Catalyst for simultaneous conversion reaction of sugar to alcohol and acid and method for simultaneously producing alcohol and acid from sugar by using same

Abstract

The present invention relates to a catalyst for simultaneously producing an alcohol and an acid from a sugar and a method for simultaneously producing an alcohol and an acid from a sugar by using same and, more specifically, to a catalyst that is easily recoverable and enables the stable and simultaneous production of an acid and an alcohol from a sugar under mild reaction conditions with low temperature and low pressure compared with existing reaction conditions, and to a method for simultaneously producing an alcohol and an acid from a sugar by using same.

Description

Catalyst for simultaneous conversion of sugar into alcohol and acid and method for simultaneous production of alcohol and acid from sugar using the same

[0001] The present invention relates to a catalyst for a simultaneous conversion reaction of sugar into alcohol and acid, and a method for simultaneously producing alcohol and acid from sugar using the same, and more particularly, to a catalyst used in a reaction for simultaneously converting sugar into alcohol and acid, and a method for simultaneously producing alcohol and acid from sugar using the same.

[0002] Due to the finite nature of fossil fuels such as oil, gas, and coal, prices are constantly rising, and competition among nations to secure their supplies is intensifying. Furthermore, chemical products produced from fossil fuels generate global warming gases and waste as byproducts during their manufacturing processes, contributing to environmental pollution. This is rapidly declining the existing chemical industry.

[0003] In South Korea, which relies on imports for the majority of its energy, establishing a long-term energy supply and demand policy that minimizes dependence on energy imports and developing fundamentally clean alternative energy sources are essential to national security and sustainable economic growth. In this context, biomass is attracting attention as an alternative energy source that can address concerns about fossil fuel depletion and environmental pollution. The depletion of petroleum resources, the instability of oil supply due to rising oil prices, and the move toward stricter environmental regulations to curb greenhouse gas emissions from fossil fuel use are all hindering global economic development. In particular, the chemical industry, which is most directly impacted by high oil prices and environmental regulations, recognizes reducing fossil fuel dependence and shifting to an environmentally friendly industrial structure as a crucial alternative. Therefore, the development of new, environmentally friendly biochemical processes that utilize biomass as a raw material and can replace fossil-based chemical processes—that is, minimize fossil fuel consumption and the production of hazardous waste—is urgently needed.

[0004] One of the notable recent developments in environmentally friendly biochemical processes is the rise of biorefinery technology, which utilizes biomass. A biorefinery is a novel concept that manufactures biofuels and chemicals solely from biomass through biological and chemical conversion processes, without using fossil fuels. While the term "oil refinery," which refers to the refining of crude oil in the petrochemical industry, actually encompasses a core technology across the entire lifecycle, encompassing the biological and chemical conversion of biomass feedstocks to produce all biochemical products, including biofuels.

[0005] Just as oil refineries, which produce industrial / transportation fuels and various chemical products using crude oil, have been developed as integrated processes, biorefineries are being developed as integrated processes that utilize biomass as a raw material to produce biofuels such as ethanol, butanol, and acetone, as well as chemical raw materials such as sorbitol, xylitol, lactic acid, and succinic acid, along with the technology to implement these processes and a comprehensive plant system. In particular, alcohols such as sorbitol and xylitol, and acids such as xylic acid and gluconic acid are widely used in food additives, pharmaceuticals, and cosmetics, and interest in them is growing significantly.

[0006] These alcohols are mostly produced by hydrogenation reactions of their corresponding sugars, and representative examples are as follows. As a hydrogenation method, U.S. Patent Nos. 3,586,537, 4,008,285, and 6,414,201 disclose methods for producing xylitol by hydrogenating xylose using a Raney nickel catalyst. This hydrogenation method has the disadvantage of being performed at high temperature and high pressure, requiring a catalyst recovery process, and requiring separate reactions and different catalysts to produce acids such as xylic acid and gluconic acid in addition to sugar alcohols, which increases the production cost.

[0007] [Prior Art Literature]

[0008] [Patent Document]

[0009] (Patent Document 1) U.S. Patent No. 3,586,537 (Registration Date: June 22, 1971)

[0010] (Patent Document 2) U.S. Patent No. 4,008,285 (Registration Date: February 15, 1977)

[0011] (Patent Document 3) U.S. Patent No. 6,414,201 (Registration Date: July 2, 2002)

[0012] The main purpose of the present invention is to provide a catalyst for the simultaneous conversion of sugar into alcohol and acid, which is created to solve the above-mentioned problem and allows easy recovery of the catalyst, and can stably produce acid and alcohol simultaneously from sugar under mild reaction conditions of low temperature and low pressure compared to existing reaction conditions.

[0013] In addition, another object of the present invention is to provide a method for simultaneously producing alcohol and acid from sugar in the presence of the above catalyst and base.

[0014] In order to solve the above problem, the present invention provides a catalyst for a simultaneous sugar acid and alcohol conversion reaction that simultaneously produces an acid and an alcohol from sugar in the presence of a base.

[0015] The above catalyst may be characterized in that platinum is supported as a catalytically active metal on a metal oxide containing at least one metal selected from the group consisting of zirconium (Zr), aluminum (Al), cerium (Ce), zinc (Zn), titanium (Ti), hafnium (Hf), nickel (Ni), cobalt (Co), iron (Fe), manganese (Mn), aluminum (Al), gallium (Ga), and indium (In) as a catalyst support.

