KR101105460B1 - Method for preparing sugar alcohols using ruthenium zirconia catalyst - Google Patents

Abstract

The present invention relates to a method for producing a sugar alcohol using a ruthenium zirconia catalyst, while supporting a zirconia carrier so that the dispersibility of ruthenium is 10% or more, while using a catalyst having a chlorine content of less than 100 ppm sugars under relatively mild reaction conditions The present invention relates to a method for producing sugar alcohols by corresponding hydrogenation thereof. In the process of the present invention, by producing a high-purity sugar alcohol in a continuous process at a low temperature, low pressure and mild conditions without dissolving the catalyst component during the hydrogenation reaction, almost no by-products and wastes are generated, and sugar alcohols can be prepared without a complicated separation process. Can be.

Description

Method for producing sugar alcohols using ruthenium zirconia catalyst {METHOD FOR PREPARING SUGAR ALCOHOLS USING RUTHENIUM ZIRCONIA CATALYST}

The present invention relates to a method for preparing sugar alcohols corresponding thereto by hydrogenation of sugars using a catalyst in which ruthenium is supported on a zirconia carrier. More specifically, ruthenium is supported on a zirconia carrier with a dispersibility of 10% or more, and a chlorine content of less than 100 ppm is used to hydrogenate saccharides at low temperature and low pressure without dissolution of the catalyst component during hydrogenation to produce sugar alcohols corresponding thereto. It is about how to.

Sugar alcohols such as xylitol, sorbitol, mannitol, maltitol and the like are useful substances widely used in food additives, pharmaceuticals, cosmetics, and the like. In general, sugar alcohols are mostly prepared by hydrogenation of the corresponding sugars, and representative examples are as follows.

As a hydrogenation method, US Pat. Nos. 3,586,537, 4,008,285 and the like disclose a method for producing xylitol by hydrogenating xylose in a batch reactor using a Ranickel catalyst. Such a production method requires a complicated separation and purification process and a catalyst recovery process due to a large amount of by-products, metals are melted into the solution, and catalysts are inactivated.

Recently, in order to overcome the disadvantages of the batch reaction, a continuous hydrogenation production method using a nickel-based catalyst has been reported. US Pat. No. 6,414,201 describes a process for producing xylitol in 98% yield by continuously hydrogenating a saccharide such as xylose at a hydrogen pressure of 120 ° C. and 150 kg / cm ² using a Ranickel-alumina catalyst. However, this method has a disadvantage in that the reaction activity is lowered over time.

In addition, US Pat. No. 6,124,443 reports a process for the continuous hydrogenation of xylose using a nickel-iron-zirconia alloy catalyst. The method has the advantage of converting to xylitol of 99.6% purity after crystallization by hydrogenating xylose under hydrogen pressure of 300 ° C. and 300 kg / cm ² , but requires a high pressure resistant reaction facility and does not expose the catalyst to an air atmosphere. It has the disadvantage of being manufactured and processed.

Meanwhile, in the prior art, patents have been reported for using a ruthenium catalyst in a hydrogenation reaction. U.S. Patent No. 3,963,788 discloses a method of hydrogenating saccharides by supporting ruthenium on a zeolite carrier having a silica / alumina molar ratio of 3 or more. In this patent, zeolite is added to an aqueous solution of ruthenium chloride and stirred in a slurry form at 80 ° C. to replace ruthenium by ion exchange, followed by filtration and washing with distilled water to remove unsubstituted ruthenium chloride from the carrier, followed by drying and reduction. Was prepared, and the catalyst used after the hydrogenation reaction was claimed to be renewable through pickling. However, this method uses the ion exchange method in the preparation of the catalyst, the loss of the ruthenium precursor, difficult to control the ruthenium content, the addition of the catalyst regeneration process, and also has a low yield of 97% to separate the high purity sugar alcohol production Separation process is required.

