Hydrogenation catalysts

Abstract

The present invention relates to a hydrogenation catalyst, and more particularly to a hydrogenation catalyst that enables high selectivity and conversion in a hydrogenation reaction that converts a carboxylic acid functional group, an aldehyde functional group, or a ketone functional group into an alcohol functional group.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority based on Korean Patent Application No. 10-2022-0187904, filed December 28, 2022, and all contents disclosed in the documents of said Korean patent application are incorporated herein by reference.

[0002] The present invention relates to a hydrogenation catalyst, and more particularly to a hydrogenation catalyst that enables high selectivity and conversion in a hydrogenation reaction that converts a carboxylic acid functional group, an aldehyde functional group, or a ketone functional group into an alcohol functional group. [Background technology]

[0003] Generally, compounds containing an alcohol functional group correspond to organic compounds having a hydroxyl group, and a great number of alcohol compounds are extremely important compounds that are widely used in various industrial fields.

[0004] Examples of alcohols with one hydroxyl group (monohydric alcohols) include methanol, ethanol, and n-propanol. Many monohydric alcohols are frequently used as raw materials for chemical synthesis or as solvents. Examples of alcohols with two hydroxyl groups (dihydric alcohols or diols) include ethylene glycol, propylene glycol, and 1,4-butanediol. These diol compounds are widely used as materials in various basic industries, such as polyesters, polyurethanes, varnishes, adhesives, and pharmaceuticals.

[0005] Many of these important alcohol compounds are mass-produced industrially. In particular, one known method for industrially producing primary alcohols (alcohols having a hydroxymethyl group, -CHOH) is the hydration of olefins, which is primarily used to produce ethanol. Another known method for producing alcohols other than ethanol with three or more carbon atoms, such as n-propanol, n-butanol, or 1,4-butanediol, is the hydrogenation of carboxylic acid esters in the presence of a copper-containing catalyst under high-temperature and high-pressure conditions. However, existing hydrogenation reactions require the production of an esterified compound from a carboxylic acid, followed by hydrogenation of the ester compound, which inevitably complicates the primary alcohol production process.

[0006] Furthermore, there has been a significant increase in demand for environmentally friendly and biodegradable diol compounds. These diol compounds can be converted from dicarboxylic acids or their derivatives using a hydroprocessing catalyst. Most existing catalytic processes that enable this are based on Cu-Cr or Zr-Cr catalysts, or ruthenium oxides or ruthenium-carbon composites. However, these catalytic processes require high-pressure (200-300 bar) operating conditions.

[0007] Additionally, Mitsubishi Chemical Corporation (MCC) and Asahi Kasei have filed patent applications for RuPtSn / C catalysts as dicarboxylic acid-to-dicohol catalysts (US6294703, US6495730), but Pt has the disadvantage of being a more expensive metal with higher price fluctuations than Ru. Lotte Chemical has also filed a patent application (WO2015 / 156582) for the same metal (RuPtSn) supported on Y-zeolite, but similarly has the disadvantage of incurring high catalyst costs and requiring an additional delaminated process when applied to hydrothermal reactions.

[0008] Therefore, there is a demand for the development of a catalyst that can efficiently carry out the hydrogenation reaction of carboxylic acids or carboxylic acid-esters under relatively low pressure conditions without using expensive precious metals such as platinum (Pt), and without excessive reaction time or high temperature conditions. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Japanese Patent Application Publication No. 07 (1995)-165644 [Patent Document 2] China Patent Publication No. 001911504 [Patent Document 3] U.S. Patent No. 6,294,703 [Patent Document 4] U.S. Patent No. 6,495,730 [Patent Document 5] International Publication No. 2015 / 156582 Summary of the Invention [Problem to be solved by the invention]

[0010] The present invention provides a hydrogenation catalyst that can achieve high selectivity and conversion rate in a hydrogenation reaction for converting a carboxyl functional group, an aldehyde functional group, or a ketone functional group into an alcohol functional group under relatively low pressure conditions without excessive reaction time or high temperature conditions.

[0011] The present invention also provides a method for producing the above-mentioned hydrogenation catalyst. [Means for solving the problem]

[0012] According to one embodiment of the present invention, there is provided a hydrogenation catalyst comprising ruthenium and tin as catalytically active metals, wherein the ruthenium content is 30% by weight or more and less than 55% by weight and the tin content is more than 45% by weight and less than 70% by weight, based on the total weight of the ruthenium and tin, and the ratio (A2 / A1) of the hydrogen adsorption amount (A2) at a temperature of 523 K or less to the total hydrogen adsorption amount (A1) of the catalyst is 70 mol% to 99 mol%, as measured by hydrogen-temperature programmed reduction (H-TPR) analysis.

[0013] According to another embodiment of the present invention, there is provided a method for producing the hydrogenation catalyst.

[0014] According to yet another embodiment of the present invention, there is provided a hydrogenation method for carrying out a hydrogenation reaction using the above-described catalyst. [Effects of the Invention]

[0015] The hydrogenation catalyst according to the present invention has an excellent effect in that it can achieve high selectivity and conversion rate under relatively low pressure conditions without excessive reaction time or high temperature conditions in the hydrogenation reaction of converting a carboxylic acid functional group, an aldehyde functional group, or a ketone functional group into an alcohol functional group. [Brief explanation of the drawings]

[0016] [Figure 1] FIG. 2 is a diagram showing hydrogen adsorption curves of passivation layers by hydrogen temperature programmed reduction (H2-TPR) analysis for Examples 1 and 2 and Comparative Examples 1 to 3 according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0017] The terms used in this specification are merely used to describe exemplary embodiments and are not intended to limit the present invention. The singular expressions include the plural expressions unless the context clearly indicates otherwise.

[0018] In this specification, the terms "comprises," "comprises," or "having" are intended to describe embodied features, numbers, steps, components, or combinations thereof, and do not exclude the possibility of one or more other features, numbers, steps, components, combinations, or additions thereof.

[0019] Furthermore, terms of degree such as "about," "substantially," and the like used throughout this specification are used in the sense of a numerical value or a value close to that value when given the inherent manufacturing and material tolerances, and are used to prevent unscrupulous infringers from unfairly exploiting the disclosure in which precise or absolute numerical values ​​are recited for the purpose of understanding this application.

[0020] For reference, in this specification, "part by weight" refers to a relative concept in which the weight of a certain substance is used as a basis to express the weight of the remaining substance as a ratio. For example, in a mixture containing 50 g of substance A, 20 g of substance B, and 30 g of substance C, the amounts of substance B and substance C based on 100 parts by weight of substance A are 40 parts by weight and 60 parts by weight, respectively.