[0016] The above base may be a hydroxide salt of an alkali metal and / or a hydroxide salt of an alkaline earth metal, and may be at least 1 mole per 1 mole of sugar.

[0017] The above platinum may be 0.1 wt% to 20 wt% based on the total weight of the catalyst, and the concentration of sugar in the above reaction may be 1 mol or more.

[0018] The above sugar may be at least one selected from the group consisting of erythrose, ribose, arabinose, xylose, lyxose, allose, altrose, glucose, mannose, galactose, talose, hexose, maltose, lactose, fructose, lactulose, isomaltulose, rhamnose, sucrose, starch sugar, starch hydrolysate, cellulose hydrolysate, and hemicellulose hydrolysate.

[0019] In addition, the present invention provides a method for simultaneously producing an acid and an alcohol from sugar by reacting sugar in the presence of a base and a catalyst, wherein the catalyst is a catalyst support containing at least one metal selected from the group consisting of zirconium (Zr), aluminum (Al), cerium (Ce), zinc (Zn), titanium (Ti), hafnium (Hf), nickel (Ni), cobalt (Co), iron (Fe), manganese (Mn), aluminum (Al), gallium (Ga), and phosphorus (In), and platinum is supported as a catalytically active metal.

[0020] In the manufacturing method of the present invention, the base may be a hydroxide salt of an alkali metal and / or a hydroxide salt of an alkaline earth metal, the amount of the base used may be 1 mol or more per 1 mol of sugar, the concentration of sugar in the reaction may be 1 mol or more, the platinum may be 0.1 wt% to 20 wt% with respect to the total weight of the catalyst, and the reaction may be performed at 0°C to 200°C.

[0021] The catalyst according to the present invention uses Pt as an active metal and a metal oxide as a support, so that acid and alcohol can be simultaneously produced from sugar under mild single reaction conditions of low temperature and low pressure. At the same time, compared to existing Pt / C catalysts, the recovery and reuse of the catalyst are advantageous even under strongly alkaline conditions, so that when the catalyst of the present invention is used, it can exhibit stable recycling efficiency over a long period of time.

[0022] In addition, the present invention enables the simultaneous production of alcohol and acid under mild single reaction conditions of low temperature and low pressure, rather than the conventional process of producing alcohol and acid separately from sugar in the presence of different catalysts, thereby shortening the conventional process of producing alcohol and acid, which was complicated and took a long time, and thus has the effect of improving the productivity of alcohol and acid from sugar.

[0023] Figure 1 illustrates a conversion reaction mechanism of glucose according to one embodiment of the present invention.

[0024] Figure 2 illustrates a conversion reaction mechanism of xylose according to one embodiment of the present invention.

[0025] Figure 3 is a graph showing XRD pattern measurements of catalysts manufactured in Manufacturing Examples 1, 3, and 5 of the present invention.

[0026] Figure 4 is a graph showing the results of measuring the catalytic activity according to the reuse of the catalysts manufactured in Manufacturing Examples 4 and 10 of the present invention. (a) is a graph showing the measurement of xylose conversion, xylosan acid, and xylitol yield for the catalyst of Manufacturing Example 4, and (b) is a graph showing the measurement of xylose conversion, xylosan acid, and xylitol yield for the catalyst of Manufacturing Example 10.

[0027] Figure 5 is an SEM image taken before and after the reaction of the catalysts manufactured in Manufacturing Examples 4 and 10 of the present invention, (a) is an SEM image before the catalytic reaction of Manufacturing Example 4, (b) is an SEM image after the catalytic reaction of Manufacturing Example 4, (c) is an SEM image before the catalytic reaction of Manufacturing Example 10, and (b) is an SEM image after the catalytic reaction of Manufacturing Example 10.

[0028] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.

[0029] The terms “comprising,” “including,” or “having” used in this specification indicate the presence of features, values, steps, operations, components, parts, or combinations thereof described in the specification, and do not exclude the possibility that other features, values, steps, operations, components, parts, or combinations thereof that are not mentioned may be present or added.

[0030] The reactions and mixing described below can be carried out at room temperature and pressure unless otherwise specified, and can be carried out under typical reaction and mixing conditions without additional additions. However, this should not be interpreted in a way that deviates from matters clearly understood by those skilled in the art.

[0031] The present invention relates to a catalyst used in a reaction for simultaneously producing an acid and an alcohol by converting a sugar in the presence of a base, and to a method for simultaneously producing an acid and an alcohol from sugar using the same. The sugar conversion reaction is a reaction for simultaneously producing an acid and an alcohol by reacting a sugar in the presence of a base and a catalyst, and the catalyst is characterized in that platinum is supported as a catalytically active metal on a specific metal oxide catalyst support.

[0032] The above catalytically active metal, platinum (Pt), may be supported at 0.1 wt% to 20 wt%, preferably 0.1 wt% to 10 wt%, and more preferably 1 wt% to 8 wt%, based on the total weight of the catalyst. If the platinum is less than 0.1 wt% based on the total weight of the catalyst, there is a problem that the reactivity is reduced because there is not enough active component in the sugar conversion reaction, and if it exceeds 20 wt%, the dispersion of platinum is low, so the activity increase effect according to the amount of platinum is relatively low, and rather, the CC bond is broken, so the selectivity is lowered, so the activity increase effect is not large compared to the platinum content, which may not be economical.