U.S. Patent No. 4,380,679 discloses a method of hydrogenating saccharides by preparing a catalyst having a Group 8 metal such as ruthenium on a pyropolymer carrier complexed with an inorganic oxide such as alumina. In this patent, a catalyst was prepared by treating an inorganic oxide such as alumina with an organic pyrolytic substance at high temperature, dissolving it with an acid or a base, and then supporting the metal on a carbonaceous pyropolymer carrier, followed by calcining and reducing. In comparison with the general alumina carrier catalyst, it was claimed that the stability and the reaction activity against hot water are excellent. However, although the degree of dissolution of the carrier is relatively improved during the hydrogenation reaction compared with the case of using the gamma alumina carrier, aluminum is still dissolved in several ppm units and there is a disadvantage in that the reaction selectivity is low.

U.S. Patent No. 4,950,812 describes a method of converting polysaccharides to monosaccharide alcohols by simultaneously performing hydrolysis and hydrogenation using a catalyst having an increased dispersibility of ruthenium by ion-exchanging ruthenium amine complex salts in an acidic carrier such as zeolite. The zeolite carrier substituted with ammonium ion was added to an aqueous solution of hexaamine ruthenium chloride, followed by ion exchange to obtain a zeolite substituted with rutheniumamine, followed by filtration and washing to remove residual ruthenium salt and ammonium chloride, and dried at room temperature and then reduced in a hydrogen atmosphere. To the hydrogenation reaction. This method can be supported by ruthenium amine complex salts with high dispersion during ion exchange, and has the advantage of simultaneously performing hydrolysis and hydrogenation by using an acidic carrier, but the reaction temperature during hydrolysis is relatively high. It is easy and thus difficult to selectively produce a sugar alcohol, there is a problem that the carrier component silicon and aluminum are dissolved during the reaction. In addition, there is a disadvantage in that expensive ruthenium amine complex salts must be used as compared to ruthenium chloride.

U.S. Pat.No. 6,177,598 discloses hydrogenation of sugars using a catalyst in which a Group 8 transition metal, including ruthenium, is supported on a carrier such as alumina having an appropriate ratio of 2 to 50 nanometers of mesopores and 50 to 10,000 nanometers of large pores. In case of the reaction, it was claimed that 99% purity sugar alcohols were prepared without the problem of melting metal during the reaction. However, this method also requires a separate purification process in order to obtain a high-pressure equipment and high purity products, there is a problem that the catalyst is deactivated.

In addition, WO 02/100537 reports a method of hydrogenating xylose at 100 ° C. and 50 kg / cm ² by reducing a dry catalyst without firing using a ruthenium precursor without a halogen element in a silica carrier. Compared to ruthenium chloride used in the present invention, an expensive ruthenium precursor is used, and there is a problem in that a silica component as a carrier is dissolved during the hydrogenation reaction. In addition, the selectivity of xylitol is low to 97%, there is a disadvantage that requires separation and purification after the reaction.

US Pat. No. 6,570,043 discloses a method of hydrogenating saccharides at 100 ° C. and 100 kg / cm ² using a catalyst loaded with ruthenium in titania, but still exhibits low selectivity for sugar alcohols at high conversion rates. It was.

On the other hand, techniques for converting sugars such as xylose to xylitol using enzymes have been reported, unlike the hydrogenation method. U.S. Patent No. 5,998,181 discloses a method for preparing xylitol by fermentation for 48 hours using a Candida tropicicalis strain. The fermentation method has an advantage that the separation and purification process is easy compared to the batch hydrogenation method, but has a long reaction time and low productivity.

Technical Challenge

Accordingly, an object of the present invention is to solve the above problems by using a heterogeneous catalyst having a higher activity and life under milder conditions than the prior art by selectively hydrogenating saccharides without dissolution of the catalyst component during the hydrogenation reaction by-products and It provides a high-purity sugar alcohol production method in a simple process that generates little waste and does not require a complicated purification process.

Technical solution

According to the present invention, a zirconia carrier is loaded with a ruthenium dispersity of 10% or more and a catalyst having a chlorine content of less than 100 ppm, using a reaction temperature of 20 to 150 ° C. and a reaction pressure of 5 to 300 kg / cm ² . There is provided a process for preparing the corresponding sugar alcohols by hydrogenation of sugars in

Hereinafter, the present invention will be described in more detail.