[0021] On the other hand, "% by weight" refers to the absolute concept of the weight of a substance expressed as a percentage of the total weight. In the example mixture, the contents of substance A, substance B, and substance C are 50%, 20%, and 30% by weight, respectively, out of a total weight of 100%.

[0022] Although the present invention can be embodied in various forms through various modifications, specific embodiments are described in detail below by way of example, but it should be understood that this is not intended to limit the present invention to the specific disclosed embodiments, and that the present invention encompasses all modifications, equivalents, and alternatives falling within the spirit and technical scope of the present invention.

[0023] The hydrogenation catalyst of the present invention, the method for producing the same, and the hydrogenation method using the same will be described in more detail below.

[0024] Hydrogenation catalysts According to one embodiment of the present invention, there is provided a hydrogenation catalyst that can achieve high selectivity and conversion rate in a hydrogenation reaction that converts a carboxylic acid group, an aldehyde group, or a ketone group into an alcohol group under relatively low pressure conditions without excessive reaction time or high temperature conditions.

[0025] The catalyst for hydrogenation reactions according to one embodiment of the present invention contains ruthenium and tin as catalytically active metals.

[0026] Specifically, the hydrogenation catalyst has a ruthenium content of 30% by weight or more and less than 55% by weight, and a tin content of more than 45% by weight and less than 70% by weight, relative to the total weight of the ruthenium and tin. The ratio (A2 / A1) of the hydrogen adsorption amount (A2) at a temperature of 523 K or less to the total hydrogen adsorption amount (A1) of the catalyst, measured by hydrogen temperature programmed reduction (H2-TPR) analysis, is 70 mol% to 99 mol%.

[0027] In particular, the hydrogenation catalyst according to one embodiment of the present invention contains catalytically active metals ruthenium and tin in specific ranges, with the ruthenium and tin forming a homogeneous alloy state. Among the noble metals typically used in hydrogenation catalysts, platinum (Pt) is known to have high hydrogen adsorption capacity, promote the reduction of Sn species, and prevent Sn leaching out during hydrothermal reactions, thereby improving catalyst performance and stability. However, the hydrogenation catalyst described above exhibits superior hydrogenation results without the use of expensive platinum (Pt), and is characterized by the absence of Sn leaching out during the reaction.

[0028] Specifically, the hydrogenation catalyst's reduction mechanism for carboxylic acid groups in the composite metal (Ru-Sn) phase is as follows: Ruthenium (Ru, ruthenium) metal adsorbs hydrogen to form a metal-hydride compound, and tin (Sn, tin) acts as a Lewis acid site to activate the carboxylic acid group. The metal-hydride then binds to the activated carboxylic group, aldehyde functional group, or ketone functional group, converting it into an alcohol functional group.

[0029] Meanwhile, in the case of selective hydrogenation reactions that convert carboxylic acid (-(C=O)OH) functional groups, aldehyde (-(C=O)H) functional groups, or ketone (-(C=O)-) functional groups into alcohol (-OH) functional groups, as in the present invention, different metal components result in different metal properties, resulting in different hydrogen adsorption strengths and adsorption amounts. In fact, when comparing Ru-Sn and Ni-Sn metals used in similar carboxylic acid group reduction reactions, the use of Ni metal can result in longer reaction times and higher reaction temperatures under similar conditions. This is due to Ru metal's significantly better hydrogen adsorption capacity than Ni metal.

[0030] Specifically, the hydrogenation catalyst has a ruthenium content of 30% by weight or more but less than 55% by weight, and a tin content of more than 45% by weight but less than 70% by weight, based on the total weight of the ruthenium and tin. More specifically, the ruthenium content may be 30.5% by weight or more, or 30.8% by weight or more, and 54.5% by weight or less, or 53% by weight or less, or 50% by weight or less, or 47% by weight or less. Furthermore, the tin content may be 45.5% by weight or more, or 47% by weight or more, or 50% by weight or more, or 53% by weight or more, and 69.5% by weight or less, or 69.2% by weight or less.

[0031] Furthermore, a hydrogenation catalyst according to one embodiment of the present invention is characterized in that it contains ruthenium as the catalytically active metal in an effective range for catalytic activity. Specifically, the catalytically active metal ruthenium may be contained in an amount of 1 to 11 parts by weight, based on the total weight of the catalyst. More specifically, the catalytically active metal ruthenium may be contained in an amount of 1.5 to 10.5 parts by weight, or 2 to 10 parts by weight, or 3.5 to 9.5 parts by weight, or 4.5 to 9 parts by weight, or 4.8 to 8 parts by weight, or 5.0 to 7.5 parts by weight, or 5.1 to 7 parts by weight. In particular, when ruthenium is contained in a high content, i.e., when the content of ruthenium is more than 11 parts by weight, the cost of the catalyst becomes high. In addition, the size of the active metals containing ruthenium and tin that make up the catalyst increases, resulting in lower selectivity to the target product, which can lead to additional costs in the process.Furthermore, if ruthenium is contained in an amount of less than 1 part by weight, the conversion efficiency is low, which can lead to a decrease in the production efficiency of 1,4-butanediol (1,4-BDO) in the hydrogenation reaction.

[0032] The catalytically active metal tin may be contained in an amount of 1 to 12 parts by weight, or 1.5 to 11 parts by weight, or 2 to 10.8 parts by weight, or 4.5 to 10.5 parts by weight, or 5 to 10.2 parts by weight, or 5.5 to 10 parts by weight, or 5.9 to 9.8 parts by weight, relative to the total weight of the catalyst.

[0033] Furthermore, the tin among the catalytically active metals may be contained in a weight ratio relative to the ruthenium of 0.1 to 3.0, or 0.5 to 2.8, or 0.8 to 2.67, or 0.9 to 2.5, or 1.0 to 2.4, or 1.1 to 2.3 on a weight basis.

[0034] The hydrogenation catalyst according to one embodiment of the present invention preferably contains ruthenium and tin as catalytically active metals within the above-described ranges. If the content is less than the above-described range, the conversion efficiency of the reaction may decrease, or the selectivity of the target product may decrease, resulting in excessive separation and recovery costs. That is, if the content of ruthenium among the catalytically active metals in the hydrogenation catalyst is less than 1 part by weight, the conversion efficiency to the target product, a compound containing an alcohol functional group, such as 1,4-butanediol (BDO), may decrease when hydrogenating a carboxylic acid group, aldehyde group, or ketone group to an alcohol functional group. On the other hand, if the content exceeds the above-described range, the metal dispersion may decrease and the crystal size may increase, resulting in low conversion efficiency.