[0033] In addition, the catalyst support may be a metal compound containing at least one metal selected from the group consisting of titanium (Ti), zirconium (Zr), cerium (Ce), hafnium (Hf), zinc (Zn), nickel (Ni), cobalt (Co), iron (Fe), manganese (Mn), aluminum (Al), gallium (Ga), and indium (In) in terms of sugar conversion rate and acid and alcohol selectivity while having excellent stability even under alkaline conditions, and zirconium (Zr), cerium (Ce), titanium (Ti), hafnium (Hf), etc. may be preferable in terms of high long-term stability. At this time, in the catalyst support, the metal compound may be a metal oxide represented by MO (M = Zn, etc.), MO2 (M = Ti, Zr, Ce, Hf, etc.), M2O3 (M = Al, etc.), or MOOH (M = Ni, Co, Fe, Mn, Al, Ga, In, etc.).

[0034] Meanwhile, the catalyst according to the present invention can be applied without limitation to any method capable of supporting platinum on a catalyst support, and specifically, platinum can be supported on the catalyst support using a method known in the technical field to which the present invention pertains, such as an impregnation method, a co-precipitation method, a solid-phase support method, a vapor deposition method, a wash coating method, a sol-gel method, or a hydrothermal synthesis method.

[0035] In one embodiment, the impregnation-based support comprises a step of impregnating a platinum precursor solution into a catalyst support and a step of drying and calcining the catalyst support on which the platinum precursor solution is supported.

[0036] The above impregnation can be performed by dissolving a platinum precursor in a solvent, dividing it into several stages, and evenly dispersing the platinum precursor dissolved in the solvent on the catalyst support, and performing wet impregnation at 10°C to 200°C. The impregnation time can be sufficient to impregnate the catalyst support, depending on the situation, and for example, the impregnation can be performed for 1 to 12 hours.

[0037] The platinum precursor may be at least one selected from platinum-containing nitrates, sulfates, phosphoric acids, halogen salts, alkoxide salts, oxynitrates, oxalates, acetate salts, alkyl salts, hydrates thereof, etc., and preferably, a halogen salt hydrate may be used. The solvent may be any known solvent capable of dissolving the platinum precursor, such as a glycol solvent such as water, ethylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, diethylene glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, trimethylol propane, or an alcohol solvent such as methanol, ethanol, isopropyl alcohol (IPA), butanol, etc. The solvent content may be used without limitation as long as it is an amount capable of uniformly dispersing the platinum precursor, and for example, based on 100 parts by weight of the platinum precursor, 100 parts by weight to It can be 500 parts by weight.

[0038] Next, the platinum-supported catalyst support can be dried and calcined by controlling the time and temperature according to conditions such as the amount of catalytically active metal supported, the size and quantity of the catalyst support, etc. For example, after drying at 10°C to 100°C, it can be calcined at 400°C to 1,100°C for 3 to 10 hours. In addition, it is preferable to manufacture it by gradually increasing the temperature because rapid temperature changes during the calcination process can cause cracks and pores to be generated due to rapid evaporation and oxidation of the solvent, which significantly reduces the strength.

[0039] The calcined catalyst can then undergo an activation step prior to the sugar conversion reaction. Specifically, the activation step can activate the catalyst by reducing it in a reducing atmosphere at a temperature (100°C to 600°C) at which the catalyst can be reduced. In one embodiment, after mounting the catalyst in a reactor, the catalyst can be reduced by flowing 1 to 10% hydrogen (H2) gas at a flow rate of 50 ml / min to 300 ml / min at 100°C to 600°C for 0.5 to 4 hours.

[0040] The above-mentioned reduced catalyst can be installed in a reactor and then used to perform a sugar conversion reaction in the presence of a base. The sugar conversion reaction performed in the present invention can be performed in an open or closed reactor, and can be performed in batch or continuous modes.

[0041] At this time, the sugar used as a raw material may include monosaccharides, disaccharides and polysaccharides, and specifically, may include a mixture of sugars selected from the group consisting of erythrose, arabinose, xylose, glucose, mannose, galactose, talose, maltose, lactose, fructose, lactulose, isomaltulose, rhamnose, sucrose, ribose, lyxose, allose, altrose, hexose, starch sugar, starch hydrolysate, cellulose hydrolysate and hemicellulose hydrolysate, and preferably xylose, It can be glucose, galactose, mannose, lactose, arabinose, etc.

[0042] Since sugar is generally in a solid state at room temperature, it is preferable to dissolve the sugar in an appropriate solvent to improve the reaction efficiency. The solvent used for this purpose may be any solvent that can dissolve the raw material sugar, but it is generally preferable to use water or alcohol alone or a mixture thereof. The alcohol may include methanol, ethanol, propanol, isopropanol, or a mixture thereof. More preferably, water may be used alone or a mixture of water and ethanol may be used. When a solvent is used, the concentration of sugar in the solution is not limited, but may be 1 wt% to 60 wt% based on the total weight of the solvent and sugar.

