Catalysts for hydrogenation

Abstract

The present invention relates to a catalyst for a hydrogenation reaction, and more specifically, to a catalyst for a hydrogenation reaction that enables high selectivity and conversion rate in a hydrogenation reaction in which a carboxylic acid functional group, an aldehyde functional group, or a ketone functional group is converted into an alcohol functional group.

Description

Technology Field

[0001] The present invention relates to a catalyst for a hydrogenation reaction, and more specifically, to a catalyst for a hydrogenation reaction that enables high selectivity and conversion rate in a hydrogenation reaction in which a carboxylic acid functional group, an aldehyde functional group, or a ketone functional group is converted into an alcohol functional group. Background Technology

[0003] Generally, compounds containing alcohol functional groups correspond to organic compounds having hydroxyl groups, and a very large number of alcohol compounds are very important compounds widely used in various industrial fields.

[0005] Among these, examples of alcohols having 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. In addition, examples of alcohols having two hydroxyl groups (dihydric alcohols or diols) include ethylene glycol, propylene glycol, and 1,4-butanediol. These diol compounds are widely used as materials for various base industries, such as polyesters, polyurethanes, varnishes, adhesives, and pharmaceuticals.

[0007] Many of these important alcohol compounds are mass-produced industrially. In particular, regarding the industrial production of primary alcohols (alcohols containing a hydroxymethyl group, -CH2OH), a method involving the hydration reaction of olefins is known, for example, and is mainly used for the production of ethanol. Additionally, for the production of alcohols other than ethanol that have three or more carbon atoms, such as n-propanol, n-butanol, or 1,4-butanediol, a method involving the hydrogenation reaction of carboxylic acid esters under high temperature and high pressure conditions in the presence of a copper-containing catalyst is known. However, conventional hydrogenation reactions involve producing an esterified compound from a carboxylic acid and then performing the hydrogenation reaction on the produced ester compound, which inevitably makes the production process of primary alcohols complex.

[0009] Furthermore, there has been a significant recent increase in demand for environmentally friendly and biodegradable diol compounds. These diol compounds can be converted from dicarboxylic acids or their derivatives via hydroprocessing catalysts. While most existing catalytic processes enabling this are based on Cu-Cr or Zr-Cr catalysts, or on ruthenium oxide or ruthenium-carbon complexes, the aforementioned processes require high-pressure operating conditions (200-300 bar).

[0011] In addition, Mitsubishi Chemical Corporation (MCC) and Asahi Kasei have filed patents for RuPtSn / C catalysts as dicarboxylic acid-to-dicohol catalysts (US6294703, US6495730), but Pt has the disadvantage of being a metal with higher price volatility and a higher cost than Ru. Lotte Chemical has also filed a patent (WO 2015-156582) for supporting the same metal (RuPtSn) on Y-zeolite, but this also incurs high catalyst costs and requires the additional introduction of a delaminated process when applied to hydrothermal reactions.

[0013] Accordingly, there is a need to develop a catalyst that can efficiently carry out the hydrogenation reaction of carboxylic acids or carboxylic acid esters under relatively low pressure conditions without excessive reaction time or high temperature conditions, while not using expensive precious metals such as Pt.

[0015] Accordingly, there is a need to develop a catalyst that can efficiently carry out the hydrogenation reaction of carboxylic acids or carboxylic acid esters under relatively low pressure conditions without excessive reaction time or high temperature conditions, while not using expensive precious metals such as platinum (Pt). Prior art literature

[0017] Japanese Patent Publication No. 1995-165644 Chinese Patent Publication No. 001911504 U.S. Patent Publication No. 6294703 U.S. Patent Publication No. 6495730 International Patent Publication No. WO 2015-156582 The problem to be solved

[0018] The present invention aims to provide a catalyst for a hydrogenation reaction that enables high selectivity and conversion rate under relatively low pressure conditions without excessive reaction time or high temperature conditions in a hydrogenation reaction that converts a carboxyl functional group, an aldehyde functional group, or a ketone functional group into an alcohol functional group.

[0020] The present invention also aims to provide a method for manufacturing the aforementioned catalyst for a hydrogenation reaction. means of solving the problem

[0022] According to one embodiment of the present invention, a catalyst for a hydrogenation reaction is provided, comprising ruthenium and tin as catalytic active metals, wherein the ruthenium content is 30 wt% or more to less than 55 wt% relative to the total weight of the ruthenium and tin, the tin content is greater than 45 wt% to 70 wt% or less, and the ratio (A2 / A1) of the hydrogen adsorption amount (A2) at a temperature of 523 K or lower to the total hydrogen adsorption amount (A1) of the catalyst, as measured by a method according to hydrogen-temperature program reduction (H2-TPR) analysis, is 70 mol% to 99 mol%.

[0024] According to another embodiment of the present invention, a method for manufacturing the catalyst for the hydrogenation reaction is provided.

[0026] According to another embodiment of the present invention, a hydrogenation method is provided for performing a hydrogenation reaction using the catalyst described above. Effects of the invention

[0028] The catalyst for a hydrogenation reaction according to the present invention has an excellent effect of enabling high selectivity and conversion rate under relatively low pressure conditions without excessive reaction time or high temperature conditions in a hydrogenation reaction that converts carboxylic acid functional groups, aldehyde functional groups, or ketone functional groups into alcohol functional groups. Brief explanation of the drawing

[0030] FIG. 1 shows the hydrogen adsorption curves of the passivation layer according to the Hydrogen-Temperature Program Reduction (H2-TPR) analysis for Examples 1 to 2 and Comparative Examples 1 to 3 according to one embodiment of the present invention. Specific details for implementing the invention

[0031] The terms used in this specification are used merely to describe exemplary embodiments and are not intended to limit the invention. The singular expression includes the plural expression unless the context clearly indicates otherwise.

[0033] In this specification, terms such as “comprising,” “comprising,” or “having” are used to describe features, numbers, steps, components, or combinations thereof that are implemented, and do not exclude one or more other features, numbers, steps, components, combinations thereof, or the possibility of addition.

[0035] Additionally, terms such as "approximately" and "substantially" used throughout this specification are used to mean at or near the stated value when inherent manufacturing and material tolerances are presented in the stated meaning, and are used to prevent unscrupulous infringers from unfairly exploiting the disclosure in which precise or absolute values ​​are mentioned to aid in understanding the invention.

[0037] For reference, in this specification, "part by weight" refers to a relative concept in which the weight of one substance is expressed as a ratio to the weight of another substance. 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 are 40 parts by weight and 60 parts by weight, respectively, based on 100 parts by weight of substance A.

[0039] Meanwhile, "weight % (% by weight)" refers to an absolute concept in which the weight of a substance is expressed as a percentage of the total weight. In the mixture given as an example above, the content of substance A, substance B, and substance C is 50 weight%, 20 weight%, and 30 weight%, respectively, out of 100% of the total weight of the mixture.