[0035] On the other hand, the particle size of the active metal in the hydrogenation catalyst may be about 3 nm to about 15 nm, specifically about 3.5 nm to about 14 nm, or about 4 nm to about 13 nm, or about 4.2 nm to about 12 nm, or about 4.3 nm to about 11 nm, or about 4.4 nm to about 10 nm. The particle size of the metal may be the average particle size measured, or may be the particle size value of 100 specimens measured, for example, with a transmission electron microscope. Specifically, the average particle size of the active metal may be about 3.8 nm to about 12 nm, or about 4.0 nm to about 10 nm, or about 4.2 nm to about 9 nm, or about 4.3 nm to about 8 nm, or about 4.5 nm to about 7.5 nm. For example, the particle size of the active metal in the hydrogenation catalyst may be about 3 nm to about 6 nm, and the average particle size of the active metal may be about 4 nm to about 5 nm, or the particle size of the active metal in the hydrogenation catalyst may be about 4 nm to about 12 nm, and the average particle size of the active metal may be about 7 nm to about 8 nm.

[0036] In particular, the hydrogenation reaction using the catalyst of the present invention is, for example, a conversion reaction to linear alcohols by selective hydrogenation of dicarboxylic acids. In this hydrogenation reaction, the catalyst acts as a medium that absorbs hydrogen from the reducing agent and supplies it as a reactant. However, if hydrogen transfer does not occur smoothly, a reverse reaction (oxidation) of the converted product may occur. Therefore, to ensure efficient forward hydrogenation, it is preferable that the catalytically active metals ruthenium and tin are contained within the above-mentioned content ranges.

[0037] Meanwhile, the hydrogenation catalyst according to one embodiment of the present invention is characterized in that it contains catalytically active metals ruthenium and tin within specific ranges as described above, and the ruthenium and tin are in a homogeneous alloy state, and the ratio (A2 / A1) of the hydrogen adsorption amount (A2) at a temperature of 523 K or less to the total hydrogen adsorption amount (A1) of the catalyst, as measured by H2-TPR (Hydrogen-Temperature Program Reduction) analysis, is 70 mol% to 99 mol%.

[0038] In this case, H2-TPR (temperature programmed reduction) is an analytical method that measures the behavior of gases adsorbed and desorbed according to the catalyst temperature, and the adsorption behavior characteristics vary depending on the type of metal, the amount of metal loaded, and the distribution of the metal. In particular, even if the ruthenium and tin meet a specific weight ratio in the catalyst, if they are segregated rather than in a metal alloy state, the catalytic activity may rapidly decrease.

[0039] Specifically, the hydrogenation catalyst may have a ratio (A2 / A1) of the hydrogen adsorption amount (A2) at a temperature of 523 K or less to the total hydrogen adsorption amount (A1) of the catalyst, as measured by H2-TPR (Hydrogen-Temperature Program Reduction) analysis, of 75 mol% or more, or 80 mol% or more, or 82 mol% or more, or 85 mol% or more, or 87 mol% or more, and 98 mol% or less, or 97 mol% or less, or 96 mol% or less, or 95 mol% or less, or 94.5 mol% or less.

[0040] A specific method for analyzing the hydrogen-temperature program reduction (H2-TPR) of the hydrogenation catalyst according to one embodiment of the present invention is as described in Example 1 below.

[0041] For example, the hydrogen temperature programmed reduction (H2-TPR) analysis is an analytical method to evaluate the amount of hydrogen adsorbed on metal at a specific reaction temperature, and the detailed measurement method is as follows.

[0042] -Pre-treatment: Pre-treatment of catalyst and stabilization of TCD signal (1) Inert gas (Ar or N2) is passed through the catalyst bed and the temperature is raised to 373 K at a rate of 5 K / min; (2) Inert gas is passed through the catalyst bed and maintained at 373 K for 30 min; (3) Inert gas is passed through the catalyst bed and cooled to 323K; (4) The inert gas and hydrogen were mixed and flowed through the catalyst layer for 60 minutes to stabilize the TCD signal. At this time, the volume ratio between the inert gas and H2 was fixed at 1:0.05.

[0043] -H2-TPR analysis ​(1) Analyte gas: H2 / Ar 5% mixed gas 30sccm (standard cubic centimeter per minute) (2) Heat up to 1073K at a rate of 5K / min

[0044] More specifically, in the present invention, the area corresponding to the number of moles of total hydrogen adsorption amount adsorbed by the passivation layer surrounded by the H2-TPR curve and baseline from the initial temperature of 333 K to the metal reduction temperature of 973 K is defined as A1, and the area corresponding to the number of moles of hydrogen adsorption amount within the hydrogenation reaction temperature range surrounded by the H2-TPR curve and baseline from the initial temperature of 333 K to the hydrogenation reaction temperature of 523 K is defined as A2, and the ratio (mol%) of A2 to A1 can be measured.

[0045] By carrying out the H2-TPR analysis as described above, the ratio of the hydrogen adsorption amount at temperatures below 523K to the total hydrogen adsorption amount of the catalyst can be measured.

[0046] In particular, the catalyst adsorbs hydrogen during the hydrogenation reaction, which converts a carboxylic acid functional group, an aldehyde functional group, or a ketone functional group into an alcohol functional group. However, since hydrogen adsorbed to the catalyst above the reaction temperature does not participate in the reaction, the amount of hydrogen adsorbed and desorbed below 523 K has a significant impact on reaction activity. Therefore, the hydrogenation catalyst must satisfy the above-mentioned range of hydrogen adsorption below 523 K in the H2-TPR graph.

[0047] For example, the catalytic performance during hydrogenation reaction can be predicted from the hydrogen adsorption curve of the passivation layer of the hydrogenation catalyst.

[0048] Specifically, the performance of the catalyst in the present invention is measured by measuring the liquid-phase hydrothermal reaction in a batch reactor, and therefore, the reduction of the catalyst before activity evaluation can be carried out ex-situ. In particular, since metallic catalysts may be flammable, they can be handled after being stabilized by passivation after reduction. In particular, the catalyst according to one embodiment of the present invention converts reactants into target products through a hydrogenation reaction. The most important role in this process is the hydrogen adsorption behavior.

[0049] For example, a catalyst in a passivated state prior to the catalytic reaction is placed in a reactor, heated to the reaction temperature (503K), and then pressurized with hydrogen. Therefore, hydrogen adsorbed above approximately 523K cannot participate in the reaction. Furthermore, due to the catalytic reaction mechanism, the hydrogenation reaction occurs on the surface of the Ru-Sn metal. In other words, if Ru-Sn forms an independent metal phase rather than forming an alloy, by-products such as gamma-butyrolactone or gasification reactions are produced rather than the conversion to the desired product, 1,4-butanediol.