[0043] In addition, the concentration of the sugar may be 0.1 mol or more, preferably 1 mol to 3 mol. When the concentration of the sugar is less than 0.1 mol, the amount of hydrogen generated during the dehydrogenation reaction of the sugar may be small, which may result in a problem of low alcohol yield.

[0044] The above sugar conversion reaction can be carried out under strong alkaline conditions of pH 13 or higher by adding a base to increase the reaction efficiency. At this time, the base to be added may be an alkali metal hydroxide salt or an alkaline earth metal hydroxide salt, and specifically, may be at least one selected from KOH, NaOH, LiOH, CsOH, RbOH, Ca(OH)2, Mg(OH)2, Sr(OH)2, Ba(OH)2, NH4OH, etc., and preferably may be KOH, NaOH, etc.

[0045] At this time, the base can be used in an amount of 0.5 mol or more per 1 mol of sugar, and preferably 0.5 to 3 mol in terms of reaction activity. If the salt is used in an amount of less than 0.5 mol per 1 mol of sugar, the dehydrogenation efficiency of the sugar may decrease, resulting in a problem of lowering the yield of acid and alcohol.

[0046] The sugar conversion reaction using the catalyst of the present invention can simultaneously produce acid and alcohol from sugar under mild single conditions compared to existing catalysts.

[0047] For example, in the above sugar conversion reaction, as shown in FIGS. 1 and 2, when the sugar is glucose, gluconic acid and sorbitol can be simultaneously produced by the conversion reaction of glucose in the presence of a base and a catalyst, and when the sugar is xylose, xylic acid and xylitol can be simultaneously produced by the conversion reaction of xylose in the presence of a base and a catalyst.

[0048] At this time, the sugar conversion reaction can be carried out at 0 ℃ to 200 ℃, and more preferably, at 0 ℃ to 60 ℃. If the reaction temperature is lower than 0 ℃, energy consumption due to the low-temperature process is high, and if it exceeds 200 ℃, side reactions such as CC decomposition reactions may increase.

[0049] In this way, the acid and alcohol produced by the method of the present invention are simultaneously produced from sugar without dissolution of the catalyst component under mild single conditions of low temperature and low pressure compared to conventional methods, so that byproducts and waste are hardly generated and can be produced without a complicated separation process, and the catalyst that participated in the reaction can be recovered and repeatedly used in the sugar conversion reaction, and can be used without the catalyst component being dissolved or deactivated even when repeatedly reused.

[0050] Hereinafter, the catalytic activity of the catalyst for the simultaneous sugar-alcohol-acid conversion reaction according to the present invention will be examined through examples. It should be noted that the following examples are provided to illustrate one or more preferred embodiments of the present invention, but the present invention is not limited to these embodiments. Numerous modifications to the examples below may be made within the scope of the present invention.

[0051] <Manufacturing Example: Catalyst Manufacturing>

[0052] Manufacturing Example 1: Manufacturing of 1 wt% Pt / ZrO2 catalyst

[0053] Zr(OH)2 powder was calcined at 600°C to obtain monoclinic ZrO2, and then 4.95 g of the obtained ZrO2 was dispersed in 50 ml of deionized water to prepare a ZrO2 slurry. Then, 0.13 g of H2PtCl6ㆍ6H2O was dissolved in 30 ml of deionized water to obtain a platinum precursor solution, and the obtained platinum precursor solution was slowly added to the constantly stirred ZrO2 slurry to obtain a mixture. The obtained mixture was dried in an oven at 100°C for 24 hours and calcined in a kiln at 500°C for 4 hours to prepare a Pt / ZrO2 catalyst loaded with 1 wt% Pt. Thereafter, the prepared catalyst was activated by reducing it at 300°C for 2 hours under a 5% H2 / Ar flow.

[0054] Manufacturing Example 2: Manufacturing of 2 wt% Pt / ZrO2 catalyst

[0055] A Pt / ZrO2 catalyst was manufactured using the same method as in Manufacturing Example 1, but a platinum precursor solution containing 0.26 g of H2PtCl6ㆍ6H2O dissolved in 30 ml of deionized water was slowly added to the ZrO2 slurry to manufacture a Pt / ZrO2 catalyst loaded with 2 wt% of Pt.

[0056] Manufacturing Example 3: Manufacturing of 3 wt% Pt / ZrO2 catalyst

[0057] A Pt / ZrO2 catalyst was manufactured using the same method as in Manufacturing Example 1, but a platinum precursor solution containing 0.39 g of H2PtCl6ㆍ6H2O dissolved in 30 ml of deionized water was slowly added to the ZrO2 slurry to manufacture a Pt / ZrO2 catalyst loaded with 3 wt% of Pt.

[0058] Manufacturing Example 4: Manufacturing of 5 wt% Pt / ZrO2 catalyst

[0059] A Pt / ZrO2 catalyst was manufactured using the same method as in Manufacturing Example 1, but a platinum precursor solution containing 0.65 g of H2PtCl6ㆍ6H2O dissolved in 30 ml of deionized water was slowly added to the ZrO2 slurry to manufacture a Pt / ZrO2 catalyst loaded with 5 wt% of Pt.

