrogenation catalyst of the present invention, it can be identified that the catalyst particles are phosphided platinum group metal by comparing peaks measured by X-ray diffraction (XRD) with known peaks. As a known peak, for example, ruthenium phosphide is described in Liu, T. et al., “A Highly Efficient Hydrogen Evolution Reaction Electrocatalyst in Both Acidic and Alkaline Media”, Chem. Commun., 2018, 54, 3343-3346. Rhodium phosphide is described in Pu, Z. et al., "Activating Rhodium Phosphide-Based Catalysts for the pH-universal Hydrogen Evolution Reaction", Nanoscale, 2018, 10, 12407-12412, and palladium phosphide is described in Layan Savithra, G. H. et al., "Mesoporous Matrix Encapsulation for the Synthesis of Monodisperse Pd5P2 Nanoparticle Hydrodesulfurization Catalysts", ACS Appl. Mater. Interfaces, 2013, 5, 5403-5407; Universal Strategy for Carbon-Supported Transition Metal Phosphides as High-Performance Bifunctional Electrocatalysts towards Efficient Overall Water Splitting", ACS Appl. Mater. Interfaces, 2020, 12, 19447-19456.

In the hydrogenation catalyst of the present invention, the catalyst particles themselves can be used as a hydrogenation catalyst, but in addition to facilitating separation of the catalyst from the reaction system and improving the durability of the catalyst, reuse can also be expected, and it is industrially advantageous, so that it is preferably supported on a catalyst carrier.

The catalyst carrier capable of supporting the catalyst particles is not particularly limited, and various catalyst carriers having a large specific surface area and being widely used for catalytic applications can be used. The specific surface area value of the catalyst support can be appropriately changed according to the type of the catalyst support. For example, in the case of silica, it is preferably 200 to 600 m ² /g.

Catalyst carriers include inorganic carriers. Examples of inorganic carriers include carbon carriers such as activated carbon, fine particles of metal oxides such as alumina, silica, titania, ceria, zirconia and magnesia, as well as inorganic oxide carriers such as combinations of these metal oxides, hydroxyapatite (HAP ), hydrotalcite (HT), and other composite oxide supports.
The term "fine particles" as used herein refers to particles having a larger particle diameter than the supported catalyst particles. and the like.

The method for supporting the catalyst particles on the catalyst carrier is not particularly limited. A method of impregnating a catalyst carrier with a platinum group compound salt or a phosphorus compound, followed by reduction, drying, or calcination to support the platinum group element phosphide on the catalyst carrier; Examples include a method of impregnating a catalyst carrier, a method of mixing a solution in which catalyst particles of a platinum group element of phosphide are dispersed, and a catalyst carrier.

As one aspect of the method for supporting catalyst particles on a catalyst carrier, the catalyst carrier is introduced into a solution containing a platinum group compound salt and a phosphorus compound when preparing a platinum group phosphide, and a platinum group compound salt and a phosphorus compound are added. A method of impregnating a catalyst carrier with a compound and then carrying out reduction, drying and calcination to support a platinum group element phosphide on the catalyst carrier will now be described.
First, a catalyst carrier is added to an aqueous solution of a halogen compound of a platinum group element or the like, stirred, and then dried under reduced pressure. Next, the obtained catalyst precursor is heated and further dried, and then added to an aqueous solution of a phosphorus compound. After stirring the aqueous solution, it is dried under reduced pressure and heated at 500 to 600° C. under reflux of hydrogen. In this manner, the catalyst particles can be supported on the catalyst carrier.

The shape of the catalyst particles of the hydrogenation catalyst of the present invention is not particularly limited, and may be cylindrical or spherical. The average particle diameter of the catalyst particles is preferably 0.1 to 1000 nm, more preferably 0.5 to 500 nm, even more preferably 1 to 300 nm.
The average particle size is a value calculated as the average value of the observation results of about 200 particles observed with an electron microscope such as a transmission electron microscope.

[Method for producing hydrogenated compound]
The method for producing a hydrogenated compound of the present invention includes a hydrogenation step of reacting a raw material compound with hydrogen molecules using the hydrogenation catalyst described above.
In one aspect of the method for producing a hydrogenated compound, the hydrogenation step is carried out in the presence of a poisoning substance having at least one atom selected from the group consisting of a sulfur atom, a nitrogen atom, a phosphorus atom, and a halogen atom. .
In another aspect of the method for producing a hydrogenated compound, a starting compound having a functional group containing at least one atom selected from the group consisting of sulfur, nitrogen, phosphorus and halogen atoms is used.

