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

Abstract

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

Description

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

[0001] The present invention relates to a catalyst for a sugar alcohol and acid conversion reaction 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 maintaining 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 strengthening of 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 affected 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 originated from the oil refinery, which refers to the refining of crude oil in the petrochemical industry, it actually encompasses a core technology for the entire lifecycle of biochemicals, including biofuels, through biological and chemical conversion processes from biomass feedstocks.

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

[0006] These hexoses and pentoses 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 and 4,008,285 disclose methods for producing xylitol by hydrogenating xylose in a batch reactor using a Raney nickel catalyst. This production method not only requires a complicated separation and purification process and a catalyst recovery process due to the production of a large amount of by-products, but also has the problem that nickel, the active ingredient of the catalyst, dissolves in the reaction products, and the catalyst gradually becomes inactive after a certain period of reaction.

[0007] In addition, U.S. Patent No. 6,124,443 reports a method for continuous hydrogenation of xylose using a nickel-iron-zirconia alloy catalyst. The method is disclosed at 60°C and 300 kg / cm. 2 There is an advantage in that xylose is hydrogenated under hydrogen pressure and then crystallized to convert it into xylitol with a purity of 99.6%, but there are disadvantages in that it requires a reaction facility that can withstand high pressure, nickel and iron, which are active components of the catalyst, dissolve in the reaction products, and the catalyst gradually becomes inactive as the reaction proceeds for a long time, and in order to produce sugar acids such as xylic acid and gluconic acid in addition to sugar alcohols, a separate reaction and different catalysts are applied, which increases the manufacturing cost.

[0008] Recently, to overcome the shortcomings of these hydrogenation methods, new sugar conversion methods have been reported that facilitate catalyst recovery and simultaneously produce sugar alcohols and sugar acids at relatively low temperatures and pressures. However, since these sugar conversion methods are performed in an alkaline atmosphere due to the presence of metal hydroxides, there is a need for catalysts that exhibit high catalytic activity even in alkaline environments.

[0009] [Prior Art Literature]

[0010] [Patent Document]

[0011] (Patent Document 1) U.S. Patent No. 3,586,537 (Registration Date: June 22, 1971)

[0012] (Patent Document 2) U.S. Patent No. 4,008,285 (Registration Date: February 15, 1977)

[0013] (Patent Document 3) U.S. Patent No. 6,124,443 (Registration Date: September 26, 2000)

[0014] The main purpose of the present invention is to provide a catalyst for sugar alcohol and acid conversion reactions, which is created to solve the above-mentioned problem, and which allows easy catalyst recovery, can produce acids and alcohols from sugars under mild reaction conditions of low temperature and low pressure compared to existing reaction conditions, and can selectively control the yields of acids and alcohols by the type of catalytically active metal.

[0015] 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.

[0016] In order to solve the above problem, the present invention provides a catalyst for the simultaneous conversion reaction of sugar into acid and alcohol, characterized in that at least one metal element selected from the group consisting of ruthenium (Ru), silver (Ag), gold (Au), tin (Sn), and rhodium (Rh) and platinum (Pt) are supported on a catalyst support.

[0017] In one embodiment of the catalyst of the present invention, the molar number of the metal element may be 0.01 to 10 times the molar number of platinum, and the catalytically active metal may be 0.1 to 20 wt% with respect to the total weight of the catalyst.

[0018] In one embodiment of the catalyst of the present invention, the catalyst may be characterized in that at least one metal element selected from the group consisting of silver (Ag), gold (Au), tin (Sn), and rhodium (Rh) and platinum (Pt) are supported on a catalyst support, and the selectivity to alcohol is increased compared to a catalyst in which at least one metal element other than platinum is not supported.

[0019] In one embodiment of the catalyst of the present invention, the catalyst may be characterized in that ruthenium (Ru) and platinum (Pt) are supported on a catalyst support, and the selectivity toward an acid is increased compared to a catalyst in which ruthenium is not supported together with platinum.

[0020] In one embodiment of the catalyst of the present invention, the catalyst support may be characterized by being a metal oxide compound 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), copper (Cu), iron (Fe), manganese (Mn), aluminum (Al), gallium (Ga), and phosphorus (In), and the base may be characterized by being a hydroxide of an alkali metal and / or a hydroxide of an alkaline earth metal.

[0021] In addition, the present invention provides a method for simultaneously producing an acid and an alcohol from sugar, which comprises reacting sugar in the presence of a catalyst supported on a catalyst support, wherein the catalyst support includes at least one metal element selected from the group consisting of ruthenium (Ru), silver (Ag), gold (Au), tin (Sn), and rhodium (Rh) and a catalytically active metal including platinum (Pt).

[0022] In the method for simultaneously producing an acid and an alcohol of the present invention, the molar number of the metal element may be 0.01 to 10 times the molar number of platinum, the catalytically active metal may be 0.1 to 20 wt% based on the total weight of the catalyst, the base may be a hydroxide of an alkali metal and / or a hydroxide of an alkaline earth metal, and the simultaneous production reaction of an acid and an alcohol may be performed at 0°C to 200°C.