[0060] Manufacturing Example 5: Manufacturing of 9 wt% Pt / ZrO2 catalyst

[0061] A Pt / ZrO2 catalyst was manufactured using the same method as in Manufacturing Example 1, but a platinum precursor solution containing 1.17 g of H2PtCl6ㆍ6H2O dissolved in 60 ml of deionized water was slowly added to the ZrO2 slurry to manufacture a Pt / ZrO2 catalyst loaded with 9 wt% of Pt.

[0062] Manufacturing Example 6: Manufacturing of 5 wt% Pt / CeO2 catalyst

[0063] Ce(CH3COO)3ㆍxH2O powder was calcined at 600℃ to obtain CeO2, and then 4.75 g of the obtained CeO2 was dispersed in 50 ml of deionized water to prepare a CeO2 slurry. Thereafter, 0.65 g of H2PtCl6ㆍ6H2O was dissolved in 30 ml of deionized water to obtain a platinum precursor solution, and the obtained platinum precursor solution was slowly added to the constantly stirred CeO2 slurry to obtain a mixture. The obtained mixture was stirred at room temperature for 6 hours, and the water was evaporated to recover the solid. The recovered solid was dried in an oven at 100℃ for 24 hours, and calcined in a kiln at 500℃ for 4 hours to prepare a Pt / CeO2 catalyst loaded with 5 wt% Pt. The catalyst thus manufactured was activated by reduction at 300°C for 2 hours under a 5% H2 / Ar flow.

[0064] Manufacturing Example 7: Manufacturing of 5 wt% Pt / Al2O3 catalyst

[0065] A γ-Al2O3 slurry was prepared by dispersing 4.75 g of gamma alumina (γ-Al2O3) in 90 ml of deionized water. 0.65 g of H2PtCl6ㆍ6H2O was dissolved in 30 ml of deionized water to obtain a platinum precursor solution, which was then slowly added to the constantly stirred γ-Al2O3 slurry to obtain a mixture. The mixture was stirred at room temperature for 6 hours, and the water was evaporated to recover the solid. The recovered solid was dried in an oven at 100°C for 24 hours and calcined in a kiln at 500°C for 4 hours to produce a Pt / Al2O3 catalyst loaded with 5 wt% Pt. The calcined catalyst was then activated by reduction at 300°C for 2 hours under a 5% H2 / Ar flow.

[0066] Manufacturing Example 8: Manufacturing of 5 wt% Pt / ZnO catalyst

[0067] A ZnO2 slurry was prepared by dispersing 4.75 g of ZnO2 in 40 ml of deionized water. 0.65 g of H2PtCl6ㆍ6H2O was dissolved in 30 ml of deionized water to obtain a platinum precursor solution, which was then slowly added to the constantly stirred ZnO2 slurry to obtain a mixture. The resulting mixture was stirred at room temperature for 6 hours, and the water was evaporated to recover the solid. The recovered solid was dried in an oven at 100°C for 24 hours and calcined in a kiln at 500°C for 4 hours to prepare a Pt / ZnO catalyst loaded with 5 wt% Pt. The calcined catalyst was then activated by reduction at 300°C for 2 hours under a 5% H2 / Ar flow.

[0068] Manufacturing Example 9: Manufacturing of 5 wt% Pt / TiO2 catalyst

[0069] A TiO2 slurry was prepared by dispersing 4.75 g of TiO2 in 40 ml of deionized water. 0.65 g of H2PtCl6ㆍ6H2O was dissolved in 30 ml of deionized water to obtain a platinum precursor solution, which was then slowly added to the constantly stirred TiO2 slurry to obtain a mixture. The resulting mixture was stirred at room temperature for 6 hours, and the water was evaporated to recover the solid. The recovered solid was dried in an oven at 100°C for 24 hours and calcined in a kiln at 500°C for 4 hours to produce a Pt / TiO2 catalyst loaded with 5 wt% Pt. The calcined catalyst was then activated by reduction at 300°C for 2 hours under a 5% H2 / Ar flow.

[0070] Manufacturing Example 10: Manufacturing of 5 wt% Pt / C catalyst

[0071] A Pt / C catalyst (CAS Number 7440-06-4) loaded with 5 wt% Pt purchased from Sigma-Aldrich was used.

[0072] Manufacturing Example 11: Manufacturing of 5 wt% Ru / ZrO2 catalyst

[0073] Zr(OH)4 powder was calcined at 600°C to obtain ZrO2, and then 4.75 g of the obtained ZrO2 was dispersed in 40 ml of deionized water to prepare a ZrO2 slurry. Then, 0.51 g was dissolved in 30 ml of deionized water to obtain a ruthenium precursor solution, and the obtained ruthenium precursor solution was slowly added to the constantly stirred ZrO2 slurry to obtain a mixture. The obtained mixture was stirred at room temperature for 6 hours, and the water was evaporated to recover the solid. The recovered solid was dried in an oven at 100°C for 24 hours, and calcined in a box furnace at 500°C for 4 hours under a constant air flow of 150 mL / min to prepare a Ru / ZrO2 catalyst loaded with 5 wt% Ru. The subsequently manufactured catalyst was further activated by reduction at 300 °C for 2 h under a 5% H2 / Ar flow of 150 mL / min.