As described above, the hydrogenation catalyst has improved catalytic activity and improved poisoning resistance against atoms, such as sulfur atoms, that act as catalyst poisoning, compared to conventional platinum group element-supported catalysts. Therefore, even in the presence of a poisoning substance or when using a raw material compound having a functional group containing at least one atom selected from the group consisting of a sulfur atom, a nitrogen atom, a phosphorus atom, and a halogen atom, , the desired hydrogenation step can be carried out.

In any aspect, the hydrogenation step is carried out by heating in a hydrogen-containing atmosphere under normal pressure or pressurized conditions with a sufficient amount of hydrogenation catalyst for hydrogenating the raw material compound present in the reaction system. . More specifically, the amount of the hydrogenation catalyst is preferably 0.1 to 10 mol %, more preferably 0.25 to 5 mol %, still more preferably 0.3 to 5 mol %, and 0.1 to 10 mol % relative to the raw material compound. 5 to 3 mol % is particularly preferred.
The heating conditions are usually 60 to 180°C, preferably 70 to 150°C, more preferably 80 to 150°C.
Normal pressure or pressurized conditions are usually 0.1 to 10 MPa, preferably 0.3 to 5 MPa.
The reaction time is usually 30 minutes to 48 hours, preferably 30 minutes to 24 hours.

The hydrogen-containing atmosphere includes hydrogen gas or a mixed gas of hydrogen gas and an inert gas such as argon. When the hydrogenation step is performed using a solvent, the solvent is not particularly limited, and includes nonpolar solvents such as n-dodecane, tetrahydrofuran, and toluene, various alcohols such as 2-propanol, and protic solvents such as water. Polar solvents and the like can be used.
These solvents can be used singly or in combination of two or more.

[One aspect]
In one aspect of the method for producing a hydrogenated compound, in the presence of a poisoning substance having at least one atom selected from the group consisting of a sulfur atom, a nitrogen atom, a phosphorus atom, and a halogen atom, A hydrogenation step is performed to react the molecules.
Examples of raw material compounds in one embodiment include unsaturated compounds having double bonds or triple bonds, aldehyde compounds, carbonyl compounds, nitrile compounds, nitro compounds, and the like. Among these, nitro compounds are preferred, and p-nitrotoluene and nitrobenzene are more preferred.

Nitrogen compounds such as amines; sulfur molecules; thioanisole, thiourea, 1,1,3,3-tetramethylthiourea, sodium dithionite, thiophene, dibenzothiophene, dimethyldibenzothiophene, ethyl sulfide phosphorus compounds such as phosphine; and halides such as ammonium chloride. One aspect of the poisoning substance includes sulfur molecules or sulfur compounds, more specifically thiophene and thioanisole.
The content of the poisoning substance in the reaction system is usually 0.01 to 10 equivalents, preferably 0.1 to 1 equivalents, relative to the substrate. Although it is preferable that the amount of poisoning substances is as small as possible, the reaction can proceed without deactivation of the hydrogenation catalyst even when poisoning substances within the above range are present due to the raw materials, reaction conditions, and the like.

[Other aspects]
In another aspect of the method for producing a hydrogenated compound, a raw material compound having a functional group containing at least one atom selected from the group consisting of a sulfur atom, a nitrogen atom, a phosphorus atom, and a halogen atom, and a hydrogen molecule are combined. A hydrogenation step for reacting is performed.
The functional group is preferably a functional group containing a sulfur atom, and more preferably at least one selected from the group consisting of a sulfinyl group, a sulfide (thioether) group, a thiol group and a thienyl group.

As the functional group, a functional group containing a nitrogen atom is also preferable, and at least one selected from the group consisting of a nitro group, an optionally substituted amino group, and a cyano group is more preferable. Substituents with which the amino group is substituted are not particularly limited, and examples thereof include alkyl groups, aryl groups, heteroaryl groups, and the like.

Specific examples of starting compounds in other embodiments include the compounds described in (1a) to (1q) below and the compounds described in (3a) to (3k) below.

EXAMPLES Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

[XRD measurement]: Measurement was performed by irradiating characteristic X-rays (45 kV, 40 mA) of Cu-Kα using an X-ray diffractometer (trade name "X'Pert-MPD diffractometer", manufactured by Philips).

[Average particle size]: A transmission electron microscope photograph was measured using a transmission electron microscope (FEI Tecnai G2 20 ST) at an accelerating voltage of 200 kV, and the average value of the catalyst particles in the photograph was calculated.