[0050] Therefore, when the Ru-Sn metals are well mixed, one hydrogen adsorption peak appears in the H2-TPR analysis, and the broadness is determined by the difference in heating rate (5°C / min) and the size of the Ru-Sn metals.

[0051] As a result, the hydrogen adsorption curve of the passivation layer of the hydrogenation catalyst according to one embodiment of the present invention can predict the hydrogen adsorption curve of the ruthenium and tin composite metal (Ru-Sn alloy) that participates in the actual catalytic reaction.

[0052] In particular, even if similar hydrogen adsorption curves are observed in H2-TPR (Hydrogen-Temperature Program Reduction) analysis, there may be limitations to the metals that can participate in hydrogenation reactions as hydrogenation catalysts. Commonly known single catalysts such as Pd, Ru, Ni, and Pt exhibit hydrogen adsorption behavior within a similar range, but their catalytic activity is reduced due to poor activation of carbonyl groups (C=O) in the reactants. In other words, for the carbonyl group hydrogenation reaction pathway to occur efficiently, a ruthenium-tin (Ru-Sn) composite metal catalyst containing ruthenium and tin in the optimal range as catalytically active metals, as mentioned above, requires activation by an oxygen-friendly metal such as tin to facilitate stable hydrogen adsorption to carbonyl groups (C=O).

[0053] However, in order to enhance the overall process stability and reaction efficiency, the hydrogenation catalyst according to one embodiment of the present invention may further include one or more metals selected from the group consisting of palladium (Pd), rhodium (Rh), platinum (Pt), iron (Fe), rhenium (Re), and gallium (Ga) in addition to the ruthenium and tin described above as catalytically active metals. When a catalytically active metal is further included, for example, when Pt is further included, the reduction of Sn species is promoted and the leaching out of Sn generated during the reaction is prevented, thereby achieving higher performance.

[0054] When the catalytically active metal contains one or more transition metals selected from the group consisting of palladium (Pd), rhodium (Rh), platinum (Pt), iron (Fe), rhenium (Re), and gallium (Ga) in addition to ruthenium and tin, the amount of the one or more metals, in terms of their atomic ratio to ruthenium, may be preferably 5 or less or 0.1 to 5, and more preferably 2 or less or 0.2 to 2. For example, the atomic ratio of one or more additional transition metals selected from palladium (Pd), rhodium (Rh), platinum (Pt), iron (Fe), rhenium (Re), and gallium (Ga) (atomic ratio of ruthenium:additional transition metal) based on the atomic ratio of ruthenium (Ru) may be 1:5 or less or 1:0.001 to 1:5, preferably 1:0.1 to 1:5, and more preferably 1:2 or less or 1:0.2 to 1:2.

[0055] However, the inclusion of such additional metals has the disadvantage of increasing the overall catalyst manufacturing cost. In particular, the hydrogenation catalyst according to one embodiment of the present invention contains the catalytically active metals ruthenium and tin in specific ranges, and optimizes the ratio of hydrogen adsorption amounts according to H-TPR (Hydrogen-Temperature Program Reduction) analysis to form a homogeneous alloy state, thereby demonstrating superior hydrogenation reaction results without using the above-mentioned expensive Pt (about twice the price of Ru), and is characterized by no Sn elution during the reaction.

[0056] Therefore, the hydrogenation catalyst according to one embodiment of the present invention preferably contains only ruthenium and tin as catalytically active metals.

[0057] Meanwhile, the catalytically active metal is supported on a porous carbon-based support.

[0058] According to one embodiment of the present invention, a ruthenium and tin (Ru-Sn) composite metal catalyst containing ruthenium and tin in an optimal range as catalytically active metals undergoes a hydrogenation reaction under high-temperature hydrothermal reaction conditions in actual applications, and therefore a carbon-based, particularly a porous carbon-based, support is suitable. When a known alumina or silica-based support is used, it is unstable under hydrothermal reaction conditions, and phase transformation occurs, resulting in a significant decrease in catalytic activity when used as a catalyst support.

[0059] The porous carbon support may be, but is not limited to, at least one selected from the group consisting of activated carbon, carbon black, graphite, graphene, ordered mesoporous carbon (OMC), and carbon nanotubes. Preferably, the carbon black may have a high mesopore ratio. Specific examples of the activated carbon include SX ULTRA, CGSP, PK1-3, SX 1G, DRACO S51HF, CA-1, A-51, GAS 1240 PLUS, KBG, CASP, and SX PLUS. Examples of the carbon black include, but are not limited to, BLACK PEARLS®, ELFTEX®, VULCAN®, MOGUL®, MONARCH®, EMPEROR®, and REGAL®.

[0060] For example, the porous carbon support has a pore volume of 0.1 cm 3 / g~1.5cm 3 / g, or 0.3 cm 3 / g~1.5cm 3 / g, or 0.6 cm 3 / g~1.5cm 3 / g.

[0061] Here, in the carbon-based support, the carbon may have a volume ratio of mesopores with a pore size of 2 nm to 50 nm of 50% or more of the total pores. Preferably, the carbon in the carbon support has a volume ratio of mesopores of 70% or more of the total pores, and more preferably, the carbon in the carbon support has a volume ratio of mesopores of 75% or more of the total pores.

[0062] If the volume ratio of the mesopores is less than 50%, problems may occur in the microscopic mass transfer rate of reactants and products within the carbon support, and if the average size of the pores exceeds 50 nm, problems may occur in the physical strength of the support. Therefore, the above range is preferable.

[0063] The carbon-based support has a BET specific surface area of ​​100 m 2 / g~1,500m 2 / g. Preferably, the carbon has a specific surface area (BET) of 200 m 2 / g~1,000m 2 / g range.

[0064] At this time, the specific surface area of ​​the carbon-based support is 100 m 2 If the concentration is less than 1,500 m / g, it becomes difficult to highly disperse the active metals (Ru, Sn), and the specific surface area of ​​the carbon is 1,500 m / g. 2 If it exceeds 1 / g, the ratio of mesopores may become low, so the above range is preferable.

[0065] On the other hand, the hydrogenation catalyst has a BET specific surface area of ​​100 m 2 / g~1,500m 2 / g, or 200m 2 / g~1,500m 2 / g, or 350m 2 / g~800m 2 / g, or 550-670m 2 / g.

[0066] The hydrogenation catalyst may have an average pore diameter of 2.0 nm to 5.5 nm, or 2.5 nm to 5.0 nm, or 3.0 nm to 4.8 nm, or 4.0 nm to 4.5 nm.

[0067] A hydrogenation catalyst according to one embodiment of the present invention contains catalytically active metals ruthenium and tin within specific ranges, and the ruthenium and tin form a homogeneous alloy state, thereby effectively converting a carboxylic acid group, an aldehyde group, or a ketone group directly into an alcohol group, for example, a primary alcohol, by hydrogenation without esterification. In this hydrogenation reaction, high selectivity and conversion can be achieved under relatively low pressure conditions without excessive reaction time or high temperature conditions.