Best Mode for Carrying Out the Invention

According to the method of the present invention, unlike the conventional method, by hydrating saccharides using a catalyst having high concentration of ruthenium on a zirconia carrier, sugars having high purity can be efficiently obtained under relatively mild reaction conditions without complicated separate separation process. It can manufacture.

In general, the hydrogenation reaction of the Group 8 to 11 transition elements of the periodic table is used a lot, especially ruthenium and nickel are reported to have high activity in the hydrogenation of sugars, but due to high pressure reaction conditions, isomerization, decomposition, polymerization There was a problem that by-products are generated and the catalyst is deactivated.

In view of the above problems, in the present invention, a catalyst in which a zirconia is selected as a carrier while stable in the reaction solution and has a high dispersion of ruthenium is used. By using such a ruthenium-supported zirconia carrier catalyst, sugars can be hydrogenated under relatively mild reaction conditions to produce sugar alcohols with high purity without dissolving the catalyst components during the reaction. In addition, the activity of the catalyst can be stably maintained by controlling the content of chlorine in the preparation of the catalyst.

Zirconia can be used as a carrier in the present invention. At this time, at least 90% by weight of the total weight of the carrier should be made of zirconia, and the remaining carrier components may be selected as necessary, but the content of impurities such as iron and sulfur in the carrier is less than 0.2% by weight for each component It is preferable to be. If the carrier component contains less than 90% by weight of zirconia, the amount of binder, such as silica, alumina, clay, etc., which may be the remaining carrier component, increases, so that such components are dissolved during the reaction and the catalyst is broken or There is a problem that the activity is sharply reduced. In addition, when components such as titania, sulfur, etc., which are poorly dissolved during the reaction, increase in the carrier, the specific surface area of the carrier is rapidly reduced or poisoned.

As the zirconia used in the present invention, monocrystalline, tetragonal, amorphous zirconia may be used. The surface area of the carrier to be used is preferably 10 to 500 m ² / g. If the surface area of the carrier is less than 10 m ² / g, the metal is difficult to be dispersed evenly, and if the surface area of the carrier is 500 m ² / g or more, the size of the pores is small, the reaction activity is rather low. For the continuous hydrogenation reaction using a fixed bed reactor, it is molded into an appropriate size according to the length and diameter of the reactor.

The catalyst in which ruthenium is loaded on the zirconia used in the present invention is prepared by the following method.

That is, it is prepared by dissolving ruthenium in a salt state in a small amount of water and then supporting it on a zirconia carrier by an impregnation method generally known in the art. In the preparation of the ruthenium-supported catalyst of the present invention, ruthenium salts may include ruthenium chloride, ruthenium nitrate, ruthenium nitrosilnitrate, ruthenium acetylacetonate, and the like, and ruthenium chloride is particularly preferable. At this time, in the control of the chlorine content which has a significant effect on the catalytic activity, even in the case of using a precursor containing no chlorine such as ruthenium nitrosilnitrate and ruthenium acetylacetonate in addition to ruthenium chloride, other catalysts such as a carrier are prepared. Since chlorine may be present in the process, control of the chlorine content of the catalyst is required.

The catalyst carrying the ruthenium salt is dried at a temperature of 90 to 150 ° C. The dried catalyst is calcined at a temperature of 200 to 600 ° C. in nitrogen, helium or air as necessary. The dried or calcined catalyst is reduced to a temperature of 100 to 500 캜 in a reducing atmosphere such as hydrogen. The catalyst thus reduced is sufficiently washed with distilled water, aqueous ammonia, or an inorganic base aqueous solution such as sodium hydroxide or potassium hydroxide to remove chlorine and then dried again. In the case of calcined catalysts, they can be washed before reduction if necessary. Finally, the catalyst thus prepared can be used after reduction, if necessary, before use in the hydrogenation reaction.

