KR20120123202A - Ru-Zeolite based Catalyst for converting sugar to sugar alcohols by catalytic hydrogenation, Preparing method of the same and Converting sugar to sugar alcohols using the same - Google Patents

Abstract

PURPOSE: A ruthenium-zeolite-based carrier catalyst for preparing sugar alcohols by the catalytic hydrogenation of sugars, a preparing method of the same, and a method for preparing the sugar alcohols using the same are provided to collect a catalyst carrying ruthenium without a regenerating process and to repeatedly use the catalyst. CONSTITUTION: A preparing method of a carrier catalyst for preparing sugar alcohols includes the following steps: a zeolite carrier is plasticized at a temperature between 200 and 600 deg C for 1 to 15 hours; a solid product is obtained and is treated with a solution of ruthenium compound; the resultant product is dried at a temperature between 20 and 150 deg C; the dried product is reduced with nitrogen gas containing hydrogen at a temperature between 120 and 450 deg C for 1 to 10 hours; and a carrier catalyst carrying ruthenium is obtained.

Description

Ru-Zeolite based catalyst for converting sugar to sugar alcohols by catalytic hydrogenation, Preparing method for preparing sugar alcohols by catalytic hydrogenation of sugars of the same and Converting sugar to sugar alcohols using the same}

The present invention relates to a method for producing a ruthenium-zeolitic catalyst for use in producing sugar alcohols.

Fossil raw materials, such as oil, gas and coal, continue to rise in price due to the finite nature of their resources, and competition between countries is heating up to secure them. Moreover, chemical products produced from fossil raw materials generate global warming gases and wastes as by-products in the manufacturing process, resulting in environmental pollution, which is rapidly declining the existing chemical industry.

In Korea, where most of the energy depends on imports, it is essential to establish long-term energy supply and demand policies and fundamentally develop clean alternative energy that can reduce the dependence on energy imports as much as possible to maintain national security and sustainable economic growth. In this reality, biomass is attracting attention as a field of alternative energy that can solve the concern about depletion of fossil fuel and environmental pollution. Reinforcement of environmental regulations such as depletion of oil resources, unstable oil supply and demand due to high oil prices, and the suppression of greenhouse gas emissions caused by the use of fossil fuels are hindering the development of the global economy. In particular, the chemical industry, which is most directly affected by high oil prices and environmental regulations, is recognized as an important alternative to reducing the dependency on fossil fuels and changing to an environmentally friendly industrial structure. Therefore, there is a need for the development of a new eco-friendly biochemical process that uses biomass as a raw material that can replace the chemical process based on fossil material, that is, minimize the consumption of fossil material and the production of waste harmful to humankind. It is becoming.

One of the notable moves in recent years as a way to develop environmentally friendly biochemical processes is that the biorefinery industry using biomass stands out. Biorefinery is a new concept that produces biofuels and chemicals without the use of fossil raw materials and only through biological and chemical conversion from biomass. Although it was born with the term oil-refinery, which means crude oil refining in the petrochemical industry, all biochemical products including biofuels have gone through biological and chemical conversion process from biomass feedstock. Refers to the whole-cycle core technology to produce.

Biorefiner is a biomass-based raw material such as ethanol, butanol, acetone, and other chemicals such as sorbitol, which is a biomass-based oil refinery that produces industrial / transport fuels and various chemical products. It is being developed as an integrated process that builds a technology for making xyitol, lactic acid and succinic acid and a comprehensive plant system to implement it.

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

U.S. Patent Nos. 3,586,537, 4,008,285 and the like disclose a process for producing xylitol by hydrogenating xylose in a batch reactor using a Ranickel catalyst. Such a production method requires complex separation and purification and catalyst recovery as a large amount of by-products are generated, and nickel, which is an active ingredient of the catalyst, is dissolved in the reaction product, and the catalyst is gradually deactivated after a certain time of reaction. have.

US Pat. No. 6,414,201 discloses 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 in a continuous hydrogenation reactor. It is describing. However, this method also has a disadvantage in that nickel, which is an active ingredient of the catalyst, is dissolved in the reaction product, and the reaction activity of the catalyst gradually decreases after the reaction for a predetermined 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 60 ° C. and 300 kg / cm ² , but requires a high pressure-resistant reaction equipment, which is an active ingredient of the catalyst in the reaction product. Nickel and iron are dissolved, there is a problem that gradually deactivate the catalyst when the reaction proceeds for a long time.

On the other hand, the prior art has been reported a patent for using a ruthenium catalyst in the hydrogenation reaction that does not dissolve in the solution during the reaction, such as nickel. 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 regenerated by pickling. However, this method has the disadvantages of complicated catalyst preparation method, long catalyst production time, high loss of ruthenium precursor, difficult control of ruthenium content, additional catalyst regeneration process, and high yield by using ion exchange method. As low as%, a separate separation process is required for the production of high purity sugar alcohols.

U. S. Patent No. 4,380, 679 discloses a process for hydrogenating saccharides by preparing a catalyst carrying a Group 8 metal such as ruthenium and nickel on a carbon pyropolymer carrier. In this patent, the inorganic oxide surface was treated with an organic pyrolytic material at a high temperature, and then the inorganic material was dissolved in an acid or a base, and a catalyst was prepared by supporting a metal on the remaining carbon pyropolymer carrier. It was claimed to be excellent in stability and reaction activity. However, there are disadvantages in that the preparation method of the carbon pyropolymer carrier is complicated and the reaction selectivity is low compared with the case of using a gamma alumina carrier.