[0068] Method for producing catalyst for hydrogenation reaction Therefore, according to another embodiment of the present invention, there is provided a method for producing the above-mentioned hydrogenation catalyst.

[0069] Specifically, the method for producing the hydrogenation catalyst includes the steps of: dissolving one or more precursor compounds containing ruthenium as a catalytically active metal and one or more precursor compounds containing tin as a catalytically active metal in an acidic aqueous solution to produce a metal precursor solution; and drying the metal precursor solution or a mixture containing the metal precursor solution, followed by a reduction treatment in the presence of hydrogen gas. The ruthenium content in the metal precursor solution is 30% by weight or more and less than 55% by weight, based on the total weight of the ruthenium and tin, and the tin content is more than 45% by weight and 70% by weight or less, based on the total weight of the ruthenium and tin.

[0070] In particular, the precursor compound containing ruthenium as the catalytically active metal is at least one selected from the group consisting of ruthenium metal, ruthenium chloride, ruthenium nitrate, ruthenium acetylacetonate, ruthenium carbonyl, ruthenium oxalate, and ruthenium nitrosyl nitrate.

[0071] The precursor compound containing tin as the catalytically active metal is at least one selected from the group consisting of tin(II) chloride, sodium stannate, tin(II) acetate, tin fluoride, and tin iodide.

[0072] In the method for preparing a hydrogenation catalyst according to the present invention, a metal precursor solution is prepared using an acidic aqueous solution to completely dissolve the precursor compound or mixture containing ruthenium and tin and completely ionize the precursor compound. By using such an acidic aqueous solution, ruthenium and tin can form an alloy in the form of a solid solution, without solidifying in a separated state. Due to this feature, a broad and symmetrical hydrogen adsorption peak can be observed in the hydrogen adsorption diagram for the hydrogenation catalyst according to one embodiment of the present invention. Therefore, the hydrogenation catalyst according to one embodiment of the present invention achieves superior hydrogenation performance without the need for additional expensive Pt, and also exhibits the excellent effect of preventing Sn leaching during the reaction.

[0073] However, if an acidic aqueous solution is not used in the preparation of the metal precursor solution, Sn and Ru are supported in a segregated state, resulting in reduced catalytic activity even when the same content of metal precursor compounds is used. In the hydrogen adsorption diagram for the final catalyst, independent hydrogen adsorption peaks for Ru and Sn are observed, and the reduction mechanism of the carboxylic acid group in the composite metal (Ru-Sn) phase is not performed properly, resulting in inefficient operation in the catalytic reaction.

[0074] The acidic aqueous solution may contain one or more of hydrochloric acid, nitric acid, and acetic acid, and may have a concentration of 0.1 wt % to 10 wt % to sufficiently dissolve the precursor compound or a mixture thereof. For example, ion-exchanged water containing 1 wt % to 5 wt % hydrochloric acid may be used as the acidic aqueous solution. If an excessive amount of acidic aqueous solution is used in the method for producing a hydrogenation catalyst, excessive corrosive gases such as HCl may be generated during the subsequent reduction treatment, which may cause corrosion of the reactor or process and act as a catalyst poison. Therefore, it is preferable to use the minimum amount within the above range.

[0075] The ruthenium content in the metal precursor solution is 30% by weight or more and less than 55% by weight based on the total weight of ruthenium and tin, and the tin content is more than 45% by weight and 70% by weight or less based on the total weight of ruthenium and tin.

[0076] The objective of the metal precursor solution is to contain the catalytically active metals ruthenium and tin in a specific optimized range, and to ensure that the ruthenium and tin are in a homogeneous alloy state in the final composite metal catalyst.

[0077] Specifically, the ruthenium content in the metal precursor solution may be 1 to 11 parts by weight, based on the total weight of the catalyst to be produced. More specifically, the ruthenium content in the metal precursor solution may be 1.5 to 10.5 parts by weight, or 2 to 10 parts by weight, or 3.5 to 9.5 parts by weight, or 4.5 to 9 parts by weight, or 4.8 to 8 parts by weight, or 5.0 to 7.5 parts by weight, or 5.1 to 7 parts by weight, based on the total weight of the catalyst to be produced. In particular, a high ruthenium content, i.e., more than 11 parts by weight, can result in a higher catalyst price. Furthermore, the size of the active metals, including ruthenium and tin, that make up the catalyst increases, potentially resulting in lower selectivity to the target product and resulting in additional process costs. Furthermore, if ruthenium is contained in an amount less than 1 part by weight, the conversion efficiency is low, which may result in a problem of reduced production efficiency of the target product, a compound containing an alcohol functional group, such as 1,4-butanediol (BDO), in the hydrogenation reaction.

[0078] The tin content in the metal precursor solution may be 1 to 11 parts by weight, or 2 to 10.8 parts by weight, or 4.5 to 10.5 parts by weight, or 5 to 10.2 parts by weight, or 5.5 to 10 parts by weight, or 5.9 to 9.8 parts by weight, relative to the total weight of the catalyst to be produced.

[0079] Furthermore, the tin content in the metal precursor solution may be, on a weight basis, 0.8 to 2.67, 0.9 to 2.5, 1.0 to 2.4, or 1.1 to 2.3, based on the weight of the ruthenium content. If the weight ratio exceeds the above range, the ruthenium and tin are in their independent metallic forms rather than an alloy, and the efficiency of the selective reduction reaction of the carbonyl group decreases, resulting in conversion to an intermediate product, an esterified compound such as gamma-butyrolactone (GBL) or an ether compound such as tetrahydrofuran (THF), rather than the target product, a compound containing an alcohol functional group, such as 1,4-butanediol (BDO), resulting in low conversion efficiency.

[0080] In the metal precursor solution, the specific content ranges and weight ratios of the catalytically active metals ruthenium and tin may be applied at levels that allow the final composite metal catalyst to achieve the ranges described above in relation to the hydrogenation catalyst, and the specific details thereof will not be repeated here.

[0081] Meanwhile, the method for preparing a hydrogenation catalyst according to the present invention is characterized in that, in order to allow the ruthenium and tin contained in the catalyst to be contained in a specific optimized range as described above, the catalyst is prepared by supporting Ru and Sn precursors by an impregnation method, for example, an incipient wetness impregnation method, followed by drying and reduction.

[0082] Specifically, the method for preparing a hydrogenation catalyst may further include, after preparing a metal precursor solution as described above, mixing the metal precursor solution with a porous carbon-based support, which may be part of a step of supporting ruthenium and tin as catalytically active metals on the porous carbon-based support.