The amount of ruthenium metal supported on the zirconia carrier is in the range of 0.1 to 10% by weight, based on the catalyst composition. If the ruthenium metal is less than 0.1% by weight, the rate of hydrogenation is slowed, and if it is more than 10% by weight, expensive noble metals are used in excess of the required amount, thereby lowering the economics of the process.

It is preferable to control by washing and / or baking so that the chlorine content in a ruthenium-supported catalyst may be less than 100 ppm. In the case of using a catalyst containing more than 100ppm chlorine, the deactivation proceeds quickly and an excessive byproduct is generated.

In one embodiment of the present invention, the dispersion degree of ruthenium supported on the carrier is preferably maintained at 10% or more. If the ruthenium dispersity is less than 10%, there is a disadvantage in that the catalytic activity is low in the mild reaction conditions desired in the present invention, so that a high purity sugar alcohol product cannot be easily produced. In addition, by increasing the temperature in order to increase the activity of the catalyst having a low dispersion degree, there is a problem in that by-product generation is increased. The dispersion degree is a value expressed as a percentage of the number of metal atoms exposed on the surface based on the total number of metal atoms in the catalyst, and the number of metal atoms exposed on the surface is measured by chemical adsorption of carbon monoxide. .

The amount of ruthenium metal supported on the zirconia carrier is in the range of 0.1 to 10% by weight. If the ruthenium metal is less than 0.1% by weight, the rate of hydrogenation is slow. If the ruthenium metal is less than 10% by weight, expensive noble metals are used in excess of the required amount, thereby degrading the economics of the process.

As described above, by using a catalyst loaded with zirconia with a dispersion of ruthenium of 10% or more, sugars can be hydrogenated under milder conditions to obtain sugar alcohols of high purity.

The hydrogenation reaction type carried out in the present invention may be carried out in a batch or continuous reaction type, in view of the operating cost and the reaction efficiency is more preferably a continuous reaction using a tubular fixed bed reactor.

The saccharides hydrogenated in the present invention include erythrose, xylose, arabinose, glucose, galactose, manos, fructose, lactose, lactulose, maltose, isomaltulose, talos, rhamnose, sucrose, starch sugar, One sugar or more sugar mixture selected from the group consisting of starch hydrolyzate, cellulose hydrolyzate, hemicellulose hydrolyzate.

Since the saccharide is generally solid at room temperature, it is preferable to dissolve the saccharide in an appropriate solvent in order to improve the reaction efficiency. As a solvent used for this purpose, both solvents capable of simultaneously dissolving sugars as raw materials and sugar alcohols as a reaction product are used, but it is generally preferable to use water or alcohol alone or a mixture thereof. Alcohols include methanol, ethanol, propanol, isopropanol or mixtures thereof. More preferably, water is used alone or in combination with water and ethanol. In the case of using a solvent, the concentration of sugars in the solution is not limited, but is preferably 1 to 60% by weight.

In the method of the present invention, the hydrogenation reaction of saccharides is preferably performed at a temperature of 20 to 150 ° C, more preferably 30 to 130 ° C. If the temperature is lower than 20 ° C., the reaction rate becomes slow. If the temperature is lower than 150 ° C., the side reaction increases, and there is a problem such as showing a color after the reaction.

The hydrogenation reaction of the saccharides by the method of the present invention is preferably performed at a pressure in the range of 5 to 300 kg / cm ² , more preferably 10 to 200 kg / cm ² . If the reaction pressure is lower than 5 kg / cm ² , the reaction rate is slow. If the reaction pressure is higher than 300 kg / cm ² , there is no problem in the reaction, but the economical efficiency of the process is reduced due to the increase of the equipment cost by using high pressure. do.

The amount of hydrogen introduced into the hydrogenation reaction is preferably 1 to 50 mol times the amount of saccharide used.

When the type of hydrogenation reaction is a continuous reaction, the weight space velocity of the saccharides introduced relative to the weight of the catalyst is suitably in the range of about 0.05 to 10 h ⁻¹ . At this time, if the weight space velocity is too slow, economic efficiency is lowered due to an increase in operating costs, and if the weight space velocity is too fast, there is a problem in that the reaction does not occur sufficiently.