[0023] The catalyst according to the present invention can simultaneously produce alcohol and acid from sugar under mild reaction conditions of low temperature and low pressure compared to existing reaction conditions, and can selectively control the yield of either alcohol or acid depending on the type of catalytically active metal, and can exhibit stable recycling efficiency over a long period of time since recovery and reuse of the catalyst are advantageous even under strongly alkaline conditions.

[0024] In addition, the method for simultaneously producing alcohol and acid from sugar according to the present invention produces alcohol and acid simultaneously under a single mild reaction condition of low temperature and low pressure, instead of producing alcohol and acid separately from sugar under different reaction conditions in the presence of two or more different catalysts, thereby shortening the process for producing alcohol and acid, which was complicated and took a long time in the past, and thus has the effect of improving the productivity of alcohol and acid from sugar.

[0025] Figure 1 illustrates a conversion reaction mechanism of glucose according to one embodiment of the present invention.

[0026] Figure 2 illustrates a conversion reaction mechanism of xylose according to one embodiment of the present invention.

[0027] Figure 3 is an XRD measurement graph of the catalysts manufactured in Manufacturing Examples 1 to 3 and 14 of the present invention.

[0028] Figure 4 is a TEM measurement graph of the catalysts manufactured in Manufacturing Examples 1 to 3 and 14 of the present invention.

[0029] Figure 5 is a graph showing the glucose conversion rate, gluconic acid yield, and sorbitol yield measured in Examples 1, 10, 13 to 15 of the present invention and Comparative Example 5.

[0030] Figure 6 is a graph showing the glucose conversion rate, gluconic acid yield, and sorbitol yield measured in Examples 1, 6 to 9 and Comparative Examples 5 and 6 of the present invention.

[0031] Figure 7 is a graph showing the glucose conversion rate, gluconic acid yield, and sorbitol yield measured in Examples 10 and 12 and Comparative Examples 1 and 5 of the present invention.

[0032] Figure 8 is a graph showing the glucose conversion rate, gluconic acid yield, and sorbitol yield measured in Examples 1 to 5 of the present invention.

[0033] Figure 9 is a graph showing the glucose conversion rate, gluconic acid yield, and sorbitol yield measured in Examples 16 and 17 of the present invention.

[0034] Figure 10 is a graph showing the glucose conversion rate, gluconic acid yield, and sorbitol yield measured in Examples 1, 5, 6, 10, and 11 of the present invention, and Comparative Examples 5 and 6.

[0035] The advantages and features of the present invention, and the methods for achieving them, will become clearer with reference to the embodiments described in detail below together with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various different forms. These embodiments are provided solely to ensure that the disclosure of the present invention is complete and to fully inform those skilled in the art of the scope of the invention, and the present invention is defined solely by the scope of the claims.

[0036] In describing the present invention, if it is determined that a detailed description of a related known technology may unnecessarily obscure the gist of the present invention, the detailed description is omitted.

[0037] In the specification, when "includes," "has," "consists of," and "consists of" are used, other parts may be added unless "only" is used. When a component is expressed in the singular, it includes the plural unless otherwise explicitly stated.

[0038] The present invention relates to a catalyst used in a conversion reaction for simultaneously producing sugar into an acid and an alcohol 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 sugar in the presence of a base and a catalyst, and the catalyst is characterized in that a catalytically active metal including at least one metal element selected from the group consisting of ruthenium (Ru), silver (Ag), gold (Au), tin (Sn), and rhodium (Rh) and platinum (Pt) is supported on a catalyst support.

[0039] The catalyst according to the present invention can selectively control the selectivity between alcohol and acid by the type of catalytically active metal supported on the catalyst support.

[0040] Specifically, in order to increase the selectivity of alcohol among the alcohols and acids produced by the sugar conversion reaction, a catalyst support may be supported with one or more metal elements selected from the group consisting of silver (Ag), gold (Au), tin (Sn), and rhodium (Rh) and a catalytically active metal including platinum (Pt), and in order to increase the selectivity of acid, a catalytically active metal including ruthenium (Ru) and platinum (Pt) may be supported on the catalyst support.

[0041] At this time, the molar number of at least one metal element selected from the group consisting of ruthenium (Ru), silver (Ag), gold (Au), tin (Sn), and rhodium (Rh), which are the catalytically active metals, may be supported on the catalyst support in an amount of 0.01 to 10 times, preferably 0.1 to 1.0 times, the molar number of platinum. When the molar number of at least one metal element selected from the group consisting of ruthenium (Ru), silver (Ag), gold (Au), tin (Sn), and rhodium (Rh) is in a range of 0.01 to 10 times the molar number of platinum, an economically high sugar-to-acid and alcohol-to-conversion activity can be maintained.

[0042] As the catalytically active metal, at least one metal element selected from the group consisting of ruthenium (Ru), silver (Ag), gold (Au), tin (Sn), and rhodium (Rh) and platinum may be supported in an amount of 0.1 wt% to 20 wt% based on the total weight of the catalyst, preferably 0.1 wt% to 10 wt%, and more preferably 1.0 wt% to 8 wt%. When the catalytically active metal is 0.1 wt% or more based on the total weight of the catalyst, the reactivity can be increased as a sufficient catalytically active component in the sugar conversion reaction, and when it is 20 wt% or less, the dispersion of the catalytically active metal can be appropriately maintained, so that sufficient activity of the catalytically active metal can be maintained, and the catalytically active component can be used economically.