(Production example 1)
0.91 g of a silica carrier was added to 50 ml of an aqueous solution containing 0.16% by mass of ruthenium chloride, stirred for one hour, and then dried under reduced pressure. After sufficiently drying the obtained Ru/SiO ₂ catalyst precursor at 110° C., it was added to an aqueous ammonium hypophosphite solution, stirred for 1 hour, and dried under reduced pressure. The concentration of the ammonium hypophosphite aqueous solution was adjusted so that the P/Ru molar ratio was 0.86.
The obtained Ru—P/SiO ₂ catalyst precursor was placed in an oven set at a heating rate of 5° C./min under reflux of hydrogen to reach 550° C., and then held for an additional hour for alloying treatment. rice field. The resulting catalyst was designated as Ru--P/SiO ₂ catalyst. When the obtained catalyst was evaluated by XRD, a peak specific to ruthenium phosphide was observed. The average particle size of the catalyst particles of the prepared Ru—P/SiO ₂ catalyst was 3.0 nm.
FIG. 1 shows a chart of the Ru—P/SiO ₂ catalyst measured using XRD, and FIG. 2 shows a transmission electron micrograph of the Ru—P/SiO ₂ catalyst produced.

(Production example 2)
A Rh—P/SiO ₂ catalyst was produced under the same conditions as in Production Example 1, except that ruthenium chloride was changed to rhodium chloride. The average particle size of the catalyst particles of the prepared Rh--P/SiO ₂ catalyst was 2.9 nm.
FIG. 1 shows a chart of the Rh--P/SiO ₂ catalyst measured by XRD, and FIG. 2 shows a transmission electron micrograph of the Rh--P/SiO ₂ catalyst produced.

(Production example 3)
Ruthenium chloride was changed to (NH ₃ ) ₄ PdCl ₂ , and the resulting Pd/SiO ₂ precursor was heated to 500° C. at 5° C./min and calcined for 1 hour in an air atmosphere. Next, under the same conditions as in Production Example 1, except that the concentration of the aqueous ammonium hypophosphite solution brought into contact with the Pd/SiO ₂ precursor after firing was adjusted so that the P/Pd molar ratio was 3.0, A Pd—P/SiO ₂ catalyst was prepared. The average particle size of the catalyst particles of the prepared Pd—P/SiO ₂ catalyst was 6.7 nm.
FIG. 1 shows a chart of the Pd—P/SiO ₂ catalyst measured by XRD, and FIG. 2 shows a transmission electron micrograph of the produced Pd—P/SiO ₂ catalyst.

(Production example 4)
Pt—P / _SiO2 catalyst was prepared. The average particle size of the catalyst particles of the prepared Pt—P/SiO ₂ catalyst was 2.6 nm.
FIG. 1 shows a chart for measuring the Pt--P/SiO ₂ catalyst using XRD, and FIG. 2 shows a transmission electron micrograph of the produced Pt--P/SiO ₂ catalyst.

(Comparative Production Examples 1 to 4)
Ru/SiO ₂ , Rh/SiO ₂ , Pd/SiO ₂ , Pt/SiO ₂ catalysts were prepared in the same manner as in Production Examples 1 to 4, respectively, except that the step of adding the ammonium hypophosphite aqueous solution was not performed. manufactured. The average particle sizes of the catalysts were 3.7 nm, 3.2 nm, 9.3 nm and 3.0 nm, respectively.

(Example 1-1: Deoxygenation reaction from diphenyl sulfoxide (1a) to diphenyl sulfide (2a) (hydrogenation step))
A reaction solution containing 2.5 mmol of diphenyl sulfoxide (1a), 5 mL of n-dodecane, and 0.5 mol % (calculated as Ru) of the Ru—P/SiO ₂ catalyst produced in Production Example 1 was mixed with H ₂ (1 Bar), The reaction was carried out at 100°C for 30 minutes.
After the reaction, the obtained post-reaction solution was analyzed by GC-MS using an internal standard method to determine the yield. Table 1 shows the results.

(Examples 1-2 to 1-4, Comparative Examples 1-2 to 1-4)
The Ru—P/SiO ₂ catalyst of Example 1-1 was changed to the catalyst shown in Table 1, and 0.5 mmol of diphenyl sulfoxide (1a), 3 mL of n-dodecane, and a catalyst amount of 2.5 mol % (platinum group The hydrogenation step was carried out in the same manner as in Example 1-1, except that the reaction time was changed to 60 minutes, and the yield was determined in the same manner. Table 1 shows the results.