[0041] The present invention is capable of various modifications and may take various forms, and specific embodiments are illustrated and described in detail below. However, this is not intended to limit the invention to the specific disclosed forms, and it should be understood that the invention includes all modifications, equivalents, and substitutions that fall within the spirit and scope of the invention.

[0043] Hereinafter, the catalyst for a hydrogenation reaction according to the present invention, the method for manufacturing the same, and the hydrogenation method using the same will be described in more detail.

[0045] catalyst for hydrogenation reaction

[0046] According to one embodiment of the present invention, a catalyst for a hydrogenation reaction is provided that enables high selectivity and conversion rate under relatively low pressure conditions without excessive reaction time or high temperature conditions in a hydrogenation reaction that converts a carboxylic acid group, an aldehyde group, or a ketone group into an alcohol group.

[0048] A catalyst for a hydrogenation reaction according to one embodiment of the present invention comprises ruthenium and tin as catalytically active metals.

[0050] Specifically, the catalyst for the hydrogenation reaction is characterized in that the ruthenium content is 30 weight% or more to less than 55 weight% relative to the total weight of the ruthenium and tin, the tin content is greater than 45 weight% to 70 weight% or less, and the ratio (A2 / A1) of the hydrogen adsorption amount (A2) at a temperature of 523 K or lower to the total hydrogen adsorption amount (A1) of the catalyst, as measured by the method according to the Hydrogen-Temperature Program Reduction (H2-TPR) analysis, is 70 mol% to 99 mol%.

[0052] In particular, the catalyst for a hydrogenation reaction according to one embodiment of the present invention is a catalyst intended to include ruthenium and tin, which are catalytically active metals, within a specific range, and to form a homogeneous alloy status with ruthenium and tin. Generally, as a catalyst for a hydrogenation reaction, platinum (Pt) among precious metals is known to have a high hydrogen adsorption capacity, which promotes the reduction of Sn species and prevents the leaching out of Sn that occurs during hydrothermal reactions, thereby improving the performance and stability of the catalyst. However, the above-mentioned catalyst for a hydrogenation reaction exhibits superior hydrogenation reaction performance without using such expensive platinum (Pt), and has the characteristic that no leaching of Sn occurs during the reaction.

[0054] Specifically, the reduction mechanism of the carboxylic acid group on the composite metal (Ru-Sn) of the above-mentioned catalyst for hydrogenation reaction is as follows. Ruthenium (Ru) metal adsorbs hydrogen to form a metal-hydride, and tin (Sn) acts as a Lewis acid site to activate the carboxylic acid group. Subsequently, the metal-hydride binds to the activated carboxylic acid group, aldehyde functional group, or ketone functional group and is converted into an alcohol functional group.

[0056] Meanwhile, in the case of selective hydrogenation reactions that convert carboxylic acid (-(C=O)OH), aldehyde (-(C=O)H), or ketone (-(C=O)-) functional groups into alcohol (-OH) functional groups, as in the present invention, the properties of the metal change depending on the composition of the metal, resulting in variations in the adsorption strength and amount of hydrogen adsorption. In fact, when comparing Ru-Sn and Ni-Sn metals used in the reduction reaction of similar carboxylic acid groups, using Ni metal may result in the need for longer reaction times and higher reaction temperatures under similar conditions. This is a result of the fact that Ru metal has significantly superior hydrogen adsorption capabilities compared to Ni metal.

[0058] Specifically, the catalyst for the hydrogenation reaction has a ruthenium content of 30% or more to less than 55% by weight relative to the total weight of the ruthenium and tin, and a tin content of more than 45% by weight to 70% by weight or less. 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. Additionally, 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.

[0060] In addition, a catalyst for a hydrogenation reaction according to one embodiment of the present invention is characterized by including ruthenium as the catalytic active metal in a range effective for catalytic action. Specifically, ruthenium as the catalytic active metal may be included in an amount of 1 part by weight or more to 11 parts by weight or less relative to the total weight of the catalyst. More specifically, ruthenium as the catalytic active metal may be included in an amount of 1.5 parts by weight or more to 10.5 parts by weight or less, or 2 parts by weight or more to 10 parts by weight or less, or 3.5 parts by weight or more to 9.5 parts by weight or less, or 4.5 parts by weight or more to 9 parts by weight or less, or 4.8 parts by weight or more to 8 parts by weight or less, or 5.0 parts by weight or more to 7.5 parts by weight or less, or 5.1 parts by weight or more to 7 parts by weight or less relative to the total weight of the catalyst. In particular, when ruthenium is included in a high content, that is, when ruthenium is included in an amount exceeding 11 parts by weight, there is a disadvantage that the price of the catalyst increases. In addition, there is a problem that additional process costs may occur as the size of the active metals, including ruthenium and tin, constituting the catalyst increases, leading to a decrease in the selectivity of the target product. Furthermore, if ruthenium is included in an amount of less than 1 weight part, the conversion efficiency is low, which may result in a decrease in the production efficiency of 1,4-butanediol (1,4-BDO) in the hydrogenation reaction.

[0062] And, the tin as the catalyst active metal may be included 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.

[0064] In addition, among the catalyst active metals, the tin may be included in a weight ratio 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 relative to the ruthenium on a weight basis.

[0066] In a catalyst for a hydrogenation reaction according to one embodiment of the present invention, it is preferable to include ruthenium and tin as catalytic active metals within the range described above. If included below the above-described content range, the conversion efficiency of the reaction may decrease or the selectivity of the target product may be reduced, potentially leading to excessive separation and recovery costs during the process. Specifically, if the content of ruthenium among the catalytic active metals in the hydrogenation reaction catalyst is less than 1 weight part, when a hydrogenation reaction is performed using a carboxylic acid group, an aldehyde group, or a ketone group as an alcohol group, the conversion efficiency to a target product containing an alcohol group, such as 1,4-butanediol (BDO), decreases. Conversely, if included in excess of the above-described content range, the dispersion of the metal decreases, causing the crystal size to increase, which may also result in a decrease in conversion efficiency.

[0068] Meanwhile, the particle size of the active metal among the catalysts for the hydrogenation reaction 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 value of the measured particles, for example, the value of the particle size of 100 samples measured by 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 reaction 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 reaction 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.

[0070] In particular, the hydrogenation reaction using the catalyst of the present invention is, for example, a conversion reaction into a linear alcohol through the selective hydrogenation of a dicarboxylic acid. In such a hydrogenation reaction, the catalyst acts as a medium that adsorbs hydrogen, a reducing agent, and supplies it to the reactants; however, if smooth hydrogen transfer does not occur, a reverse reaction (oxidation reaction) of the converted product may occur. Therefore, in order for the forward hydrogenation reaction to occur efficiently, it is desirable to include ruthenium and tin, which are catalytically active metals, within the content range described above.