[0043] Meanwhile, the catalyst support on which the catalytically active metal is supported may be a metal oxide compound 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), copper (Cu), iron (Fe), manganese (Mn), gallium (Ga), and phosphorus (In), which has excellent long-term stability even under basic conditions and has excellent sugar conversion rate and acid and alcohol selectivity. At this time, in the catalyst support, the metal oxide compound may be represented by MO (M = Zn, etc.), MO2 (M = Ti, Zr, Ce, Hf, etc.), M2O3 (M = Al), MOOH (M = Ni, Co, Fe, Mn, Al Ga, In, etc.), MO(OH)2 (M = Zr), or AB2O4 of spinel structure (wherein A metal is +2 ion of Mg, Zn, Fe, Cu, Ni, Mn, B metal is +3 ion of Al, Fe, Cr, etc.), and in terms of high long-term stability, it may preferably be a metal oxide such as zirconium (Zr), cerium (Ce), titanium (Ti), hafnium (Hf), and a material of spinel structure of AB2O4.

[0044] The present invention is characterized in that, in addition to platinum (Pt), at least one metal element selected from the group consisting of ruthenium (Ru), silver (Ag), gold (Au), tin (Sn), and rhodium (Rh) is further added as an active metal, and when at least one metal element selected from the group consisting of silver (Ag), gold (Au), tin (Sn), and rhodium (Rh) is selected as an active metal other than platinum (Pt), the selectivity of sugar to alcohol increases compared to a catalyst on which at least one metal element other than platinum is not supported, such as platinum, and when ruthenium (Ru) is selected as an active metal other than platinum (Pt), the selectivity of sugar to acid increases compared to a catalyst on which ruthenium is not supported, such as platinum.

[0045] The method for manufacturing a catalyst in which the above catalytically active metal is supported on a catalyst support can be applied without limitation as long as it is a method capable of supporting the catalytically active metal on the catalyst support, and specifically, the catalytically active metal 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, a hydrothermal synthesis method, etc.

[0046] In one embodiment, the impregnation-based support includes the steps of impregnating a precursor of a catalytically active metal into a catalyst support to support the catalytically active metal; and drying and calcining the catalyst support on which the catalytically active metal is supported.

[0047] The above impregnation can be performed by dissolving the precursor of the catalytically active metal in a solvent, dividing it into several stages, and evenly dispersing the precursor of the catalytically active metal dissolved in the solvent on the catalyst support, and performing wet impregnation at 10°C to 200°C. The impregnation time can be applied without limitation as long as it can be sufficiently supported depending on the situation, and can be performed for, for example, 1 hour to 12 hours.

[0048] At this time, in the present invention, the precursor of the catalytically active metal may be at least one selected from the group consisting of the catalytically active metal, that is, ruthenium (Ru), silver (Ag), gold (Au), tin (Sn), and rhodium (Rh), and at least one metal element selected from the group consisting of platinum, and a nitrate, sulfate, phosphoric acid, halogen salt, alkoxide salt, oxynitrate, hydrate, acetate salt, alkyl salt, hydrate thereof, etc., and preferably, a halogen salt hydrate may be used.

[0049] In addition, as a solvent capable of dissolving the precursor of the catalytically active metal, any known solvent capable of dissolving the catalytically active metal of the present invention can be used, and specifically, it can be 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., and the solvent content can be used without limitation as long as it is an amount capable of uniformly dispersing the precursor of the catalytically active metal, and for example, it can be 100 to 500 parts by weight with respect to 100 parts by weight of the precursor of the catalytically active metal.

[0050] Next, the catalyst support impregnated with the catalytically active metal 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 ℃ to 100 ℃, it can be calcined at 400 ℃ to 1,100 ℃ 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 cause cracks and pores to be generated due to rapid evaporation and oxidation of the solvent, which significantly reduces the strength.

[0051] The catalyst that has been calcined thereafter may undergo an activation step prior to the sugar conversion reaction. Specifically, the activation step may activate the catalyst by reducing the catalyst at a temperature at which the catalyst can be reduced in a reducing atmosphere. In one example, after mounting the catalyst in a reactor, the catalyst may be reduced by flowing 1.0% to 10% hydrogen (H2) gas at a flow rate of 50 ml / min to 300 ml / min at 100°C to 700°C for 0.5 to 8 hours.

[0052] The present invention also provides a method for simultaneously producing an acid and an alcohol from sugar. The method for simultaneously producing an acid and an alcohol of the present invention is characterized by simultaneously producing an acid and an alcohol by reacting sugar in the presence of a catalyst according to the present invention.

[0053] The method for producing an acid and alcohol according to the present invention can perform a sugar conversion reaction in the presence of a base after installing the catalyst according to the present invention in a reactor. At this time, the catalyst can perform the reaction after being reduced.