[0074] Manufacturing Example 12: Manufacturing of 5 wt% Au / ZrO2 catalyst

[0075] Zr(OH)4 powder was calcined at 600°C to obtain monoclinic ZrO2, and then 4.75 g of the obtained ZrO2 was dispersed in 40 ml of deionized water to prepare a ZrO2 slurry. Then, 0.5 g was dissolved in 30 ml of deionized water to obtain a gold precursor solution, and the obtained gold precursor solution was slowly added to the constantly stirred ZrO2 slurry to obtain a mixture. The obtained mixture was stirred at room temperature for 6 hours, and the water was evaporated to recover the solid. The recovered solid was dried in an oven at 100°C for 24 hours, and calcined in a box furnace at 500°C for 4 hours under a constant air flow of 150 mL / min to prepare an Au / ZrO2 catalyst loaded with 5 wt% Au. The calcined catalyst was then further reduced and activated at 300 °C for 2 h under a 5% H2 / Ar flow of 150 mL / min.

[0076] Manufacturing Example 13: Manufacturing of 5 wt% Pd / C catalyst

[0077] A Pd / C catalyst (Commercial 205680-50G) loaded with 5 wt% Pd purchased from Sigma-Aldrich was used.

[0078] Manufacturing Example 14: Manufacturing of 5 wt% Rh / C catalyst

[0079] A 5 wt% Rh / C catalyst (Commercial 206164-5G) purchased from Sigma-Aldrich was used.

[0080] <Experimental Example 1: Catalyst Characteristics Analysis>

[0081] In order to analyze the characteristics of the catalyst according to the Pt content, the specific surface area, pore size, and pore volume of the catalysts manufactured in Manufacturing Examples 1, 3 to 5 were analyzed using BET (Brunauer-Emmett-Teller analysis), and the content and size of the supported platinum were analyzed using ICP (inductively coupled plasma analysis) and TEM (transmission electron microscopy analysis). The dispersion of the supported platinum was analyzed through CO2-chemisorption, and the results are shown in Table 1, respectively. In addition, in order to measure the composition of these catalysts, XRD (X-ray diffraction analysis) patterns were measured, and the results are shown in Fig. 3. In this case, ZrO2 of Reference Example 1 in Table 1 below means ZrO2 obtained by calcining Zr(OH)4 powder at 600°C.

[0082] [Table 1]

[0083]

[0084] As shown in Fig. 3 and Table 1, the catalyst surface area and the content and size of platinum increased as the content of Pt increased, while the pore size and pore volume decreased. It was also confirmed that the platinum dispersion decreased as the amount of platinum supported increased.

[0085] <Example: Simultaneous production of acid and alcohol from sugar>

[0086] Example 1

[0087] 0.4 g of the catalyst (5 wt% Pt / ZrO2) manufactured in Manufacturing Example 4, 2.18 g (12 mmol) of glucose, 0.75 g (12 mmol) of KOH, and 6 ml of distilled water were charged into a reactor, and nitrogen gas was purged into the reactor to completely replace the air in the reactor. Thereafter, the reactor was stirred at 1,400 rpm for 6 hours at 25°C, and the reaction product generated after the reaction was analyzed through liquid chromatography.

[0088] Example 2

[0089] Gluconic acid and sorbitol were simultaneously produced from glucose in the same manner as in Example 1, but the catalyst (5 wt% Pt / CeO2) produced in Production Example 6 was added and the reaction was performed.

[0090] Example 3

[0091] 0.4 g of the catalyst (1 wt% Pt / ZrO2) manufactured in Manufacturing Example 1, 1.8 g (12 mmol) of xylose, 0.75 g (12 mmol) of KOH, and 6 ml of distilled water were charged into a reactor, and nitrogen gas was purged into the reactor to completely replace the air in the reactor. Thereafter, the reactor was stirred at 1,400 rpm and reacted at 25°C for 6 hours, and the reaction product generated after the reaction was analyzed using liquid chromatography.

[0092] Example 4

[0093] Xylic acid and xylitol were simultaneously produced from xylose in the same manner as in Example 3, but the catalyst (2 wt% Pt / ZrO2) produced in Manufacturing Example 2 was added and the reaction was performed.

[0094] Example 5

[0095] Xylic acid and xylitol were simultaneously produced from xylose in the same manner as in Example 3, but the catalyst (3 wt% Pt / ZrO2) produced in Manufacturing Example 3 was added and the reaction was performed.

[0096] Example 6

[0097] Xylic acid and xylitol were simultaneously produced from xylose in the same manner as in Example 3, but the catalyst (5 wt% Pt / ZrO2) produced in Manufacturing Example 4 was added and the reaction was performed.

[0098] Example 7

[0099] Xylic acid and xylitol were simultaneously produced from xylose in the same manner as in Example 3, but the catalyst (9 wt% Pt / ZrO2) produced in Manufacturing Example 5 was added and the reaction was performed.

[0100] Example 8

[0101] Xylic acid and xylitol were simultaneously produced from xylose in the same manner as in Example 3, but the catalyst (5 wt% Pt / CeO2) produced in Manufacturing Example 6 was added and the reaction was performed.