[0072] Meanwhile, a catalyst for a hydrogenation reaction according to one embodiment of the present invention is characterized by including ruthenium and tin, which are catalytically active metals as described above, within a specific range, and having ruthenium and tin in a homogeneous alloy status, with the ratio (A2 / A1) of the amount of hydrogen adsorbed at a temperature of 523 K or lower to the total amount of hydrogen adsorbed by the H2-TPR (Hydrogen-Temperature Program Reduction) analysis being 70 mol% to 99 mol%.

[0074] In this context, the H2-TPR (temperature programmed reduction) method is an analytical technique that measures the behavior of gases adsorbed or desorbed according to the catalyst temperature; however, the adsorption behavior characteristics can vary depending on the type of metal, the loading amount, and the distribution pattern of the metals. In particular, even if ruthenium and tin satisfy a specific weight ratio within the catalyst, a problem may arise where catalytic activity decreases sharply if the metals are segregated rather than forming an alloy status.

[0076] Specifically, the hydrogenation reaction catalyst may have a ratio (A2 / A1) of the hydrogen adsorption amount (A2) at a temperature of 523 K or lower relative to the total hydrogen adsorption amount (A1) of the catalyst, measured by the H2-TPR (Hydrogen-Temperature Program Reduction) analysis method, 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.

[0078] A specific method for H2-TPR (Hydrogen-Temperature Program Reduction) analysis of a catalyst for a hydrogenation reaction according to one embodiment of the present invention is as described in Example 1 below.

[0080] For example, Hydrogen-Temperature Program Reduction (H2-TPR) analysis is an analytical method for evaluating the amount of hydrogen adsorbed onto a metal at a specific reaction temperature, and the detailed measurement method is as follows.

[0082]

[0083] - Pre-treatment: Catalyst pretreatment and TCD signal stabilization

[0084] ① Inert gas (Ar or N2) is flowed through the catalyst bed and the temperature is increased to 373 K at a rate of 5 K / min;

[0085] ② Flow inert gas through the catalyst bed and maintain at 373 K for 30 minutes;

[0086] ③ Cooling to 323 K while flowing inert gas through the catalyst bed;

[0087] ④ Inert gas and hydrogen were mixed and flowed through the catalyst bed 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.

[0089] - H2-TPR analysis

[0090] ① Analytical gas: H2 / Ar 5% mixture 30 sccm (standard cubic centimeter per minute)

[0091] ② Increase temperature to 1073 K at a rate of 5 K / min

[0093] ​More specifically, in the present invention, the area corresponding to the total moles of hydrogen adsorbed by the passivation layer surrounded by the H2-TPR curve 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 moles of hydrogen adsorbed within the hydrogenation reaction temperature surrounded by the H2-TPR curve and baseline in the range 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.

[0095] By performing analysis with H2-TPR in the manner described above, the ratio of the amount of hydrogen adsorbed at a temperature of 523K or lower to the total amount of hydrogen adsorbed by the catalyst can be measured.

[0097] In particular, during a hydrogenation reaction that converts carboxylic acid, aldehyde, or ketone functional groups into alcohol functional groups, the catalyst adsorbs hydrogen. Since hydrogen adsorbed by the catalyst at temperatures above the reaction temperature does not participate in the reaction, the amount of hydrogen adsorbed / desorbed at 523 K or lower has a significant effect on the reaction activity. Therefore, the hydrogenation catalyst must satisfy the aforementioned range for hydrogen adsorption at 523 K or lower in the H2-TPR graph.

[0099] For example, the catalytic performance when performing a hydrogenation reaction can be predicted from the hydrogen adsorption curve of the passivation layer for the above-mentioned hydrogenation reaction catalyst.

[0101] Specifically, since the performance of the catalyst in the present invention is measured by a liquid-phase hydrothermal reaction in a batch reactor, the reduction of the catalyst prior to activity evaluation can be carried out ex-situ. In particular, because the catalyst in a metallic state is flammable, it can be handled after being stabilized through passivation following reduction. In particular, the catalyst according to one embodiment of the present invention converts reactants into target products through a hydrogenation reaction. At this time, the hydrogen adsorption behavior characteristic plays the most important role.

[0103] For example, since a catalyst in a passivated state is introduced into the reactor before the catalytic reaction and hydrogen is pressurized after the temperature is raised to the reaction temperature (503 K), hydrogen adsorbed at approximately 523 K or higher cannot participate in the reaction. In addition, due to the mechanism of the catalytic reaction, a hydrogenation reaction occurs on the surface of the Ru-Sn metal. That is, if Ru-Sn does not form an alloy form and forms an independent metal phase, by-products are generated through gamma-butylactone or gasification reactions rather than conversion to the target product, such as 1,4-butanediol.

[0105] Therefore, when Ru-Sn metals are well mixed, a single hydrogen adsorption peak occurs in H2-TPR analysis, and the difference in heating rate (5 o Broadness is determined by the size of the Ru-Sn metal and the C / min.

[0107] Thus, for a hydrogenation reaction catalyst according to one embodiment of the present invention, the hydrogen adsorption curve of the passivation layer can predict the hydrogen adsorption curve of the ruthenium and tin composite metal (Ru-Sn alloy) participating in the reaction in the actual catalytic reaction.

[0109] In particular, even if similar hydrogen adsorption curves are observed through H2-TPR (Hydrogen-Temperature Program Reduction) analysis, there may be limitations on the metal series capable of participating in the hydrogenation reaction as catalysts. While commonly known single catalysts from the noble metal series, such as Pd, Ru, Ni, and Pt, exhibit hydrogen adsorption behavior within a similar range, their catalytic activity is reduced due to poor activation performance of carbonyl groups (C=O) among the reactants. In other words, for the reduction reaction to occur efficiently in the hydrogenation pathway of carbonyl groups, as mentioned above, a ruthenium-tin (Ru-Sn) composite metal catalyst containing ruthenium and tin in optimal ranges as catalytic active metals requires an activation reaction by an oxygen-friendly metal such as tin to facilitate stable hydrogen adsorption to carbonyl groups (C=O).

[0111] However, in order to reinforce overall process stability or reaction efficiency, the catalyst for a hydrogenation reaction 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 catalytic active metals. When additional catalytic active metals are included in this way, for example, when Pt is additionally included, the reduction of Sn species is promoted and the leaching out of Sn occurring during the reaction is prevented, thereby achieving higher performance.

[0113] In addition to ruthenium and tin as the catalytic active metals, if one or more transition metals selected from the group consisting of palladium (Pd), rhodium (Rh), platinum (Pt), iron (Fe), rhenium (Re), and gallium (Ga) are additionally contained, the amount of one or more metals may preferably be 5 or less or 0.1 to 5, more preferably 2 or less or 0.2 to 2, in terms of their atomic ratio to ruthenium. For example, based on the atomic ratio of ruthenium (Ru), the atomic ratio of one or more additional transition metals among palladium (Pd), rhodium (Rh), platinum (Pt), iron (Fe), rhenium (Re), and gallium (Ga) (ruthenium: atomic ratio of additional transition metals) 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.