[0054] The sugar conversion reaction performed in the present invention can be performed in an open or closed reactor. To increase acid selectivity, it can be performed in an open reactor, and to increase alcohol selectivity, it is preferably performed in a closed reactor. In this case, the reaction can be performed in a batch or continuous manner, but is not limited thereto.

[0055] At this time, the sugar used as a raw material may include a monosaccharide, an oligosaccharide in which 2 to 10 or more monomer molecules are connected, and a polysaccharide in which more than 10 monosaccharide molecules are connected, and specifically, a sugar 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. Or it may include a mixture of these, preferably xylose, glucose, galactose, mannose, lactose, arabinose, etc.

[0056] Since the above 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 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.

[0057] In addition, the concentration of the sugar may be 0.1 mol or more, preferably 1 mol to 3 mol, in the conversion reaction. When the concentration of the sugar is 0.1 mol or more, the amount of hydrogen generated during the sugar reaction is sufficient, so that the acid and alcohol yields can be maintained at high levels.

[0058] 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 of the conversion reaction. At this time, the base to be added may be an alkali metal hydroxide or an alkaline earth metal hydroxide, 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.

[0059] At this time, the base can be used in an amount of 0.5 mol or more per 1 mol of sugar, and in terms of reaction activity, it can be preferably used in an amount of 1 mol to 4 mol. If the salt is used in an amount of 0.5 mol or more per 1 mol of sugar, the reaction efficiency of the sugar is appropriately controlled, thereby increasing the yield of alcohol and acid.

[0060] In addition, the base can selectively control the selectivity of alcohol and acid among the reaction products by adjusting the concentration. Specifically, to increase the selectivity of acid among the reaction products, 1 to 2 moles of base can be used per 1 mole of sugar, and to increase the selectivity of alcohol, 0.5 to 1 mole of base can be used per 1 mole of sugar.

[0061] The sugar conversion reaction using the catalyst of the present invention can produce acids and alcohols from sugars under mild single conditions compared to existing catalysts.

[0062] 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.

[0063] At this time, the above sugar conversion reaction can be performed at 0 ℃ to 200 ℃ at normal pressure, and more preferably, at 0 ℃ to 100 ℃.

[0064] In this way, the acid and alcohol produced by the method of the present invention are produced simultaneously from sugar without dissolution of the catalyst component under a mild single condition of low temperature and low pressure compared to the conventional method, 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.

[0065] Hereinafter, the catalytic activity of the catalyst for sugar alcohol and acid conversion reactions 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.

[0066] <Manufacturing Example: Catalyst Manufacturing>

[0067] Manufacturing Example 1: Manufacturing of 3 wt% Pt-Sn(3:1) / ZrO2 catalyst

[0068] 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. Thereafter, 0.3 g of H2PtCl6ㆍ6H2O and 0.111 g of SnCl4ㆍ5H2O were dissolved in 50 ml of deionized water to obtain a precursor solution of a catalytically active metal, and the ZrO2 slurry was slowly added to the obtained precursor solution of the catalytically active metal while constantly stirring to obtain a mixture. The obtained mixture was dried in a 100 ℃ oven for 24 hours, heated to 500 ℃ at a rate of 3 ℃ / min, and then calcined in a kiln for 4 hours to prepare a Pt-Sn / ZrO2 catalyst in which the total mass of Pt and Sn, which are catalytically active metals, was 3 wt% based on the total mass of the catalyst and the molar ratio of Pt and Sn was 3:1. Thereafter, the prepared catalyst was heated to 500 ℃ at a rate of 3 ℃ / min under a 5% H2 / Ar flow injected at a rate of 150 ml / min, and then reduced for 6 hours to activate the catalyst.

[0069] Manufacturing Example 2: Manufacturing of 3 wt% Pt-Sn(9:1) / ZrO2 catalyst

[0070] A Pt-Sn / ZrO2 catalyst in which Pt and Sn are 3 wt% of the total catalyst weight was prepared in the same manner as in Manufacturing Example 1, but a ZrO2 slurry was slowly added to a precursor solution of a catalytically active metal in which 0.36 g of H2PtCl6ㆍ6H2O and 0.05 g of SnCl4ㆍ5H2O were dissolved in 50 ml of deionized water, thereby preparing a Pt-Sn / ZrO2 catalyst in which the molar ratio of Pt and Sn was 9:1.

[0071] Manufacturing Example 3: Manufacturing of 3 wt% Pt-Sn(1:1) / ZrO2 catalyst

[0072] A Pt-Sn / ZrO2 catalyst in which Pt and Sn are 3 wt% of the total catalyst weight was prepared in the same manner as in Manufacturing Example 1, but a ZrO2 slurry was slowly added to a precursor solution of a catalytically active metal in which 0.2 g of H2PtCl6ㆍ6H2O and 0.22 g of SnCl4ㆍ5H2O were dissolved in 50 ml of deionized water, thereby preparing a Pt-Sn / ZrO2 catalyst in which the molar ratio of Pt and Sn was 1:1.