[0083] The specific types and ranges of physical properties of the porous carbon support are as described above, and a detailed description thereof will be omitted.

[0084] In particular, the metal precursor solution or a mixture containing the same is dried at a temperature of 323K to 473K, and then subjected to a reduction treatment at a temperature of 473K to 773K in the presence of hydrogen gas.

[0085] The method may further include, after the reduction treatment, passivating the reduction product produced in the reduction treatment to form a passivation layer.

[0086] The passivation step involves passivating the reduced material with a nitrogen mixed gas containing 0.1 to 20% oxygen by volume.

[0087] Hydrogenation Method Therefore, according to another embodiment of the present invention, there is provided a hydrogenation method in which a hydrogenation reaction is carried out using the above-mentioned catalyst.

[0088] The hydrogenation method according to the present invention is characterized by carrying out a hydrogenation reaction to convert a carboxylic acid group, an aldehyde group, or a ketone group into an alcohol group in the presence of the hydrogenation catalyst.

[0089] Specifically, the hydrogenation reaction is carried out under a reaction pressure of 50 bar to 150 bar, at a reaction temperature of 410 K to 560 K, and for a reaction time of 0.5 hours to 10 hours.

[0090] Meanwhile, the carboxylic acid compound containing a carboxylic acid functional group is at least one selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, formic acid, acetic acid, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, maleic acid, cyclohexanecarboxylic acid, benzoic acid, and anhydrides thereof. Specifically, the carboxylic acid compound containing a carboxylic acid functional group may be one or more of succinic acid, succinic anhydride, maleic acid, and maleic anhydride, or two or more of these.

[0091] The aldehyde compound containing an aldehyde functional group may be one or more selected from the group consisting of formaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, valeraldehyde, 2-methylbutyraldehyde, 3-methylbutyraldehyde, 2,2-dimethylpropionaldehyde, capronaldehyde, 2-methylvaleraldehyde, 3-methylvaleraldehyde, 4-methylvaleraldehyde, 2-ethylbutyraldehyde, 2,2-dimethylbutyraldehyde, 3,3-dimethylbutyraldehyde, caprylaldehyde, capricaldehyde, and glutaric dialdehyde. Specifically, the aldehyde compound containing an aldehyde functional group may be n-butyraldehyde.

[0092] The ketone compound containing a ketone functional group is at least one selected from the group consisting of acetone, butanone, pentanone, hexanone, cyclohexanone, and acetophenone. Specifically, the ketone compound containing a ketone functional group may be butanone.

[0093] Meanwhile, the hydrogenation reaction has a conversion rate represented by the following formula 1 of 70% or more, or from 70% to 100%.

number

[0094] The conversion rate is a calculated value of the molar ratio of reactants consumed in the hydrogenation reaction to reactants containing a carboxylic acid functional group, an aldehyde functional group, or a ketone functional group supplied to the hydrogenation reaction when a compound containing an alcohol functional group is obtained by the hydrogenation reaction, and the conversion rate may be preferably 90% or more, or 90% to 99.9%.

[0095] The hydrogenation reaction has a selectivity represented by the following formula 2 of 50% or more, or from 50% to 90%.

number

[0096] The selectivity is a calculated value of the molar ratio of the compound containing an alcohol functional group corresponding to the target compound of the present invention in the product produced by the hydrogenation reaction, and the selectivity may be preferably 55% or more, or 55% to 70%.

[0097] The hydrogenation reaction has a yield represented by the following formula 3 of 50% or more, or from 50% to 90%.

number

[0098] In particular, the hydrogenation catalyst according to one embodiment of the present invention has excellent effects of obtaining a high yield of alcohol compounds by exhibiting high selectivity and conversion rate as described above under relatively low pressure conditions without excessive reaction time or high temperature conditions in a hydrogenation reaction that converts a carboxylic acid functional group, an aldehyde functional group, or a ketone functional group into an alcohol functional group.

[0099] The present invention will be described in more detail with reference to the following examples, but the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention. [Example]

[0100] Example 1 Activated carbon (pore volume: 0.65 cm) was used as the porous carbon support. 3 / g), and the porous carbon support was placed in a drying oven set at a temperature of 373K and stored for 24 hours to remove the remaining moisture absorbed in the carbon support.

[0101] Additionally, an acidic aqueous solution containing hydrochloric acid was used to completely dissolve approximately 0.65 g of tin(II) chloride and SnCl2·2H2O. The acidic aqueous solution was adjusted to a total concentration of 1 wt% using 35% reagent-grade hydrochloric acid. Approximately 0.03 g of ruthenium chloride and RuCl3·3H2O were mixed and completely dissolved for approximately 3 hours to add ruthenium metal equivalent to approximately 80 wt% of the tin metal to the tin precursor solution. The weight ratio of ruthenium / (ruthenium + tin) in the metal precursor solution was adjusted to 44.4 wt%.

[0102] The metal precursor solution thus obtained was uniformly mixed with a porous carbon support in a mortar. The thoroughly mixed metal-carbon mixture was placed in a drying oven set at 373 K and dried for at least 12 hours. Prior to catalytic activity testing, the dried metal-carbon mixture was reduced in a flow of hydrogen gas at 623 K for approximately 3 hours, and the reduced powder catalyst was passivated for 3 hours using a nitrogen mixed gas containing 1% oxygen to prepare a hydrogenation powder catalyst.

[0103] The hydrogenated powder catalyst of Example 1, i.e., the passivated catalyst, prepared as described above was analyzed by H-TPR in the following manner to measure the ratio of the hydrogen adsorption amount at a temperature of 523 K or less to the total hydrogen adsorption amount of the catalyst.

[0104] Specifically, the hydrogen temperature programmed reduction (H2-TPR) analysis is an analytical method for evaluating the amount of hydrogen adsorbed on metal at a specific reaction temperature. The detailed measurement method is as follows:

[0105] ​ -Pre-treatment: Pre-treatment of catalyst and stabilization of TCD signal (1) Inert gas (Ar or N2) is passed through the catalyst bed and the temperature is raised to 373 K at a rate of 5 K / min; (2) Inert gas is passed through the catalyst bed and maintained at 373 K for 30 min; (3) Inert gas is passed through the catalyst bed and cooled to 323K; (4) The inert gas and hydrogen were mixed and flowed through the catalyst layer for 60 minutes to stabilize the TCD signal. At this time, the volume ratio between the inert gas and H2 was fixed at 1:0.05.

[0106] -H2-TPR analysis (1) Analyte gas: H2 / Ar 5% mixed gas 30sccm (standard cubic centimeter per minute) (2) Heat up to 1073K at a rate of 5K / min

[0107] The hydrogen adsorption curve of the passivation layer of the hydrogenated powder catalyst of Example 1, i.e., the passivated catalyst, analyzed by H2-TPR using the above-described method is shown in FIG.