As described above, the sugar alcohols prepared by the method of the present invention are produced in a continuous process under mild conditions of low temperature and low pressure as compared with the conventional method, and by the production of sugar alcohols selectively without dissolving the catalyst components, almost no by-products and wastes are generated. In addition to being an environmentally friendly process, high purity sugar alcohols of 99.5% or more can be prepared without complicated separation process.

Through the following examples will be described in more detail the present invention. The following examples do not limit the scope of the invention.

Example 1

Ruthenium chloride is evenly loaded so that the content of zirconia formed into a 3 mm size pellet is 99% by weight to 3% by weight, dried at 110 ° C. for 6 hours, and reduced at 350 ° C. for 6 hours while flowing hydrogen. Was carried out. The reduced catalyst was sufficiently washed with chlorine ions using an amount of 100 times the amount of the catalyst with 5% by weight of ammonia water. After washing, the mixture was re-dried at 110 ° C. for 6 hours to prepare a ruthenium catalyst having a ruthenium dispersion of 40% and a chlorine content of 50 ppm. 6 g of the catalyst was charged in a fixed bed tubular reactor made of stainless steel, and then reduced at 350 ° C. for 6 hours while flowing hydrogen at a rate of 50 cc / min. After completion of the reduction reaction, the hydrogen flow rate was adjusted to be 6 moles of xylose added, the reactor temperature was 60 ° C., the reaction pressure was 50 kg / cm ² , and then a weight space velocity of 0.10 h ⁻¹ (based on xylose) The reaction was started by adding the reaction raw materials with). Xylose was dissolved in 40 wt% of distilled water as a reaction raw material, and the reaction product was analyzed by liquid chromatography with a refractive index detector. After the reaction, an average conversion of 99.9% of xylose and a selectivity of 99.8% of xylitol were obtained for 100 hours, and thereafter, no activity was lowered even after continuous reaction for 3,000 hours or more. After the hydrogenation reaction, ruthenium and zirconium were not detected in each of 1 ppm.

Example 2

The reaction was carried out in the same manner as in Example 1 except that the reaction was used as glucose. During the 100 hours after the reaction, the average conversion of glucose was 99.9% and the selectivity of sorbitol was 99.8%. After that, no degradation was observed even after continuous reaction for 1,000 hours or more. After the reaction, ruthenium and zirconium were not detected in the solution of 1 ppm, respectively.

Example 3

The reaction was carried out in the same manner as in Example 1, except that sugars including xylose 80%, arabinose 9%, galactose 5%, and glucose 6% were used as reactants. The average purity of hydrogenated sugar alcohols for 100 hours after the reaction was 79.8% of xylitol, 9.2% of arabitol, 5% of galactitol, and 5.9% of sorbitol. Did. After the reaction, ruthenium and zirconium were not detected in the solution of 1 ppm, respectively.

Example 4

Ruthenium chloride was evenly loaded so that the content of zirconia formed into a pellet of 3 mm size was 3% by weight in a carrier having 99% by weight, dried at 110 ° C for 6 hours, and then calcined at 500 ° C in a nitrogen atmosphere for 5 hours. It was. The calcined catalyst was thoroughly washed with 5% by weight of ammonia water using 100 times the amount of the catalyst to remove chlorine, and then re-dried at 110 ° C. for 6 hours, and then reduced at 350 ° C. for 6 hours while flowing hydrogen to ruthenium. A ruthenium catalyst having a dispersity of 30% and a content of 40 ppm of chlorine was prepared. 6 g of the catalyst was charged into a fixed bed tubular reactor made of stainless steel, and then reduced at 350 ° C. for 3 hours while flowing hydrogen at a rate of 50 cc per minute. After completion of the reduction reaction, the hydrogen flow rate was adjusted to be 6 moles of xylose added, the reactor temperature was 60 ° C., the reaction pressure was 50 kg / cm ² , and then a weight space velocity of 0.10 h ⁻¹ (based on xylose) The reaction was started by adding the reaction raw materials with). Xylose was dissolved in 40 wt% of distilled water as a reaction raw material, and the reaction product was analyzed by liquid chromatography with a refractive index detector. During the 100 hours after the reaction, 99.9% of the average conversion of xylose and 99.7% of the selectivity of xylitol were obtained, and there was no deterioration in activity even after continuous reaction for 1,000 hours or more. After the reaction, ruthenium and zirconium were not detected in the solution of 1 ppm each.