[0073] Manufacturing Example 4: Manufacturing of 3 wt% Pt-Au(3:1) / ZrO2 catalyst

[0074] 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. Thereafter, 0.3 g of H2PtCl6ㆍ6H2O and 0.08 g of HAuCl4ㆍ3H2O were dissolved in 50 ml of deionized water to obtain a precursor solution of a catalytically active metal, and the ZrO2 slurry was slowly added to the obtained precursor solution of the catalytically active metal while constantly stirring to obtain a mixture. The obtained mixture was dried in an oven at 100°C for 24 hours, heated to 500°C at a rate of 3°C / min, and then calcined in a kiln for 4 hours to produce a Pt-Au / ZrO2 catalyst in which the catalytically active metals Pt and Au were 3 wt% of the total catalyst weight and the molar ratio of Pt and Au was 3:1. Thereafter, the manufactured catalyst was heated to 300°C at a rate of 3°C / min under a 5% H2 / Ar flow injected at 150 ml / min, and then reduced for 6 hours to activate the catalyst.

[0075] Manufacturing Example 5: Manufacturing of 3 wt% Pt-Au(1:1) / ZrO2 catalyst

[0076] A Pt-Au / ZrO2 catalyst having 3 wt% of Pt and Au in the total catalyst weight was prepared in the same manner as in Manufacturing Example 4. However, a ZrO2 slurry was slowly added to a precursor solution of a catalytically active metal in which 0.2 g of H2PtCl6ㆍ6H2O and 0.15 g of HAuCl4ㆍ3H2O were dissolved in 50 ml of deionized water, thereby preparing a Pt-Au / ZrO2 catalyst having a molar ratio of Pt and Au of 1:1.

[0077] Manufacturing Example 6: Manufacturing of 3 wt% Au / ZrO2 catalyst

[0078] A Pt-Au / ZrO2 catalyst having 3 wt% of Au in the total catalyst weight was manufactured using the same method as in Manufacturing Example 4. However, a ZrO2 slurry was slowly added to a precursor solution of a catalytically active metal in which 0.3 g of HAuCl4ㆍ3H2O was dissolved in 50 ml of deionized water to manufacture an Au / ZrO2 catalyst loaded with 3 wt% of Au.

[0079] Manufacturing Example 7: Manufacturing of 3 wt% Pt-Rh(3:1) / ZrO2 catalyst

[0080] 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. Thereafter, 0.13 g of H2PtCl6ㆍ6H2O and 0.08 g of RhCl3ㆍH2O were dissolved in 50 ml of deionized water to obtain a precursor solution of a catalytically active metal, and the ZrO2 slurry was slowly added to the obtained precursor solution of the catalytically active metal while constantly stirring to obtain a mixture. The obtained mixture was dried in an oven at 100°C for 24 hours, heated to 500°C at a rate of 3°C / min, and then calcined in a kiln for 4 hours to produce a Pt-Rh / ZrO2 catalyst in which the catalytically active metals Pt and Rh were 3 wt% of the total catalyst weight and the molar ratio of Pt and Rh was 3:1. Thereafter, the manufactured catalyst was heated to 300°C at a rate of 3°C / min under a 5% H2 / Ar flow injected at 150 ml / min, and then reduced for 6 hours to activate the catalyst.

[0081] Manufacturing Example 8: Manufacturing of 3 wt% Pt-Ag(3:1) / ZrO2 catalyst

[0082] 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. Thereafter, 0.3 g of H2PtCl6ㆍ6H2O and 0.06 g of AgNO3 were dissolved in 50 ml of deionized water to obtain a precursor solution of a catalytically active metal, and the ZrO2 slurry was slowly added to the obtained precursor solution of the catalytically active metal while constantly stirring to obtain a mixture. The obtained mixture was dried in an oven at 100°C for 24 hours, heated to 500°C at a rate of 3°C / min, and then calcined in a kiln for 4 hours to produce a Pt-Ag / ZrO2 catalyst in which the catalytically active metals Pt and Ag were 3 wt% of the total catalyst weight and the molar ratio of Pt and Ag was 3:1. Thereafter, the manufactured catalyst was heated to 300°C at a rate of 3°C / min under a 5% H2 / Ar flow injected at 150 ml / min, and then reduced for 6 hours to activate the catalyst.

[0083] Manufacturing Example 9: Manufacturing of 3 wt% Pt-Ru(3:1) / ZrO2 catalyst

[0084] 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. Thereafter, 0.3 g of H2PtCl6ㆍ6H2O and 0.08 g of RuCl3ㆍH2O were dissolved in 50 ml of deionized water to obtain a precursor solution of a catalytically active metal, and the ZrO2 slurry was slowly added to the obtained precursor solution of the catalytically active metal while constantly stirring to obtain a mixture. The obtained mixture was dried in an oven at 100°C for 24 hours, heated to 500°C at a rate of 3°C / min, and then calcined in a kiln for 4 hours to prepare a Pt-Ru / ZrO2 catalyst in which the catalytically active metals Pt and Ru were 3 wt% of the total catalyst weight and the molar ratio of Pt and Ru was 3:1. Thereafter, the prepared catalyst was heated to 300°C at a rate of 3°C / min under a 5% H2 / Ar flow injected at 150 ml / min, and then reduced for 6 hours to activate the catalyst.