(Comparative Example 1-1)
The hydrogenation step was performed in the same manner as in Example 1-1, except that the Ru—P/SiO ₂ catalyst in Example 1-1 was changed to the catalyst shown in Table 1, and the yield was determined in the same manner. . Table 1 shows the results.

The chemical reactions performed in Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-4 are shown below.

From Table 1, it can be seen that the non-phosphided Ru/ _SiO2 catalyst has a significantly lower yield in the deoxygenation reaction of sulfur compounds compared to the hydrogenation catalyst of the present invention. In addition, the yields of Rh, Pd, and Pt that are not phosphorylated were low, as was the case with Ru. On the other hand, the hydrogenation catalyst of the present invention containing catalyst particles of a phosphided platinum group element provided a high yield in the deoxygenation reaction of sulfur compounds.

(Examples 2-1 to 2-19: Examination of starting compound (1))
The hydrogenation reaction represented by the following formula was examined by changing various raw material compounds.

Using the Ru—P/SiO ₂ catalyst produced in Production Example 1 as the hydrogenation catalyst, the reaction was carried out under the conditions shown in Table 2 at H ₂ (1 Bar) and 100°C. After the reaction, the obtained post-reaction solution was analyzed by GC-MS using an internal standard method to determine the yield. Table 2 shows the results.
Example 2-2 is the result of using the recovered Ru—P/SiO ₂ catalyst again after the reaction of Example 2-1. The reaction temperature was set at 25° C. only in Example 2-3.
The recovered catalyst was a powder obtained by separating the reaction solution by centrifugation, washing with 1,2-dimethoxyethane, and drying under reduced pressure. A catalyst that was placed in an oven set to Min to reach 550° C. and held for an additional hour was used.

The types of raw material compounds and the types of hydrogenated compounds are shown below.

From Table 2, it can be seen that the hydrogenation catalyst of the present invention promotes the hydrogenation reaction with high activity without deactivation in the hydrogenation step of a raw material compound having a sulfinyl group, which is a functional group containing a sulfur atom.
In particular, from the results of Examples 2-1 and 2-2, the hydrogenation catalyst of the present invention does not show deterioration in catalytic performance even if it is reused, and is industrially very promising.

(Example 3-1: Hydrogenation reaction from 4-nitrothioanisole (3a) to 4-aminothioanisole (4a) (hydrogenation step))
A reaction solution containing 1 mmol of 4-nitrothioanisole (3a), 3 mL of toluene, and 1.25 mol % (calculated as Ru) of the Ru—P/SiO ₂ catalyst produced in Production Example 1 was added to H ₂ (1 Bar) at 70 C. for 60 minutes.
After the reaction, the obtained post-reaction solution was analyzed by GC using an internal standard method to determine the yield. Table 3 shows the results.

(Examples 3-2 to 3-4, Comparative Examples 3-1 to 3-4)
A hydrogenation reaction (hydrogenation step) was carried out in the same manner as in Example 3-1 except that the Ru—P/SiO ₂ catalyst in Example 3-1 was changed to the catalyst shown in Table 3, and the yield was obtained in the same manner. asked for Table 3 shows the results.

The chemical reactions performed in Examples 3-1 to 3-4 and Comparative Examples 3-1 to 3-4 are shown below.

From Table 3, for the raw material compound having a sulfide group, which is a functional group containing a sulfur atom, the Ru/ _SiO2 catalyst that is not phosphorylated has the following properties in the hydrogenation reaction (hydrogenation step) of the nitro group of the raw material compound: Catalytic activity was insufficient. On the other hand, it was found that the hydrogenation catalyst of the present invention using Ru--P/ _SiO.sub.2 as catalyst particles maintains high activity in the hydrogenation reaction (hydrogenation step) of the nitro group of the raw material compound.

(Examples 4-1 to 4-10: Examination of starting compound (3))
The hydrogenation reaction represented by the following formula was examined by changing various raw material compounds.

Using the Ru—P/SiO ₂ catalyst produced in Production Example 1 as the hydrogenation catalyst, the reaction was carried out under the conditions shown in Table 4 at H ₂ (1 Bar) at 70°C. After the reaction, the obtained post-reaction solution was analyzed by GC or GC-MS using an internal standard method to determine the yield. Table 4 shows the results.

The types of raw material compounds and the types of hydrogenated compounds are shown below.