Example 5

Ruthenium chloride was evenly loaded so that the content of zirconia formed into a pellet of 3 mm size was 3% by weight in a carrier having 99% by weight, dried at 110 ° C for 6 hours, and then calcined at 500 ° C in a nitrogen atmosphere for 5 hours. It was. The calcined catalyst was reduced at 350 ° C. for 6 hours while flowing hydrogen, and then thoroughly washed with 5% by weight of ammonia water using an amount 100 times the amount of the catalyst to remove chlorine. The washed catalyst was re-dried at 110 ° C. for 6 hours to prepare a ruthenium catalyst having a ruthenium dispersion of 28% and a content of 35 ppm of chlorine. 6 g of the catalyst was charged into a fixed bed tubular reactor made of stainless steel, and then reduced at 350 ° C. for 3 hours while flowing hydrogen at a rate of 50 cc per minute. After completion of the reduction reaction, the hydrogen flow rate was adjusted to be 6 moles of xylose added, the reactor temperature was 60 ° C., the reaction pressure was 50 kg / cm ² , and then a weight space velocity of 0.10 h ⁻¹ (based on xylose) The reaction was started by adding the reaction raw materials with). As a reaction raw material, xylose was dissolved in 40% by weight of distilled water, and the reaction product was analyzed by liquid chromatography with a refractive index detector. During the 100 hours after the reaction, 99.9% of the average conversion of xylose and 99.7% of the selectivity of xylitol were obtained, and there was no deterioration in activity even after continuous reaction for 1,000 hours or more. After the reaction, ruthenium and zirconium were not detected in the solution of 1 ppm each.

Comparative Example 1

The reaction was carried out in the same manner as in Example 1 except that a 3% by weight ruthenium catalyst having a dispersity of 4% and a chlorine content of 60 ppm was prepared using zirconia as a carrier. During the 100 hours after the reaction, the average conversion of xylose was 80.0% and the selectivity of xylitol was 99.8%. Due to the low dispersion, high-purity sugar alcohols could not be obtained directly, and a low recycling efficiency required a recycling reaction process.

Comparative Example 2

Evenly loaded ruthenium chloride in zirconia, dried at 110 ° C. for 6 hours, and reduced at 350 ° C. for 6 hours with flowing hydrogen without washing step to give 30% dispersion of ruthenium and 1,000 ppm of chlorine. The reaction was carried out in the same manner as in Example 1 except for preparing and using the prepared 3 wt% ruthenium catalyst. The reaction yielded 99.9% of xylose and 99.7% of xylitol selectivity for 20 hours after the reaction. The catalyst was deactivated over time to obtain 95.5% of xylose conversion after 270 hours.

Comparative Example 3

3% by weight of 3% by mass containing 70% of chlorine in an alumina carrier composed of 85.3% of large pore volume of 2 to 50 nm and 14.7% of medium pore volume of 50 to 10,000 nm. The reaction was carried out in the same manner as in Example 1 except that a ruthenium-supported catalyst was prepared and used. After the reaction, the average conversion of xylose was 82.1% and the selectivity of xylitol was 99.7% for 10 hours. The catalyst was deactivated as the reaction time passed, and the conversion of xylose was obtained at 72.1% after 48 hours. Although 1 ppm of ruthenium was not detected in the solution after the reaction, it was confirmed that 60 ppm of aluminum was dissolved in the carrier component during the reaction.