[0115] However, including additional metals in this way has the disadvantage of increasing the overall cost of manufacturing the catalyst. In particular, the catalyst for a hydrogenation reaction according to one embodiment of the present invention includes ruthenium and tin, which are catalytically active metals, within a specific range, and optimizes the ratio of hydrogen adsorption amount according to H2-TPR (Hydrogen-Temperature Program Reduction) analysis to form a homogeneous alloy status, thereby exhibiting superior hydrogenation reaction performance without using the aforementioned expensive Pt (about twice the price of Ru), and has the characteristic that no leaching of Sn occurs during the reaction.

[0117] Accordingly, a catalyst for a hydrogenation reaction according to one embodiment of the present invention preferably comprises only ruthenium and tin as catalytically active metals.

[0119] Meanwhile, the above-mentioned catalytic active metal is supported on a porous carbon-based carrier.

[0121] According to one embodiment of the present invention, a ruthenium-tin (Ru-Sn) composite metal catalyst containing ruthenium and tin as catalytically active metals in an optimal range is suitable for use with a carbon-based support, particularly a porous carbon-based support, because the hydrogenation reaction proceeds under high-temperature hydrothermal reaction conditions during actual application. If a generally known alumina or silica-based support is used, it becomes unstable under hydrothermal reaction conditions, causing a phase transformation, which can significantly reduce catalytic activity when used as a support for the catalyst.

[0123] The porous carbon-based carrier is not particularly limited, but at least one selected from the group consisting of activated carbon, carbon black, graphite, graphene, ordered mesoporous carbon (OMC), and carbon nanotubes may be used. Preferably, it may be carbon black with a high proportion of mesopores among the total pores; in specific examples, the activated carbon may be SX ULTRA, CGSP, PK1-3, SX 1G, DRACO S51HF, CA-1, A-51, GAS 1240 PLUS, KBG, CASP, and SX PLUS, etc., and the carbon black may be BLACK PEARLS ® , ELFTEX®, VULCAN®, MOGUL®, MONARCH®, EMPEROR ® and REGAL ® It may be, but is not limited to, etc.

[0125] For example, the porous carbon-based carrier has a pore volume of 0.1 cm² 3 / g to 1.5 cm 3 / g, or 0.3 cm 3 / g to 1.5 cm 3 / g, or 0.6 cm 3 / g to 1.5 cm 3 / g can be.

[0127] Here, in the carbon-based carrier, the carbon may have a volume ratio of mesopores with a pore size of 2 nm to 50 nm of 50% or more among the total pores. Preferably, in the carbon carrier, the carbon may have a volume ratio of mesopores of 70% or more among the total pores, and more preferably, in the carbon carrier, the carbon may have a volume ratio of mesopores of 75% or more among the total pores.

[0129] At this time, if the volume ratio of the above mesopores is less than 50%, there may be a problem with the microscopic mass transfer rate of reactants and products within the carbon carrier, and if the average size of the above pores exceeds 50 nm, there may be a problem with the physical strength of the carrier being weak, so the above range is suitable.

[0131] In addition, the carbon-based carrier has a BET specific surface area of ​​100 m² 2 / g to 1,500 m 2 It comprises ordered mesoporous carbon (OMC) having a range of / g. Preferably, the carbon has a specific surface area (BET) of 200 m² 2 / g to 1,000 m 2 It may include ordered mesoporous carbon (OMC) covering the range of / g.

[0133] At this time, the specific surface area of ​​the carbon-based carrier is 100 m² 2 If it is less than / g, there may be a problem with difficulty in high dispersion of active metals (Ru, Sn), and the specific surface area of ​​the carbon is 1,500 m² 2 If it exceeds / g, there may be a problem with the ratio of mesopores decreasing, so the above range is suitable.

[0135] Meanwhile, the above-mentioned catalyst for the hydrogenation reaction has a BET specific surface area of ​​100 m² 2 / g to 1,500 m 2 / g, or 200 m 2 / g to 1,500 m 2 / g, or 350 m 2 / g to 800 m 2 / g, or 550 to 670 m 2 It can be / g.

[0137] In addition, the above-mentioned catalyst for hydrogenation reaction 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.

[0139] A catalyst for a hydrogenation reaction according to one embodiment of the present invention includes ruthenium and tin, which are catalytically active metals, within a specific range, and forms a homogeneous alloy status with ruthenium and tin, thereby effectively converting carboxylic acid groups, aldehyde groups, or ketone groups into alcohol groups, such as primary alcohols, directly by hydrogenation without esterification thereof, and in such a hydrogenation reaction, high selectivity and conversion rate can be achieved under relatively low pressure conditions without excessive reaction time or high temperature conditions.

[0141] Method for preparing a catalyst for hydrogenation reaction

[0142] Accordingly, according to another embodiment of the present invention, a method for manufacturing the above-described catalyst for a hydrogenation reaction is provided.

[0144] Specifically, the method for manufacturing the catalyst for the hydrogenation reaction comprises: a step of preparing a metal precursor solution by 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; and a step of reducing the metal precursor solution or a mixture containing the same in the presence of hydrogen gas after drying; wherein the ruthenium content in the metal precursor solution is 30% by weight or more to less than 55% by weight relative to the total weight of ruthenium and tin, and the tin content is greater than 45% by weight or less to 70% by weight relative to the total weight of ruthenium and tin.

[0146] In particular, the precursor compound containing ruthenium as the catalytic active metal is one or more selected from the group consisting of ruthenium metal, ruthenium chloride, ruthenium nitrate, acetylacetonator ruthenium, ruthenium carbonyl, ruthenium oxalate, and ruthenium nitrosyl nitrate.

[0148] In addition, the precursor compound containing tin as the catalytic active metal is one or more selected from the group consisting of tin chloride (II), sodium tartrate, tin acetate (II), tin fluoride, and tin iodide.

[0150] In the method for preparing a catalyst for a hydrogenation reaction according to the present invention, a metal precursor solution is prepared using an acidic aqueous solution to completely dissolve the aforementioned precursor compound or mixture containing ruthenium and tin, thereby completely ionizing the precursor compound. By using such an acidic aqueous solution, ruthenium and tin do not solidify in a separated state, but can form an alloy in the form of a solid solution. Due to this characteristic, a broad and symmetrical hydrogen adsorption peak can be observed in the hydrogen adsorption curve graph for the catalyst for a hydrogenation reaction according to one embodiment of the present invention. Thus, the catalyst for a hydrogenation reaction according to one embodiment of the present invention achieves superior hydrogenation reaction performance without additionally using expensive Pt, and obtains excellent effects in that no leaching of Sn occurs during the reaction.

[0152] However, in the step of preparing the metal precursor solution, if an acidic aqueous solution is not used, Sn and Ru are supported in a segregated state, and even if the same amount of metal precursor compound is used, the catalytic activity may be reduced. In the hydrogen adsorption curve graph for the final prepared catalyst, independent hydrogen adsorption peaks for Ru and Sn occur, and the reduction mechanism of the carboxylic acid group on the composite metal (Ru-Sn) is not properly carried out, and thus does not operate efficiently in this catalytic reaction.