[0085] Manufacturing Example 10: Manufacturing of 3 wt% Ru / ZrO2 catalyst

[0086] A Ru / ZrO2 catalyst having 3 wt% Ru based on the total catalyst weight was manufactured using the same method as Manufacturing Example 8. However, a ZrO2 slurry was slowly added to a precursor solution of a catalytically active metal in which 0.3 g of RuCl3ㆍH2O was dissolved in 50 ml of deionized water to manufacture a Ru / ZrO2 catalyst having 3 wt% Ru loaded thereon.

[0087] Manufacturing Example 11: Manufacturing of 3 wt% Pt-Co(3:1) / ZrO2 catalyst

[0088] 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, 0.3 g of H2PtCl6ㆍ6H2O and 0.19 g of Co(NO3)2ㆍ6H2O were dissolved in 50 ml of deionized water to obtain a precursor solution of a catalytically active metal, and the ZrO2 slurry was slowly added to the obtained precursor solution of the catalytically active metal while constantly stirring to obtain a mixture. The obtained mixture was dried in an oven at 100°C for 24 hours, heated to 500°C at a rate of 3°C / min, and then calcined in a kiln for 4 hours to prepare a Pt-Co / ZrO2 catalyst in which the catalytically active metals Pt and Co were 3 wt% of the total catalyst weight and the molar ratio of Pt and Co was 3:1. Thereafter, the prepared catalyst was heated to 500°C at a rate of 3°C / min under a 5% H2 / Ar flow injected at 150 ml / min, and then reduced for 6 hours to activate the catalyst.

[0089] Manufacturing Example 12: Manufacturing of 3 wt% Pt-Ni(3:1) / ZrO2 catalyst

[0090] 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, 0.3 g of H2PtCl6ㆍ6H2O and 0.19 g of Ni(NO3)2ㆍ6H2O were dissolved in 50 ml of deionized water to obtain a precursor solution of a catalytically active metal, and the ZrO2 slurry was slowly added to the obtained precursor solution of the catalytically active metal while constantly stirring to obtain a mixture. The obtained mixture was dried in an oven at 100°C for 24 hours, heated to 500°C at a rate of 3°C / min, and then calcined in a kiln for 4 hours to produce a Pt-Ni / ZrO2 catalyst in which the catalytically active metals Pt and Ni were 3 wt% of the total catalyst weight and the molar ratio of Pt and Ni was 3:1. Thereafter, the manufactured catalyst was heated to 500°C at a rate of 3°C / min under a 5% H2 / Ar flow injected at 150 ml / min, and then reduced for 6 hours to activate the catalyst.

[0091] Manufacturing Example 13: Manufacturing of 3 wt% Pt / ZrO2 catalyst

[0092] 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. Thereafter, 0.4 g of H2PtCl6ㆍ6H2O was dissolved in 50 ml of deionized water to obtain a precursor solution of a catalytically active metal, and the ZrO2 slurry was slowly added to the obtained precursor solution of the catalytically active metal while constantly stirring to obtain a mixture. The obtained mixture was dried in an oven at 100°C for 24 hours, heated to 500°C at a rate of 3°C / min, and calcined in a kiln for 4 hours to prepare a Pt / ZrO2 catalyst in which Pt is 3 wt% of the total catalyst weight. The manufactured catalyst was then heated to 300°C at a rate of 3°C / min under a 5% H2 / Ar flow injected at 150 ml / min, and then reduced for 6 hours to activate the catalyst.

[0093] <Experimental Example 1: Catalyst Characteristics Analysis>

[0094] In order to analyze the characteristics of the catalyst according to the platinum (Pt) and tin (Sn) content, the specific surface area, pore size, and pore volume of the catalysts manufactured in Manufacturing Examples 1 to 3 and 11 were analyzed using BET (Brunauer-Emmett-Teller analysis), and the content and size of the supported platinum and tin were analyzed using ICP (inductively coupled plasma analysis) and TEM (transmission electron microscopy analysis). In order to measure the composition of these catalysts, XRD (X-ray diffraction analysis) patterns were measured, and the results are shown in Table 1 and Figures 3 and 4. In the above Fig. 4, (a-1) is a TEM image of the catalyst manufactured in Manufacturing Example 14, (a-2) is a 5-magnification image of (a-1), (b-1) is a TEM image of the catalyst manufactured in Manufacturing Example 1, (b-2) is a 5-magnification image of (b-1), (c-1) is a TEM image of the catalyst manufactured in Manufacturing Example 2, (c-2) is a 5-magnification image of (c-1), (d-1) is a TEM image of the catalyst manufactured in Manufacturing Example 3, and (d-2) is a 5-magnification image of (d-1).

[0095] [Table 1]

[0096]

[0097] As shown in Table 1, the specific surface area, pore size, and volume were virtually maintained when the platinum and tin contents were varied. Furthermore, ICP analysis confirmed that the platinum and tin contents within the catalyst matched the amounts of metal precursors added during the synthesis process.