[0102] Example 9

[0103] Xylic acid and xylitol were simultaneously produced from xylose in the same manner as in Example 3, but the catalyst (5 wt% Pt / Al2O3) produced in Manufacturing Example 7 was added and the reaction was performed.

[0104] Example 10

[0105] Xylic acid and xylitol were simultaneously produced from xylose in the same manner as in Example 3, but the catalyst (5 wt% Pt / ZnO) produced in Manufacturing Example 8 was added and the reaction was performed.

[0106] Example 11

[0107] Xylic acid and xylitol were simultaneously produced from xylose in the same manner as in Example 3, but the catalyst (5 wt% Pt / TiO2) produced in Manufacturing Example 9 was added and the reaction was performed.

[0108] Comparative Example 1

[0109] Gluconic acid and sorbitol were simultaneously produced from glucose in the same manner as in Example 1, but the catalyst (5 wt% Pt / C) produced in Production Example 10 was added and the reaction was performed.

[0110] Comparative Example 2

[0111] Xylic acid and xylitol were simultaneously produced from xylose in the same manner as in Example 3, but the catalyst (5 wt% Ru / ZrO2) produced in Manufacturing Example 11 was added and the reaction was performed.

[0112] Comparative Example 3

[0113] Xylic acid and xylitol were simultaneously produced from xylose in the same manner as in Example 3, but the catalyst (5 wt% Au / ZrO2) produced in Manufacturing Example 12 was added and the reaction was performed.

[0114] Comparative Example 4

[0115] Xylic acid and xylitol were simultaneously produced from xylose in the same manner as in Example 3, but the catalyst (5 wt% Pd / C) produced in Manufacturing Example 13 was added and the reaction was performed.

[0116] Comparative Example 5

[0117] Xylic acid and xylitol were simultaneously produced from xylose in the same manner as in Example 3, but the catalyst (5 wt% Rh / C) produced in Manufacturing Example 14 was added and the reaction was performed.

[0118] Comparative Example 6

[0119] Xylic acid and xylitol were simultaneously produced from xylose in the same manner as in Example 3, but the catalyst (5 wt% Ru / C) produced in Manufacturing Example 14 was added and the reaction was performed.

[0120] <Experimental Example 2: Evaluation of Catalytic Activity According to Simultaneous Production of Glucosan and Sorbitol from Glucose>

[0121] In order to evaluate the reaction activity according to the type of catalyst in simultaneously producing gluconic acid and sorbitol from glucose, the glucose conversion rate and the yield of gluconic acid and sorbitol in Examples 1 and 2 and Comparative Example 1, in which the reaction was carried out under the same conditions, were measured, and the results are shown in Table 2.

[0122] [Table 2]

[0123]

[0124] As shown in Table 2, both Examples 1 and 2 and Comparative Example 1 showed a glucose conversion rate of 99% or more, and a glucosan and sorbitol yield of 73% and 23% or more, respectively.

[0125] <Experimental Example 3: Evaluation of Catalytic Activity According to Simultaneous Production of Xylic Acid and Xylitol from Xylose>

[0126] In order to evaluate the reaction activity according to the type of catalyst in simultaneously producing xylose from xylic acid and xylitol, the xylose conversion rate and the yields of xylic acid and xylitol in Examples 6, 8 to 11 and Comparative Examples 1 to 5, which were carried out under the same conditions, were measured, and the results are shown in Table 3. At this time, the xylose conversion rate was measured by HPLC, and the results are shown in Table 3.

[0127] [Table 3]

[0128]

[0129] As shown in Table 3, Examples 6 to 11 and Comparative Example 1 were found to exhibit the same selectivity for xylic acid and xylitol, and in particular, the hydrogen utilization efficiency was found to be 100%, which is the theoretical maximum.

[0130] <Experimental Example 4: Catalytic Activity Evaluation According to Pt Content>

[0131] In order to evaluate the reaction activity according to the catalyst content in the simultaneous production of xylic acid and xylitol from xylose, the xylose conversion rate, the yields of xylic acid and xylitol, and the selectivities were measured in Examples 3 to 7, and the results are shown in Table 4. At this time, the xylose conversion rate was measured by HPLC, and the yields of xylic acid and sorbitol were calculated as 50:49, and the selectivities of xylic acid and sorbitol were calculated as 50:49.

[0132] [Table 4]

[0133]

[0134] As shown in Table 4, as the Pt content supported on the catalyst increased from 1 wt% to 5 wt% with respect to the total weight of the catalyst, the conversion of xylose and the yield and selectivity of xylic acid and xylitol increased, whereas at 9 wt%, the conversion of xylose and the yield and selectivity of xylic acid and xylitol decreased somewhat.

[0135] <Experimental Example 5: Catalyst Stability Evaluation According to Catalyst Reuse>

[0136] In order to evaluate the catalyst stability according to catalyst reuse, the catalysts manufactured in Manufacturing Examples 4 and 10 were used to carry out the reaction in the same manner as in Example 6, but the reaction time was changed from 6 hours to 1 hour, and the catalyst used in the reaction was reused as is to carry out the same reaction again. This experiment was repeated 5 times. After each reaction was completed, the product was recovered, and the xylose conversion rate and the yields of xylic acid and xylitol were measured, and the results are shown in Fig. 4. In addition, the catalysts of Manufacturing Examples 4 and 10 before and after the reaction was completed once were photographed using SEM, and are shown in Fig. 5.