[0154] Such acidic aqueous solutions may contain one or more of hydrochloric acid, nitric acid, and acetic acid, and an acidic aqueous solution with a concentration of 0.1% to 10% by weight may be used to sufficiently dissolve the precursor compound or a mixture thereof. For example, ion-exchanged water containing 1% to 5% by weight of hydrochloric acid may be used as the acidic aqueous solution. In a method for manufacturing a catalyst for a hydrogenation reaction, if an excessive amount of the acidic aqueous solution is used, corrosive gases such as HCl are excessively generated during the subsequent reduction process, which can cause corrosion of the reactor or process and act as a catalyst poison. Therefore, it is preferable to use it in the minimum content within the range described above.

[0156] In addition, the ruthenium content in the metal precursor solution is 30% by weight or more to less than 55% by weight relative to the total weight of ruthenium and tin, and the tin content is more than 45% by weight or less relative to the total weight of ruthenium and tin.

[0158] The objective is to include ruthenium and tin, which are catalytically active metals, in the above-mentioned metal precursor solution within a specific optimized range, so that ruthenium and tin form a homogeneous alloy status in the final composite metal catalyst.

[0160] Specifically, the ruthenium content in the metal precursor solution may be included in an amount of 1 part by weight or more to 11 parts by weight or less relative to the total weight of the catalyst produced. More specifically, the ruthenium content in the metal precursor solution may be included in an amount of 1.5 parts by weight or more to 10.5 parts by weight or less relative to the total weight of the catalyst produced, or 2 parts by weight or more to 10 parts by weight or less, or 3.5 parts by weight or more to 9.5 parts by weight or less, or 4.5 parts by weight or more to 9 parts by weight or less, or 4.8 parts by weight or more to 8 parts by weight or less, or 5.0 parts by weight or more to 7.5 parts by weight or less, or 5.1 parts by weight or more to 7 parts by weight or less relative to the total weight of the catalyst produced. In particular, when ruthenium is included in a high amount, that is, when ruthenium is included in an amount exceeding 11 parts by weight, there is a disadvantage that the price of the catalyst increases. In addition, there is a problem that additional process costs may arise as the size of the active metals, including ruthenium and tin, constituting the catalyst increases, leading to a decrease in the selectivity of the target product. Furthermore, if ruthenium is included in an amount of less than 1 weight part, the conversion efficiency is low, which may result in a decrease in the production efficiency of the target product, such as 1,4-butanediol (BDO), in the hydrogenation reaction.

[0162] And, the tin content in the metal precursor solution may be included in an amount of 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 produced.

[0164] In addition, the content of tin in the metal precursor solution may be included in a weight ratio of 0.8 to 2.67, or 0.9 to 2.5, or 1.0 to 2.4, or 1.1 to 2.3 relative to the content of ruthenium on a weight basis. Above the weight ratio range described above, the efficiency of the selective reduction reaction of the carbonyl group decreases because they exist in their respective independent metal forms rather than as an alloy of ruthenium and tin. Consequently, the conversion may result in a lower conversion efficiency, as the intermediate product, an esterified compound such as gamma-butyrolactone (GBL) or an ether compound such as tetrahydrofuran (THF), is converted rather than the target product, a compound containing an alcohol functional group such as 1,4-butanediol (BDO).

[0166] In the above metal precursor solution, the more specific content range and weight ratio of ruthenium and tin, which are catalytically active metals, can be applied at a level that enables the finally manufactured composite metal catalyst to achieve the range previously described in relation to catalysts for hydrogenation reactions, and specific details regarding this are omitted.

[0168] Meanwhile, the method for manufacturing a catalyst for a hydrogenation reaction according to the present invention is characterized by manufacturing by impregnating Ru and Sn precursors through an impregnation method, such as an initial wet impregnation method, followed by drying and reduction, in order to include ruthenium and tin contained in the catalyst as described above within a specific optimized range.

[0170] Specifically, the method for manufacturing the catalyst for the hydrogenation reaction further includes, after the step of preparing the metal precursor solution as described above, a step of mixing the metal precursor solution with a porous carbon-based support. This mixing step may be part of the step of supporting ruthenium and tin as the catalytically active metals on the porous carbon-based support.

[0172] The specific types and ranges of physical properties of the above-mentioned porous carbon-based carriers are as described above, and thus, a detailed description is omitted.

[0174] In particular, the metal precursor solution or a mixture containing it is dried under temperature conditions of 323 K to 473 K, and then reduced under temperature conditions of 473 K to 773 K in the presence of hydrogen gas.

[0176] Additionally, after the reduction treatment step, the method further includes a step of passivating the reduced product generated in the reduction treatment step to form a passivation layer.

[0178] The above passivation step is to passivate the reduction product with a nitrogen mixed gas containing 0.1 to 20% oxygen by volume.

[0180] Hydrogenation method

[0181] Accordingly, according to another embodiment of the present invention, a hydrogenation method is provided for performing a hydrogenation reaction using the catalyst described above.

[0183] The hydrogenation method according to the present invention is characterized by performing a hydrogenation reaction that converts a carboxylic acid group, an aldehyde group, or a ketone group into an alcohol group in the presence of the aforementioned catalyst for hydrogenation reaction.

[0185] Specifically, 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.

[0187] Meanwhile, the carboxylic acid compound containing the above-mentioned carboxylic acid functional group is one or more 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, isostearyl acid, oleic acid, maleic acid, sebacic acid, cyclohexanecarboxylic acid, benzoic acid, and their anhydrides. Specifically, the carboxylic acid compound containing the carboxylic acid functional group may be one or more of succinic acid, succinic anhydride, maleic acid, and maleic anhydride, or two or more of them.

[0189] In addition, the aldehyde-based compound containing the aldehyde functional group is one or more selected from the group consisting of formaldehyde, propionaldehyde, n-butylaldehyde, isobutylaldehyde, valeraldehyde, 2-methylbutylaldehyde, 3-methylbutylaldehyde, 2,2-dimethylpropionaldehyde, capronaldehyde, 2-methylvaleraldehyde, 3-methylvaleraldehyde, 4-methylvaleraldehyde, 2-ethylbutylaldehyde, 2,2-dimethylbutylaldehyde, 3,3-dimethylbutylaldehyde, caprylaldehyde, caprinaldehyde, and glutaldialdehyde. Specifically, the aldehyde-based compound containing the aldehyde functional group may be n-butylaldehyde.

[0191] In addition, the ketone compound containing the ketone functional group is one or more selected from the group consisting of acetone, butanone, pentanone, hexanone, cyclohexanone, and acetophenone. Specifically, the ketone compound containing the ketone functional group may be butanone.

[0193] Meanwhile, the above hydrogenation reaction has a conversion rate of 70% or more, represented by Formula 1 below, or from 70% or more to 100%.