From Table 4, it can be seen that the Ru—P catalyst is excellent in all hydrogenation reactions (hydrogenation steps) of the nitro group of a wide variety of raw material compounds for raw material compounds having functional groups containing atoms that act as catalyst poisoning. showed reaction activity. Specific examples of the functional group of the raw material compound include a sulfide (thioether) group, a thiol group, a thienyl group, a nitro group, an amino group, a substituted amino group, and a cyano group.

Hydrogenated compounds (4h), (4i), (4j), and (4k) are the pharmaceutical agents Quetiapine (antipsychotic), Vortioxetine (antidepressant), Albendazole, respectively. , an anthelmintic) and as an intermediate for Olanzapine (an antipsychotic). Therefore, the hydrogenation catalyst of the present invention is promising in that it can be expected to be used in the synthesis of pharmaceuticals.

(Example 5-1: Deoxygenation reaction from nitrobenzene (5a) to aminobenzene (5b) (hydrogenation step))
A reaction solution containing 5 mmol of nitrobenzene (5a), 2.5 mmol of thioanisole as a poisoning substance, 3 mL of toluene, and 0.25 mol % (calculated as Ru) of the Ru—P/SiO ₂ catalyst produced in Production Example 1 was The reaction was carried out under conditions of H ₂ (30 Bar) and 70° C. for 60 minutes.
After the reaction, the obtained post-reaction solution was analyzed by GC using an internal standard method to determine the yield. Table 5 shows the results.

(Example 5-2, Comparative Examples 5-1, 5-2)
The hydrogenation step was carried out in the same manner as in Example 5-1, except that the Ru—P/SiO ₂ catalyst in Example 5-1 was changed to the catalyst shown in Table 5, and the yield was determined in the same manner. Table 5 shows the results.

The chemical reactions performed in Examples 5-1 and 5-2 and Comparative Examples 5-1 and 5-2 are shown below.

From Table 5, even in the coexistence of a sulfur compound as a poisoning substance, the hydrogenation catalyst of the present invention having catalyst particles of Ru--P/ _SiO.sub.2 or Rh--P/ _SiO.sub.2 is resistant to poisoning from sulfide. It showed high resistance and retained catalytic activity. From this result, the hydrogenation catalyst of the present invention can be used even under reaction conditions with a large amount of poisoning substances, and is promising in that it can be expected to be used in the petroleum industry and the like.

Claims (12)

A hydrogenation catalyst comprising at least one catalyst particle selected from the group consisting of ruthenium phosphide, rhodium phosphide, palladium phosphide, iridium phosphide, and platinum phosphide. further comprising a catalyst support that is an inorganic support or a carbon support;
2. The hydrogenation catalyst according to claim 1, wherein said catalyst particles are supported on said catalyst carrier. 3. The hydrogenation catalyst according to claim 1, wherein the catalyst particles have an average particle size of 0.1 to 1000 nm. The content of phosphorus element contained in the catalyst particles is 10 to 90% by mass, and the content of platinum group elements selected from the group consisting of ruthenium, rhodium, palladium, iridium, and platinum is 10 to 90%. % by mass, the hydrogenation catalyst according to claim 1 or 2. in the presence of a poisoning substance having at least one atom selected from the group consisting of a sulfur atom, a nitrogen atom, a phosphorus atom, and a halogen atom;
3. A method for producing a hydrogenated compound, comprising a hydrogenation step of reacting a raw material compound with a hydrogen molecule using the hydrogenation catalyst according to claim 1 or 2. 6. The production method according to claim 5, wherein the poisoning substance is a sulfur molecule or a sulfur compound. 7. The production method according to claim 6, wherein the sulfur compound is thioanisole. A hydrogenation step of reacting a raw material compound with a hydrogen molecule using the hydrogenation catalyst according to claim 1 or 2,
A method for producing a hydrogenated compound, wherein the raw material compound has a functional group containing at least one atom selected from the group consisting of a sulfur atom, a nitrogen atom, a phosphorus atom, and a halogen atom. 9. The production method according to claim 8, wherein the functional group is a functional group containing a sulfur atom. 10. The production method according to claim 9, wherein the functional group containing a sulfur atom is at least one selected from the group consisting of a sulfinyl group, a sulfide group, a thiol group, and a thienyl group. 9. The production method according to claim 8, wherein the functional group is a functional group containing a nitrogen atom. 12. The production method according to claim 11, wherein the functional group containing a nitrogen atom is at least one selected from the group consisting of a nitro group, an optionally substituted amino group, and a cyano group.

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