[0098] In addition, as shown in FIGS. 3 and 4, it was confirmed that all catalytically active metal particles had an average size of 1.5 nm to 2 nm, and were distributed in a uniform size.

[0099] <Experimental Example 2: Evaluation of catalytic activity according to the type of catalytically active metal>

[0100] In order to evaluate the reaction activity according to the catalytically active metal in the simultaneous production of gluconic acid and sorbitol from glucose, the reaction was carried out as follows under the same conditions.

[0101] Each of the catalysts manufactured in Manufacturing Examples 1 to 14, 0.4 g, and a solution of glucose and KOH in 6 ml of distilled water at concentrations as shown in Table 2 were introduced into a reactor. Thereafter, the reactor was stirred at 1,400 rpm for 6 hours at 25°C, and the reaction products generated after the reaction were analyzed through liquid chromatography. The glucose conversion rate and the yields of gluconic acid and sorbitol in each example and comparative example are shown in Table 3 and Fig. 5.

[0102] [Table 2]

[0103]

[0104] [Table 3]

[0105]

[0106] As shown in Table 3 and Figure 5, it can be confirmed that in Examples 1, 10, 13 to 15, not only the glucose conversion rate but also the gluconic acid selectivity and sorbitol selectivity are significantly higher than in Comparative Examples 3 to 4.

[0107] In addition, compared to a catalyst in which Pt was supported solely as an active metal on a ZrO2 support (Comparative Example 5), it was confirmed that Examples 1, 10, 13, and 14 using Pt-Sn, Pt-Au, Pt-Rh, and Pt-Ag as a catalytically active metal were superior in terms of sorbitol selectivity, and Example 15 using Pt-Ru was superior in terms of gluconic acid selectivity.

[0108] <Experimental Example 3: Evaluation of catalytic activity according to the content ratio of catalytically active metals>

[0109] In order to evaluate the reaction activity according to the use of an open reactor or a closed reactor in the simultaneous production of gluconic acid and sorbitol from glucose, the glucose conversion rate and the yields of gluconic acid and sorbitol in examples and comparative examples in which the reaction was carried out under the same conditions were measured, and the results are shown in Figs. 6 and 7. In Fig. 6, Fig. 6a shows the measurement results measured in an open reactor, and Fig. 6b shows the measurement results measured in a closed reactor.

[0110] As shown in Fig. 6, it can be confirmed that the closed case increases the selectivity to sorbitol. In addition, it can be confirmed that the selectivity to sorbitol changes depending on the ratio of Pt-Sn, and that there is an appropriate ratio of Pt-Sn at which the selectivity to sorbitol is maximized.

[0111] In addition, as shown in Fig. 7, in the case of Examples 10 and 12, it was confirmed that not only the glucose conversion rate but also the sorbitol selectivity were higher compared to Comparative Examples 1 and 5, and it was confirmed that there was no reaction activity when Au alone was used as the catalytically active metal, and that the activity changed depending on the relative ratio of Pt and Au.

[0112] <Experimental Example 4: Evaluation of Catalytic Activity According to Base Concentration>

[0113] In order to evaluate the reaction activity according to the base concentration in the simultaneous production of gluconic acid and sorbitol from glucose, the glucose conversion rate and the yield of gluconic acid and sorbitol in examples and comparative examples in which the reaction was carried out under the same conditions were measured, and the results are shown in Fig. 8.

[0114] As shown in Fig. 8, it was confirmed that as the base concentration increased, the conversion rate of glucose and the yield of gluconic acid increased, but the selectivity for sorbitol decreased somewhat when the base concentration increased beyond 1.25 M.

[0115] <Experimental Example 5: Evaluation of Catalytic Activity According to Reaction Temperature>

[0116] In order to evaluate the reaction activity according to the reaction temperature in simultaneously producing gluconic acid and sorbitol from glucose, the glucose conversion rate and the yield of gluconic acid and sorbitol in examples and comparative examples in which the reaction was carried out under the same conditions were measured, and the results are shown in Fig. 9.

[0117] As shown in Fig. 9, it was confirmed that as the reaction temperature increased, the glucose conversion rate and the yield of gluconic acid and sorbitol increased.

[0118] <Experimental Example 6: Evaluation of Catalytic Activity According to Reactor Type>

[0119] In order to evaluate the reaction activity according to the use of an open reactor or a closed reactor in the simultaneous production of gluconic acid and sorbitol from glucose, the glucose conversion rate and the yields of gluconic acid and sorbitol in examples and comparative examples in which the reaction was carried out under the same conditions were measured, and the results are shown in Fig. 10. In Fig. 10, Fig. 10a shows the measurement results measured in a closed reactor, and Fig. 10b shows the measurement results measured in an open reactor.

[0120] As shown in Fig. 10, in the case of Examples 2, 6, 11 and Comparative Example 6 using a closed reactor, it was confirmed that the selectivity for sorbitol was higher than in the case of Examples 1, 5, 10 and Comparative Example 5 using an open reactor under the same conditions, and in the case of an open reactor, it was confirmed that the selectivity for gluconic acid was higher.