[0194] [Equation 1]

[0195] Conversion Rate (%) =

[0196] In the above Equation 1,

[0197] The number of moles of the supplied reactant represents the number of moles of the compound supplied to the hydrogenation reaction among compounds containing a carboxylic acid group, an aldehyde group, or a ketone group, and

[0198] The number of moles of consumed reactants represents the number of moles of compounds consumed in the hydrogenation reaction among compounds containing a carboxylic acid group, an aldehyde group, or a ketone group.

[0200] The above conversion rate is a value calculated by determining the molar ratio of the reactant consumed in the hydrogenation reaction to the reactant 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 through the hydrogenation reaction, and the above conversion rate may preferably be 90% or more, or 90% or more to 99.9%.

[0202] In addition, the hydrogenation reaction has a selectivity of 50% or more, represented by Formula 2 below, or from 50% or more to 90%.

[0203] [Equation 2]

[0204] Selectivity (%) =

[0205] In the above Equation 2,

[0206] The total number of moles of the product represents the total number of moles of the product produced from the hydrogenation reaction, and

[0207] The number of moles of a compound containing an alcohol functional group represents the number of moles of a compound containing an alcohol functional group converted from a carboxylic acid functional group, an aldehyde functional group, or a ketone functional group among the products generated from the hydrogenation reaction.

[0209] The above selectivity is a value calculated by determining the molar ratio of a compound containing an alcohol functional group corresponding to the target compound of the present invention among the products generated through the hydrogenation reaction, and the above selectivity may preferably be 55% or more, or 55% or more to 70%.

[0211] In addition, the above hydrogenation reaction has a yield of 50% or more, or from 50% or more to 90%, as represented by Formula 3 below.

[0212] [Equation 3]

[0213] Yield (%) =

[0215] The above yield is a value calculated for the yield of a compound containing an alcohol functional group produced through a hydrogenation reaction, and the yield may preferably be 55% or more, or 55% or more to 70%.

[0217] In particular, the catalyst for a hydrogenation reaction according to one embodiment of the present invention has excellent effects of securing alcohol compounds in high yield and having high selectivity and conversion rate as described above, even under relatively low pressure conditions and without excessive reaction time or high temperature conditions, in a hydrogenation reaction that converts carboxylic acid functional groups, aldehyde functional groups, or ketone functional groups into alcohol functional groups.

[0219] The present invention will be explained in more detail below through the following examples. However, the following examples are merely illustrative of the present invention and the scope of the present invention is not limited thereto.

[0221] [Example]

[0222] Example 1

[0223] Activated carbon as a porous carbon carrier (pore volume: 0.65 cm³) 3 / g) was used, and the porous carbon carrier was placed in a drying oven set to a temperature of 373 K and stored for 24 hours to remove residual moisture absorbed within the carbon carrier.

[0225] In addition, an acidic aqueous solution to which hydrochloric acid was added was used to completely dissolve approximately 0.65 g of tin chloride (II), SnCl2·2H2O. At this time, the acidic aqueous solution was used by adjusting the total concentration to 1 wt% using 35% grade reagent-grade hydrochloric acid. Approximately 0.03 g of ruthenium chloride, RuCl3·3H2O was mixed and completely dissolved for approximately 3 hours so that ruthenium metal equivalent to approximately 80 wt% of the tin metal could be added to the tin precursor solution. At this time, the weight ratio of ruthenium / (ruthenium+tin) in the metal precursor solution was prepared to be 44.4 wt%.

[0227] The above-mentioned metal precursor solution obtained in this way was uniformly mixed with a porous carbon support using a mortar and pestle. The well-mixed metal-carbon mixture was placed in a drying oven set to a temperature of 373 K and dried for more than 12 hours. Before the catalyst activity test, the dried metal-carbon mixture was reduced under a hydrogen gas flow at a temperature of 623 K for about 3 hours, and after reduction, the powder catalyst was passivated for 3 hours using a nitrogen mixed gas containing 1% oxygen to prepare a hydrogenated powder catalyst.

[0229] The hydrogenation powder catalyst of Example 1 prepared in this way, i.e., the passivated catalyst, was analyzed using H2-TPR in the following manner to measure the ratio of the amount of hydrogen adsorbed at a temperature of 523K or lower to the total amount of hydrogen adsorbed by the catalyst.

[0231] Specifically, Hydrogen-Temperature Program Reduction (H2-TPR) analysis is an analytical method for evaluating the amount of hydrogen adsorbed onto a metal at a specific reaction temperature, and the detailed measurement method is as follows.

[0233]

[0234] - Pre-treatment: Catalyst pretreatment and TCD signal stabilization

[0235] ① Inert gas (Ar or N2) is flowed through the catalyst bed and the temperature is increased to 373 K at a rate of 5 K / min;

[0236] ② Flow inert gas through the catalyst bed and maintain at 373 K for 30 minutes;

[0237] ③ Cooling to 323 K while flowing inert gas through the catalyst bed;

[0238] ④ Inert gas and hydrogen were mixed and flowed through the catalyst bed 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.

[0240] - H2-TPR analysis

[0241] ① Analytical gas: H2 / Ar 5% mixture 30 sccm (standard cubic centimeter per minute)

[0242] ② Increase temperature to 1073 K at a rate of 5 K / min

[0244] ​In the manner described above, the hydrogen adsorption curve of the passivation layer analyzed by H2-TPR for the hydrogenation powder catalyst of Example 1, i.e., the passivated catalyst, is shown in FIG. 1.

[0246] In addition, A1 was defined as the area corresponding to the total moles of hydrogen adsorbed by the passivation layer surrounded by the baseline and the H2-TPR curve from the initial temperature of 333 K to the metal reduction temperature of 973 K in Fig. 1, and A2 was defined as the area corresponding to the moles of hydrogen adsorbed within the hydrogenation reaction temperature surrounded by the H2-TPR curve and baseline in the range from the initial temperature of 333 K to the hydrogenation reaction temperature of 523 K, and the ratio (mol%) of A2 to A1 was shown in Table 1. The A2 / A1 ratio in Example 1 measured in this way was 94.5 mol%.

[0248] In addition, the metal content contained 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. .

[0250] The ruthenium content of the hydrogenation powder catalyst of Example 1, i.e., the passivated catalyst, was measured to be 51,600 ppm by weight and the tin content to be 59,120 ppm of the total catalyst; the size of the active metal measured by transmission electron microscopy (TEM) was approximately 3.5–5.5 nm, and the average particle size was approximately 4.5 nm. In addition, the BET specific surface area of ​​the hydrogenation powder catalyst was 603 m² 2 / g, and the average pore diameter was measured to be 4.1 nm. The specific results of measuring the physical properties of the hydrogenation powder catalyst of Example 1 are shown in Table 1 below.

[0252] Example 2

[0253] In Example 1, the hydrogenation powder catalyst of Example 3 was prepared by performing drying, reduction, passivation, etc., in the same manner as in Example 1, except that the weight ratio of ruthenium / (ruthenium+tin) in the metal precursor solution, i.e. Ru / Ru+Sn, was varied to 31 wt% and uniformly mixed on a porous carbon support.