[0137] At this time, (a) of FIG. 4 is a graph showing the xylose conversion rate, xylic acid, and xylitol yield for the catalyst of Manufacturing Example 4, and (b) is a graph showing the xylose conversion rate, xylic acid, and xylitol yield for the catalyst of Manufacturing Example 10. In addition, (a) of FIG. 5 is a SEM image before the catalytic reaction of Manufacturing Example 4, (b) is a SEM image after the catalytic reaction of Manufacturing Example 4, (c) is a SEM image before the catalytic reaction of Manufacturing Example 10, and (b) is a SEM image after the catalytic reaction of Manufacturing Example 10.

[0138] As shown in Fig. 4, in the case of the catalyst manufactured in Manufacturing Example 4, the xylose conversion rate and the yields of xylic acid and xylitol were stable even after 5 repeated uses, whereas in the case of the catalyst manufactured in Manufacturing Example 10, the activity continuously decreased, and the xylose conversion rate and the yields of xylic acid and xylitol decreased.

[0139] In addition, in the SEM measurement of Fig. 5, it was confirmed that the Pt particle size was maintained after the reaction in the case of the catalyst of Manufacturing Example 4, whereas in the case of the catalyst of Manufacturing Example 10, it was confirmed that the Pt particles were clumped together.

[0140] Accordingly, in the case of the catalyst according to the present invention, it was confirmed that the reaction activity did not decrease even when the catalyst was reused, and thus it was confirmed that it was stable in the long term even under basic conditions.

[0141] While the present invention has been described with reference to the attached drawings, these are merely exemplary, and those skilled in the art will understand that various modifications and equivalent embodiments are possible. Accordingly, the technical protection scope of the present invention should be defined by the claims below.

Claims

1. In a catalyst for the simultaneous conversion reaction of sugar to acid and alcohol, which simultaneously produces acid and alcohol from sugar in the presence of a base, The catalyst is a catalyst for the simultaneous conversion reaction of sugar into acid and alcohol, characterized in that platinum is supported on a metal oxide containing at least one metal selected from the group consisting of zirconium (Zr), aluminum (Al), cerium (Ce), zinc (Zn), titanium (Ti), hafnium (Hf), nickel (Ni), cobalt (Co), iron (Fe), manganese (Mn), aluminum (Al), gallium (Ga), and indium (In) as a catalyst support, and is a catalyst for the simultaneous conversion reaction of sugar into acid and alcohol.

2. In paragraph 1, A catalyst for simultaneous conversion of sugar into acid and alcohol, characterized in that the base is at least 1 mole per 1 mole of sugar.

3. In paragraph 1, A catalyst for simultaneous sugar acid and alcohol conversion reaction, characterized in that the sugar concentration in the above reaction is 1 mol or more.

4. In paragraph 1, A catalyst for simultaneous sugar acid and alcohol conversion reaction, characterized in that the platinum is contained in an amount of 0.1 wt% to 20 wt% based on the total weight of the catalyst.

5. In paragraph 1, A catalyst for the simultaneous conversion reaction of sugar into acid and alcohol, characterized in that the base is a hydroxide salt of an alkali metal and / or a hydroxide salt of an alkaline earth metal.

6. In paragraph 1, A catalyst for simultaneous acid and alcohol conversion reaction of sugar, characterized in that the sugar is at least one selected from the group consisting of erythrose, ribose, arabinose, xylose, lyxose, allose, altrose, glucose, mannose, galactose, talose, hexose, maltose, lactose, fructose, lactulose, isomaltulose, rhamnose, sucrose, starch sugar, starch hydrolysate, cellulose hydrolysate, and hemicellulose hydrolysate.

7. In a method for simultaneously producing acid and alcohol from sugar by reacting sugar in the presence of a base and a catalyst, A method for simultaneously producing acid and alcohol from sugar, characterized in that the catalyst is a metal oxide containing at least one metal selected from the group consisting of zirconium (Zr), aluminum (Al), cerium (Ce), zinc (Zn), titanium (Ti), hafnium (Hf), nickel (Ni), cobalt (Co), iron (Fe), manganese (Mn), aluminum (Al), gallium (Ga), and phosphorus (In) as a catalyst support, and platinum is supported as a catalytically active metal.

8. In paragraph 7, A method for simultaneously producing an acid and an alcohol from sugar, characterized in that the base is at least 1 mole per 1 mole of sugar.

9. In paragraph 7, A method for simultaneously producing acid and alcohol from sugar, characterized in that the concentration of sugar in the above reaction is 1 mol or more.

10. In paragraph 7, A method for simultaneously producing acid and alcohol from sugar, characterized in that the platinum is contained in an amount of 0.1 wt% to 20 wt% based on the total weight of the catalyst.

11. In paragraph 7, A method for simultaneously producing an acid and an alcohol from sugar, characterized in that the base is a hydroxide salt of an alkali metal and / or a hydroxide salt of an alkaline earth metal.

12. In paragraph 7, A method for simultaneously producing acid and alcohol from sugar, characterized in that the above reaction is performed at 0°C to 200°C.

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