[0108] 1, the area surrounded by the H2-TPR curve and baseline from the initial temperature of 333 K to the metal reduction temperature of 973 K, which corresponds to the number of moles of total hydrogen adsorption by the passivation layer, is defined as A1, and the area surrounded by the H2-TPR curve and baseline from the initial temperature of 333 K to the hydrogenation reaction temperature of 523 K, which corresponds to the number of moles of hydrogen adsorption within the hydrogenation reaction temperature range, is defined as A2, and the ratio (mol%) of A2 to A1 is shown in Table 1. The A2 / A1 ratio in Example 1 measured in this way was 94.5 mol%.

[0109] In addition, the metal content in the catalyst was analyzed using inductively coupled plasma atomic emission spectroscopy (ICP-AES), and the specific surface area and average pore size of the catalyst were measured using nitrogen adsorption / desorption analysis.

[0110] The ruthenium content of the hydrogenation powder catalyst of Example 1, i.e., the passivated catalyst, was measured to be 51,600 ppm and 59,120 ppm by weight in the total catalyst. The active metal size measured by transmission electron microscopy (TEM) was about 3.5-5.5 nm, with an average particle size of about 4.5 nm. The BET specific surface area of ​​the hydrogenation powder catalyst was 603 m. 2 The measured physical properties of the hydrogenation powder catalyst of Example 1 are shown in Table 1 below.

[0111] Example 2 The hydrogenation powder catalyst of Example 2 was prepared by carrying out the same processes as in Example 1, including drying, reduction, and passivation, except that the weight ratio of ruthenium / (ruthenium + tin) in the metal precursor solution, i.e., Ru / Ru + Sn, was changed to 31 wt % and uniformly mixed on the porous carbon support.

[0112] The hydrogen adsorption curve of the passivation layer of the hydrogenated powder catalyst of Example 2, i.e., the passivated catalyst, was analyzed by H2-TPR in the same manner as described above, and is shown in FIG.

[0113] The hydrogenation powder catalyst of Example 2, i.e., the passivated catalyst, was evaluated for its physical properties in the same manner as in Example 1. Specifically, the ruthenium content of the hydrogenation powder catalyst of Example 2, i.e., the passivated catalyst, was measured to be 52,480 ppm and the tin content was 117,700 ppm by weight in the total catalyst. The size of the active metal measured by TME was about 5-10 nm, and the average particle size of the active metal was about 7.5 nm. Furthermore, the BET specific surface area of ​​the hydrogenation powder catalyst was 573 m 2The measured physical properties of the hydrogenation powder catalyst of Example 2 are shown in Table 1 below.

[0114] Comparative Example 1 A hydrogenation powder catalyst of Comparative Example 1 was prepared by carrying out the same processes as in Example 1, including drying, reduction, and passivation, except that the weight ratio of ruthenium / (ruthenium + tin) in the metal precursor solution, i.e., Ru / Ru + Sn, was changed to 24 wt % and the metal precursor solution was uniformly mixed on a porous carbon support.

[0115] The hydrogen adsorption curve of the passivation layer of the hydrogenated powder catalyst of Comparative Example 1, i.e., the passivated catalyst, analyzed by H2-TPR in the same manner as described above is shown in FIG.

[0116] Furthermore, the hydrogenated powder catalyst of Comparative Example 1, ie, the passivated catalyst, was subjected to physical property evaluation in the same manner as in Example 1, and the measurement results are shown in Table 1 below.

[0117] Comparative Example 2 A hydrogenation powder catalyst of Comparative Example 2 was prepared by carrying out the same processes as in Example 1, including drying, reduction, and passivation, except that the weight ratio of ruthenium / (ruthenium + tin) in the metal precursor solution, i.e., Ru / Ru + Sn, was changed to 100 wt% and uniformly mixed on a porous carbon support.

[0118] The hydrogen adsorption curve of the passivation layer of the hydrogenated powder catalyst of Comparative Example 2, i.e., the passivated catalyst, prepared as described above was analyzed by H2-TPR in the same manner as above, and is shown in FIG.

[0119] Furthermore, the hydrogenated powder catalyst of Comparative Example 2, ie, the passivated catalyst, was subjected to physical property evaluation in the same manner as in Example 1, and the measurement results are shown in Table 1 below.

[0120] Comparative Example 3 A hydrogenation powder catalyst of Comparative Example 3 was prepared by carrying out the same processes as in Example 1, including drying, reduction, passivation, etc., except that ruthenium metal was added so that the weight ratio of ruthenium / (ruthenium+tin) in the metal precursor solution, i.e., Ru / Ru+Sn, was 47 wt %, and the metal precursor solution was prepared using an aqueous solution not containing hydrochloric acid, i.e., ion-exchanged water, instead of the acidic aqueous solution, and then uniformly mixed with the porous carbon support.

[0121] The hydrogen adsorption curve of the passivation layer of the hydrogenated powder catalyst of Comparative Example 3, i.e., the passivated catalyst, prepared as described above was analyzed by H2-TPR in the same manner as above, and is shown in FIG.

[0122] Furthermore, the hydrogenated powder catalyst of Comparative Example 3, ie, the passivated catalyst, was subjected to physical property evaluation in the same manner as in Example 1, and the measurement results are shown in Table 1 below.

[0123] In Examples 1 and 2 and Comparative Examples 1 to 3, the weight ratios of the metal components Ru and Sn in the metal precursor solutions and the measurement results of the physical properties of the produced hydrogenation powder catalysts are shown in Table 1 below.

[0124] [Table 1]

[0125] From Table 1, the percentage ratio A2 / A1 of the area A2 where hydrogen is adsorbed within the hydrogenation reaction temperature range to the total hydrogen adsorption area A1 was calculated by measuring the total hydrogen adsorption area from 333K to 973K as A1 and measuring the area A2 where hydrogen is adsorbed within the hydrogenation reaction temperature range from 333K to 523K as A2 through TPR analysis, and then calculating the percentage ratio A2 / A1.

[0126] [Experimental Example 1] Using the hydrogenation powder catalysts of Examples 1 and 2 and Comparative Examples 1 to 3, the hydrogenation reaction of succinic acid was carried out in the following manner. The measurement results for the succinic acid conversion rate (mol%) in the hydrogenation reaction, the selectivity (mol%) of the main compound in the product, and the yield (%) of 1,4-butanediol for each catalyst are shown in Table 2 below.