Comparative Example 4

The reaction was carried out in the same manner as in Example 1, except that a 3 wt% ruthenium catalyst containing 2.8% ruthenium and 50 ppm chlorine was prepared using silica as a carrier. During the 100 hours after the reaction, the average conversion of xylose was 76.0% and the selectivity of xylitol was 99.8%. Due to the low dispersion, the production efficiency per hour decreased. After the reaction, ruthenium was not detected in the solution of 1 ppm, but 20 ppm of silicon was detected to confirm that the carrier component was dissolved during the reaction.

By using a catalyst having a chlorine content of less than 100 ppm while supporting the zirconia carrier so that the dispersity of ruthenium is 10% or more, a sugar alcohol is selectively used in a continuous process under milder low temperature and low pressure without dissolving the catalyst component during the reaction. By producing the lysates, an environmentally friendly method with little generation of by-products and waste is provided, and high-purity sugar alcohols are produced efficiently and economically without complicated separate separation process.

Claims (14)

Supporting ruthenium salt on the zirconia carrier, drying at 90-150 ° C., calcining at 200-600 ° C., washing with at least one aqueous inorganic base solution selected from the group consisting of aqueous ammonia, sodium hydroxide and potassium hydroxide and drying To prepare a catalyst having a ruthenium dispersion of 10% to 100% and a chlorine content of less than 100 ppm, By using the catalyst, a method for producing a sugar alcohol to the corresponding sugar alcohols by hydrogenation under the conditions of reaction temperature 20 ~ 150 ℃, reaction pressure 5 ~ 300 kg / cm ² . Supporting a ruthenium salt in the zirconia support, dried at 90 ~ 150 ℃, as was sloppy to hydrogen reduction at a temperature of 100 ~ 500 ℃, aqueous ammonia, at least one inorganic base solution is selected from the group consisting of sodium and potassium Washing and drying, the dispersity of ruthenium is 10% -100%, A catalyst having a chlorine content of less than 100 ppm was prepared, and using the catalyst, a sugar alcohol corresponding thereto was reacted with a hydrogenated reaction under the conditions of a reaction temperature of 20 to 150 ° C. and a reaction pressure of 5 to 300 kg / cm ² . How to prepare The method for producing sugar alcohols according to claim 1 or 2, wherein 90% by weight or more of the total weight of the carrier is zirconia. The method for producing sugar alcohols according to claim 1 or 2, wherein the surface area of the carrier is 10 to 500 m ² / g. The method according to claim 1 or 2, wherein the ruthenium salt comprises from 0.1 to 10% by weight of ruthenium based on the weight of the catalyst. delete The method of claim 1, wherein before or after the step of washing and drying with at least one aqueous inorganic base solution selected from the group consisting of aqueous ammonia, sodium hydroxide and potassium hydroxide, flowing hydrogen to reduce the temperature to 100 to 500 ° C. Method for producing a sugar alcohol, characterized in that it further comprises. delete The saccharide according to claim 1 or 2, wherein the saccharide is erythrose, xylose, arabinose, glucose, galactose, manose, fructose, lactose, lactulose, maltose, isomaltulose, talos, rhamnose, susu Method for producing sugar alcohols, characterized in that it comprises one or more mixtures selected from the group consisting of cross, starch sugar, starch hydrolyzate, cellulose hydrolyzate, hemicellulose hydrolyzate. The method of claim 1 or 2, wherein the sugar can be dissolved in a solvent and used, wherein the solvent used is selected from water, alcohols or mixtures thereof.  The method of claim 10, wherein the alcohol is methanol, ethanol, propanol, isopropanol, or a mixture thereof. The method of claim 1, wherein the reaction temperature is a sugar alcohol production method, characterized in that 30 ~ 130 ℃. The method for producing sugar alcohols according to claim 1 or 2, wherein the reaction pressure is 10 to 200 kg / cm ² . The method for producing sugar alcohols according to claim 1 or 2, wherein when the hydrogenation reaction is a continuous reaction, the weight space velocity of the sugar is 0.05 to 10 h ⁻¹ .