[0121] <Experimental Example 7: Activity Evaluation According to the Type of Catalyst Support>

[0122] To evaluate the effect of the catalyst support, the catalyst was prepared as follows.

[0123] A catalyst loaded with 3 wt% of an active metal was prepared in the same manner as in Manufacturing Examples 1, 4, 7, 8, 9, 11, 12, and 13, except that one support selected from AlOOH, TiO2, and CeZrO2 was used as the catalyst support.

[0124] The above AlOOH was obtained by dissolving 40 mmol of Al(NO3)3ㆍ9H2O in 120 mL of ethanol, stirring at room temperature for 15 minutes, adding 2 M NaOH aqueous solution to the solution to adjust the pH to 11, placing it in a 250 mL hydrothermal reactor, reacting the hydrothermal reactor in an oven at 180°C for 24 hours, separating the obtained powder using centrifugation, and purifying the obtained mixture with ethanol and water, drying the obtained mixture in an oven at 65°C for 12 hours.

[0125] The above TiO2 (Titanium (IV) oxide, rutile, nanopowder (<100 nm particle size), 99.5% trace metals basis) was purchased from Sigma-Aldrich (Product No.: 637262, CAS No.: 1317-80-2) and used. CeZrO2 is a ZrO2 structure containing 5 mol% Ce. 18.55 g of ZrOCl2ㆍ8H2O, 1.30 g of Ce(NO3)3ㆍ6H2O, 36 g of Urea, and 140 mL of deionized water were placed in a 250 mL hydrothermal reactor, and the hydrothermal reactor was reacted in an oven at 200 ℃ for 20 hours. The obtained powder was separated using a centrifuge and purified with water. The obtained mixture was dried in an oven at 100 ℃ for 12 hours, heated to 400 ℃ at a rate of 5 ℃ / min, and then calcined in a kiln for 4 hours. It was synthesized by calcination.

[0126] The activity of each catalyst obtained in this way was measured by the same method as Experimental Example 2 above, and although catalysts containing the same active metal and having different supports have a slight difference in activity depending on the type of support, they are similar to each other. When a metal element selected from silver (Ag), gold (Au), tin (Sn), and rhodium (Rh) is supported as an active metal together with platinum (Pt), the selectivity for glucose to sorbitol increases compared to a catalyst supported only with platinum, and when ruthenium (Ru) and platinum (Pt) are supported simultaneously, the selectivity for glucose to gluconic acid tends to increase. Therefore, in the present invention, which includes platinum (Pt) and at least one metal element selected from the group consisting of ruthenium (Ru), silver (Ag), gold (Au), tin (Sn), and rhodium (Rh) as an active metal, it was confirmed that the selectivity for sugar to acid and alcohol changes depending on the type of the active metal.

[0127] 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 conversion reaction of sugar into 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 the catalyst support contains at least one metal element selected from the group consisting of ruthenium (Ru), silver (Ag), gold (Au), tin (Sn), and rhodium (Rh) and a catalytically active metal including platinum (Pt).

2. In paragraph 1, A catalyst for the simultaneous conversion reaction of sugar into acid and alcohol, characterized in that the molar number of the above metal element is 0.01 to 10 times the molar number of platinum.

3. In paragraph 1, A catalyst for the simultaneous conversion reaction of sugar into acid and alcohol, characterized in that the catalytically active metal is 0.1 wt% to 20 wt% based on the total weight of the catalyst.

4. In paragraph 1, The catalyst is a catalyst for the simultaneous conversion reaction of sugar into acid and alcohol, characterized in that the catalyst is supported on a catalyst support and has increased selectivity to alcohol compared to a catalyst not supported with at least one metal element selected from the group consisting of silver (Ag), gold (Au), tin (Sn), and rhodium (Rh), and platinum (Pt).

5. In paragraph 1, The above catalyst is a catalyst for the simultaneous conversion reaction of sugar into acid and alcohol, characterized in that ruthenium (Ru) and platinum (Pt) are supported on a catalyst support, and selectivity toward acid is increased compared to a catalyst in which ruthenium (Ru) is not supported in addition to platinum (Pt).

6. In paragraph 1, A catalyst for the simultaneous conversion reaction of sugar into acid and alcohol, characterized in that the catalyst support is a metal oxide compound 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), copper (Cu), iron (Fe), manganese (Mn), aluminum (Al), gallium (Ga), and phosphorus (In).

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

8. 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 supported on a catalyst support and includes at least one metal element selected from the group consisting of ruthenium (Ru), silver (Ag), gold (Au), tin (Sn), and rhodium (Rh) and a catalytically active metal including platinum (Pt).

9. In paragraph 8, A method for simultaneously producing acid and alcohol from sugar, characterized in that the molar number of the above metal element is 0.01 to 10 times the molar number of platinum.

10. In paragraph 8, A method for simultaneously producing acid and alcohol from sugar, characterized in that the catalytically active metal is 0.1 wt% to 20 wt% based on the total weight of the catalyst.

11. In paragraph 8, A method for simultaneously producing an acid and an alcohol from sugar, characterized in that the base is a hydroxide of an alkali metal and / or a hydroxide of an alkaline earth metal.

12. In paragraph 8, 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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