[0255] Figure 1 shows the hydrogen adsorption curve of the passivation layer analyzed by H2-TPR in the same manner as described above for the hydrogenation powder catalyst of Example 2 prepared in this way, i.e., the passivated catalyst.

[0257] In addition, the physical properties of the hydrogenation powder catalyst of Example 2, i.e., the passivated catalyst, were evaluated using the same method 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 by weight and the tin content was 117,700 ppm of the total catalyst; the size of the active metal measured by TME was approximately 5–10 nm, and the average particle size of the active metal was approximately 7.5 nm. Furthermore, the BET specific surface area of ​​the hydrogenation powder catalyst was 573 m² 2 / g, and the average pore diameter was measured to be 4.3 nm. The specific results of measuring the physical properties of the hydrogenation powder catalyst of Example 2 are shown in Table 1 below.

[0259] Comparative Example 1

[0260] In Example 1, the hydrogenation powder catalyst of Comparative Example 1 was prepared by performing drying, reduction, passivation, etc., in the same manner as in Example 1, except that the weight ratio of ruthenium / (ruthenium+tin) in the metal precursor solution, i.e. Ru / Ru+Sn, was varied to 24 wt% and uniformly mixed on a porous carbon support.

[0262] Figure 1 shows the hydrogen adsorption curve of the passivation layer analyzed by H2-TPR in the same manner as described above for the hydrogenation powder catalyst of Comparative Example 1 prepared in this way, i.e., the passivated catalyst.

[0264] In addition, the physical properties of the hydrogenation powder catalyst of Comparative Example 1, i.e., the passivated catalyst, were evaluated in the same manner as in Example 1, and the measurement results are shown in Table 1 below.

[0266] Comparative Example 2

[0267] In Example 1, the hydrogenation powder catalyst of Comparative Example 2 was prepared by performing drying, reduction, passivation, etc., in the same manner as in Example 1, except that the weight ratio of ruthenium / (ruthenium+tin) in the metal precursor solution, i.e. Ru / Ru+Sn, was varied to 100 wt% and uniformly mixed on a porous carbon support.

[0269] Figure 1 shows the hydrogen adsorption curve of the passivation layer analyzed by H2-TPR in the same manner as described above for the hydrogenation powder catalyst of Comparative Example 2 prepared in this way, i.e., the passivated catalyst.

[0271] In addition, the physical properties of the hydrogenation powder catalyst of Comparative Example 2, i.e., the passivated catalyst, were evaluated in the same manner as in Example 1, and the measurement results are shown in Table 1 below.

[0273] Comparative Example 3

[0274] In Example 1, 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 a metal precursor solution was prepared using an aqueous solution that does not contain hydrochloric acid, i.e., ion-exchanged water, instead of an acidic aqueous solution, and then uniformly mixed on a porous carbon support. Except for these steps, the hydrogenation powder catalyst of Comparative Example 3 was prepared by performing drying, reduction, passivation, etc., in the same manner as in Example 1.

[0276] Figure 1 shows the hydrogen adsorption curve of the passivation layer analyzed by H2-TPR in the same manner as described above for the hydrogenation powder catalyst of Comparative Example 3 prepared in this way, i.e., the passivated catalyst.

[0278] In addition, the physical properties of the hydrogenation powder catalyst of Comparative Example 3, i.e., the passivated catalyst, were evaluated in the same manner as in Example 1, and the measurement results are shown in Table 1 below.

[0280] The weight ratio between the metal components Ru and Sn in the metal precursor solution and the results of measuring the physical properties of the generated hydrogenation powder catalyst in Examples 1 to 2 and Comparative Examples 1 to 3 are as shown in Table 1 below.

[0282] Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Metal precursor solution Ru / Ru+Sn(wt%) 44.4 31 24 100 47 Sn / Ru+Sn(wt%) 55.6 69 76 0 53 Types of solvents Acidic aqueous solution containing hydrochloric acid Acidic solution containing hydrochloric acid Acidic solution containing hydrochloric acid Acidic solution containing hydrochloric acid Aqueous solution containing no hydrochloric acid Hydrogenation powder catalyst A2 (mole) 3.62 2.62 1.67 1.94 2.65 A1 (mole) 3.82 2.91 2.58 0.90 4.25 A2 / A1(mol%) 94.5 87.7 64.9 68.3 58.6 Ru (ppm) 51600 52480 51550 49950 51450 Sn (ppm) 59120 117700 163900 0 61250 Sn(ppm) / Ru(ppm) 1.1457 2.2428 3.1794 0 1.1905 BET specific surface area of ​​the catalyst (m² 2 / g) 603 573 514 687 617 Average pore diameter (nm) of the catalyst 4.1 4.3 4.2 4.4 4.6 Average particle size of active metal in catalyst (nm) 4.5 7.5 13 3.5 5.5

[0284] In Table 1 above, A2 / A1, which is the percentage ratio of the area A2 where hydrogen is adsorbed within the hydrogenation reaction temperature to the total hydrogen adsorption area A1, was calculated by analyzing with TPR to measure the total hydrogen adsorption area from 333 K to 973 K as A1, and the area A2 where hydrogen is adsorbed within the hydrogenation reaction temperature from 333 K to 523 K as A2, and then calculating the percentage ratio A2 / A1.

[0286] Experimental Example 1

[0287] The hydrogenation reaction of succinic acid was carried out in the following manner using the hydrogenation powder catalysts of Examples 1 and 2 and Comparative Examples 1 to 3, and the measurement results for the succinic acid conversion rate (mol%), the selectivity (mol%) of the major compound in the product, and the yield (%) of 1,4-butanediol according to each catalyst are shown in Table 2 below.

[0289] Specifically, the hydrogenation reaction of succinic acid was carried out using a batch reactor. Succinic acid mixed with 0.75 g of catalyst and 150 mL of 1,4-dioxane solvent was introduced into an autoclave reactor at a concentration of 2 wt%. To minimize oxidation reactions and other side reactions, air contained inside the reactor was evacuated using hydrogen as the reaction medium. Then, the reactor was secured, and the internal temperature was raised to 503 K while agitating at a speed of 300 rpm. After reaching the reaction temperature, hydrogen was pressurized to a pressure of 90 bar, and the stirring speed was increased to 1000 rpm and maintained for 6 hours. During this time, the reaction product was collected at time intervals using a sampling port attached to the reactor.

[0291] Then, the reaction products obtained after the reaction were analyzed by gas chromatography (GC) using an Agilent DB-FFAP, HP-5 column equipped with each respective column. At this time, the conversion rate of succinic acid, the selectivity of the product, and the yield of 1,4-butanediol were calculated using the following Equations 1a to 3a.