[0127] Specifically, the hydrogenation of succinic acid was carried out using a batch reactor. 0.75 g of catalyst and succinic acid mixed with 150 mL of 1,4-dioxane solvent at a concentration of 2 wt% were added to an autoclave reactor. To minimize oxidation and other side reactions, the air contained inside the reactor was expelled using hydrogen as the reaction medium. The reactor was then closed and agitated at 300 rpm, and the internal temperature of the reactor was raised to 503 K. After reaching the reaction temperature, hydrogen was added to the reactor to increase the pressure to 90 bar, and the agitation speed was increased to 1,000 rpm and maintained for 6 hours. The reaction product was collected at regular intervals using a sampling port attached to the reactor.

[0128] The reaction products obtained after the reaction were analyzed by gas chromatography (GC) equipped with Agilent DB-FFAP and HP-5 columns. The conversion rate of succinic acid, product selectivity, and 1,4-butanediol yield were calculated using the following equations 1a to 3a.

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[0129] [Table 2]

[0130] As can be seen from Table 2, the hydrogenation reaction of succinic acid was carried out using the catalysts of Examples 1 and 2, which contain catalytically active metals ruthenium and tin within a predetermined range and in which the ruthenium and tin are in a homogeneous alloy state, and as a result, it was possible to produce 1,4-butanediol in a high yield with high selectivity to the alcohol compound 1,4-butanediol and at a high conversion rate, while minimizing the conversion to gamma-butyrolactone (GBL) or tetrahydrofuran (THF), compared to Comparative Examples 1 to 3.

Claims

1. containing ruthenium and tin as catalytically active metals, the ruthenium content is 30% by weight or more and less than 55% by weight, and the tin content is more than 45% by weight and less than 70% by weight, based on the total weight of the ruthenium and tin; Hydrogen temperature-programmed reduction (H ２ - The ratio (A2 / A1) of the hydrogen adsorption amount (A2) at a temperature of 523K or less to the total hydrogen adsorption amount (A1) of the catalyst, as measured by TPR (Hydrogen-Temperature Program Reduction) analysis, is 70 mol% to 99 mol%; Catalyst for hydrogenation reactions.

2. Ruthenium is contained as the catalytically active metal in an amount of 1 part by weight or more and 11 parts by weight or less based on the total weight of the catalyst, tin as the catalytically active metal is contained in an amount of 1 part by weight or more and 12 parts by weight or less based on the total weight of the catalyst; Among the catalytically active metals, the tin is contained in a weight ratio of 0.1 to 3.0 relative to the ruthenium on a weight basis. The hydrogenation catalyst according to claim 1.

3. The catalytically active metal is supported on a porous carbon-based support. The hydrogenation catalyst according to claim 1.

4. The porous carbon-based support includes at least one selected from the group consisting of activated carbon, carbon black, graphite, graphene, ordered mesoporous carbon (OMC), and carbon nanotubes. The hydrogenation catalyst according to claim 3.

5. The porous carbon support has a pore volume of 0.1 cm ３ / g to 1.5 cm ３ / g, The hydrogenation catalyst according to claim 3.

6. The hydrogenation catalyst has a BET specific surface area of ​​100 m ２ / g~1,500m ２ / g, The hydrogenation catalyst according to claim 1.

7. The hydrogenation catalyst has an average pore diameter of 2.0 nm to 5.5 nm. The hydrogenation catalyst according to claim 1.

8. a step of dissolving one or more precursor compounds containing ruthenium as a catalytically active metal and one or more precursor compounds containing tin as a catalytically active metal in an acidic aqueous solution to prepare a metal precursor solution; drying the metal precursor solution or a mixture containing the same, and then reducing the solution in the presence of hydrogen gas; Including, The ruthenium content in the metal precursor solution is 30% by weight or more and less than 55% by weight based on the total weight of ruthenium and tin, and the tin content is more than 45% by weight and less than 70% by weight based on the total weight of ruthenium and tin. A method for producing a catalyst for hydrogenation reactions.

9. The precursor compound containing ruthenium as the catalytically active metal is at least one selected from the group consisting of ruthenium metal, ruthenium chloride, ruthenium nitrate, ruthenium acetylacetonate, ruthenium carbonyl, ruthenium oxalate, and ruthenium nitrosyl nitrate. A method for producing the hydrogenation catalyst according to claim 8.

10. The precursor compound containing tin as the catalytically active metal is at least one selected from the group consisting of tin(II) chloride, sodium stannate, tin(II) acetate, tin fluoride, and tin iodide. A method for producing the hydrogenation catalyst according to claim 8.

11. After the step of preparing the metal precursor solution, the method further comprises the step of mixing the metal precursor solution with a porous carbon-based support. A method for producing the hydrogenation catalyst according to claim 8.

12. the metal precursor solution or a mixture containing the same is dried at a temperature of 323 K to 473 K, and then subjected to a reduction treatment in the presence of hydrogen gas at a temperature of 473 K to 773 K; A method for producing the hydrogenation catalyst according to claim 8.

13. After the reduction treatment step, the method further includes a step of passivating the reduction product produced in the reduction treatment step to form a passivation layer. A method for producing the hydrogenation catalyst according to claim 8.

14. The passivation step is to passivate the reduced material with a nitrogen mixed gas containing 0.1% to 20% oxygen by volume. A method for producing the hydrogenation catalyst according to claim 13.

15. A hydrogenation method for converting a carboxyl functional group, an aldehyde functional group, or a ketone functional group into an alcohol functional group, in the presence of the catalyst according to claim 1.

16. The hydrogenation reaction has a reaction pressure of 50 bar to 150 bar, a reaction temperature of 410 K to 560 K, and a reaction time of 0.5 hours to 10 hours. The hydrogenation method according to claim 15.

17. The carboxylic acid compound containing a carboxyl functional group includes oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, and terephthalic acid. acid), formic acid, acetic acid, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, maleic acid, cyclohexanecarboxylic acid, benzoic acid, and anhydrides thereof; The hydrogenation method according to claim 15.

18. The aldehyde compound containing an aldehyde functional group is at least one selected from the group consisting of formaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, valeraldehyde, 2-methylbutyraldehyde, 3-methylbutyraldehyde, 2,2-dimethylpropionaldehyde, capronaldehyde, 2-methylvaleraldehyde, 3-methylvaleraldehyde, 4-methylvaleraldehyde, 2-ethylbutyraldehyde, 2,2-dimethylbutyraldehyde, 3,3-dimethylbutyraldehyde, caprylaldehyde, capricaldehyde, and glutaric dialdehyde. The hydrogenation method according to claim 15.

19. The ketone compound containing a ketone functional group is at least one selected from the group consisting of acetone, butanone, pentanone, hexanone, cyclohexanone, and acetophenone. The hydrogenation method according to claim 15.

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