[0292] [Equation 1a]

[0293] Succinic acid conversion rate (%) =

[0295] [Equation 2a]

[0296] Selectivity of 1,4-butanediol (%) =

[0298] [Equation 3a]

[0299] Yield of 1,4-butanediol (%) =

[0301] Conversion rate (mol%) Selectivity (mol%) 1,4-Butanediol Yield (%) gamma-butyrolactone Tetrohydrofuran 1,4-butanediol Example 1 99.5 22.7 1.7 61.4 61.1 Example 2 99.9 46.3 6.5 55.9 55.8 Comparative Example 1 65 73.5 7.6 11.2 7.3 Comparative Example 2 43 95.8 2 0.5 0.2 Comparative Example 3 56 85.0 1.5 13.5 7.6

[0303] As shown in Table 2 above, when the hydrogenation reaction of succinic acid was performed using the catalysts of Examples 1 and 2, which contain ruthenium and tin as catalytically active metals according to the present invention within a predetermined range and in which ruthenium and tin form a homogeneous alloy status, it can be seen that 1,4-butanediol can be produced in high yield with high selectivity for the alcohol compound 1,4-butanediol and a high conversion rate at the same time compared to Comparative Examples 1 to 3, while minimizing conversion to gamma-butyrolactone (GBL) or tetrahydrofuran (THF).

Claims

Claim 1 A catalyst for a hydrogenation reaction comprising ruthenium and tin as catalytically active metals, wherein the ruthenium content is 30 wt% or more to 50 wt% or less relative to the total weight of the ruthenium and tin, the tin content is 50 wt% or more to 70 wt% or less, and the ratio (A2 / A1) of the hydrogen adsorption amount (A2) at a temperature of 523 K or lower to the total hydrogen adsorption amount (A1) of the catalyst, as measured by a method according to Hydrogen-Temperature Program Reduction (H2-TPR) analysis, is 70 mol% to 99 mol%. Claim 2 A catalyst for a hydrogenation reaction according to claim 1, wherein the ruthenium as the catalytic active metal is included in an amount of 1 part by weight or more to 11 parts by weight or less relative to the total weight of the catalyst, the tin as the catalytic active metal is included in an amount of 1 part by weight or more to 12 parts by weight or less relative to the total weight of the catalyst, and the tin among the catalytic active metals is included in a weight ratio of 1.0 to 3.0 relative to the ruthenium on a weight basis. Claim 3 In claim 1, the catalyst-active metal is a catalyst for a hydrogenation reaction supported on a porous carbon-based carrier. Claim 4 A catalyst for a hydrogenation reaction according to claim 3, wherein the porous carbon-based carrier comprises at least one selected from the group consisting of activated carbon, carbon black, graphite, graphene, ordered mesoporous carbon (OMC), and carbon nanotubes. Claim 5 In paragraph 3, the porous carbon-based carrier has a pore volume of 0.1 cm 3 / g to 1.5 cm 3 / g, catalyst for hydrogenation. Claim 6 In claim 1, the catalyst for the hydrogenation reaction has a BET specific surface area of ​​100 m² 2 / g to 1,500 m 2 / g, catalyst for hydrogenation. Claim 7 In claim 1, the hydrogenation reaction catalyst is a hydrogenation reaction catalyst having an average pore diameter of 2.0 nm to 5.5 nm. Claim 8 A method for preparing a catalyst for a hydrogenation reaction, comprising: a step of preparing a metal precursor solution by 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; and a step of reducing the metal precursor solution or a mixture containing the same in the presence of hydrogen gas after drying; wherein the ruthenium content in the metal precursor solution is 30% by weight or more to 50% by weight or less relative to the total weight of ruthenium and tin, and the tin content is 50% by weight or more to 70% by weight or less relative to the total weight of ruthenium and tin. Claim 9 A method for preparing a catalyst for a hydrogenation reaction according to claim 8, wherein the precursor compound containing ruthenium as the catalytically active metal is one or more selected from the group consisting of ruthenium metal, ruthenium chloride, ruthenium nitrate, acetylacetonator ruthenium, ruthenium carbonyl, ruthenium oxalate, and ruthenium nitrosyl nitrate. Claim 10 A method for preparing a catalyst for a hydrogenation reaction according to claim 8, wherein the precursor compound containing tin as the catalytic active metal is one or more selected from the group consisting of tin chloride (II), sodium tartrate, tin acetate (II), tin fluoride, and tin iodide. Claim 11 A method for manufacturing a catalyst for a hydrogenation reaction according to claim 8, further comprising the step of mixing the metal precursor solution with a porous carbon-based carrier after the step of manufacturing the metal precursor solution. Claim 12 A method for preparing a catalyst for a hydrogenation reaction according to claim 8, wherein the metal precursor solution or a mixture containing the same is dried under temperature conditions of 323 K to 473 K, and then reduced under temperature conditions of 473 K to 773 K in the presence of hydrogen gas. Claim 13 A method for manufacturing a catalyst for a hydrogenation reaction, further comprising, in claim 8, a step of forming a passivation layer by passivating the reduced product generated in the reduction treatment step after the reduction treatment step. Claim 14 A method for manufacturing a catalyst for a hydrogenation reaction according to claim 13, wherein the passivation step is to passivate the reduction product with a nitrogen mixed gas containing 0.1% to 20% oxygen by volume. Claim 15 A hydrogenation method comprising performing a hydrogenation reaction that converts a carboxylic acid group, an aldehyde group, or a ketone group into an alcohol group in the presence of a catalyst according to claim 1. Claim 16 In claim 15, the hydrogenation reaction is a hydrogenation method in which the reaction pressure is 50 bar to 150 bar, the reaction temperature is 410 K to 560 K, and the reaction time is 0.5 hours to 10 hours. Claim 17 A hydrogenation method according to claim 15, wherein the carboxylic acid compound containing the carboxyl functional group is one or more 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, isostearyl acid, oleic acid, maleic acid, cyclohexanecarboxylic acid, benzoic acid, and anhydrides thereof. Claim 18 A hydrogenation method according to claim 15, wherein the aldehyde-based compound containing the aldehyde functional group is one or more selected from the group consisting of formaldehyde, propionaldehyde, n-butylaldehyde, isobutylaldehyde, valeraldehyde, 2-methylbutylaldehyde, 3-methylbutylaldehyde, 2,2-dimethylpropionaldehyde, capronaldehyde, 2-methylvaleraldehyde, 3-methylvaleraldehyde, 4-methylvaleraldehyde, 2-ethylbutylaldehyde, 2,2-dimethylbutylaldehyde, 3,3-dimethylbutylaldehyde, caprylaldehyde, caprinaldehyde, and glutaldialdehyde. Claim 19 A hydrogenation method according to claim 15, wherein the ketone-based compound containing the ketone functional group is one or more selected from the group consisting of acetone, butanone, pentanone, hexanone, cyclohexanone, and acetophenone. Claim 20 A catalyst for a hydrogenation reaction according to claim 1, wherein ruthenium and tin exhibit a homogeneous alloy status.

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