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 ions 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. To the hydrogenation reaction. This method can be supported by ruthenium amine complex salt with high dispersibility during ion exchange, and has the advantage of simultaneously proceeding hydrolysis and hydrogenation by using acidic carrier, but it is easy to be isomerized due to relatively high reaction temperature during hydrolysis. As a result, it is difficult to selectively prepare sugar alcohols, and there is a problem in that silicon and aluminum, which are carrier components, 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. Patent No. 6,177,598 discloses Group 8 transition metals, including ruthenium. 50 nanometers of large pore and 50? When hydrogenated saccharides using a catalyst supported on a carrier such as alumina having an appropriate proportion of 10,000 micrometers of mesopores, it was claimed that 99% purity sugar alcohols were produced without the problem of melting metals 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. There is a problem that the silica component as a carrier is dissolved during the hydrogenation reaction. In addition, the xylitol has a low selectivity of 97%, which requires a disadvantage of 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.

U.S. Patent No. 3,586,537 (June 22, 1971) U.S. Patent 4,008,285 (1977.02.15) U.S. Patent 6,414,201 (2002.07.02) U.S. Patent No. 6,124,443 (2000.09.26) U.S. Patent No. 3,963,788 (1976.06.15) U.S. Patent 4,380,679 (1983.04.19) U.S. Patent No. 4,950,812 (1990.08.21) U.S. Patent No. 6,177,598 (2001.01.23) WO 02/100537 (2002.12.19) U.S. Patent No. 6,570,043 (2003.05.27) U.S. Patent No. 5,998,181 (1999.12.07)

An object of the present invention is to provide a novel supported catalyst for producing sugar alcohols by hydrogenation of sugars.

It is an object of the present invention to provide a method for producing a novel supported catalyst for producing sugar alcohols by hydrogenation of sugars under relatively mild conditions.

It is an object of the present invention to provide a method for producing a high yield of sugar alcohols corresponding thereto by hydrogenating sugars repeatedly without regeneration of the catalyst.

According to an aspect of the present invention, there is provided a supported catalyst for preparing sugar alcohols by catalytic hydrogenation of saccharides, in which ruthenium is supported on a zeolite carrier.

According to one embodiment of the invention, the ruthenium may be supported in 0.1 to 5% by weight relative to the total weight of the supported catalyst.

According to another aspect of the present invention, there is provided a method for producing a zeolite carrier comprising the steps of: 1) calcining a zeolite carrier; 2) treating the solid obtained in the step 1) with a solution of the ruthenium compound and then drying it; And 3) reducing the dried product obtained in step 2) with nitrogen gas containing hydrogen to obtain a supported catalyst carrying ruthenium; Provided is a method for preparing a supported catalyst for producing sugar alcohols by catalytic hydrogenation of a saccharide comprising a.

According to one embodiment of the present invention, the method for preparing the supported catalyst comprises the steps of 1) calcining the zeolite carrier at 200 to 600 ° C. for 1 to 15 hours; 2) treating the solid obtained in step 1) with a solution of ruthenium compound and drying at 20 to 150 ° C; And 3) reducing the dried product obtained in step 2) with hydrogen-containing nitrogen gas at 120 to 450 ° C. for 1 to 10 hours to obtain a supported catalyst carrying ruthenium.

According to one embodiment of the invention, the ruthenium compound is a ruthenium precursor, but is not limited to, for example, ruthenium (III) chloride, ruthenium (III) acetylacetonate or ruthenium (III) nitrosyl acetate, etc. Can be.

According to one embodiment of the invention, the nitrogen gas containing hydrogen may be nitrogen gas containing 1 to 10% hydrogen.

According to another aspect of the present invention, by using the supported catalyst, a method for producing a sugar alcohol corresponding thereto by a hydrogenation reaction is provided.

In one embodiment of the present invention, the hydrogenation reaction may be carried out under the conditions of the reaction temperature of 60 to 200 ℃ and the reaction pressure of 2 to 200MPa.

In one embodiment of the present invention, the sugar may be exemplified by glucose, xylose, mannose, fructose, erythrose, galactose, sucrose, starch hydrolyzate, cellulose hydrolyzate or maltose and the like.

In one embodiment of the present invention, the sugar is used in a solvent, and the solvent is not limited so long as it dissolves the sugar, for example, may be exemplified by water, alcohol or a mixture thereof.

The ruthenium-supported catalyst of the present invention is recovered without the need for a separate regeneration process, and by-products and wastes are produced by producing high-purity sugar alcohols without dissolving or deactivating the catalyst component during repeated use of the saccharide hydrogenation reaction. It does not occur, there is an effect that can be produced sugar alcohols without complicated separation process.

FIG. 1 is a transmission electron microscope image of a catalyst (Ru / β-Zeolite) in which ruthenium prepared in Example 1 (1) is supported on beta-zeolite.
2 is an XRD profile of a catalyst (Ru / β-Zeolite) in which ruthenium prepared in Example 1 (1) is supported on beta-zeolite.
3 is a transmission electron microscope image of a catalyst (Ru / HZSM-5) in which ruthenium prepared in Example 1 (1) is supported on HZSM-5 zeolite (HZSM-5).
4 is an XRD profile of a catalyst (Ru / HZSM-5) in which ruthenium prepared in Example 2 (1) is supported on HZSM-5 zeolite (HZSM-5).

Hereinafter, the present invention will be described in detail.

One embodiment of the present invention provides a supported catalyst for preparing sugar alcohols by carrying ruthenium on a zeolite carrier and catalytic hydrogenation of sugars.

The zeolite carrier used as the carrier is not particularly limited and may be of natural origin or synthesized.

The basic characteristics of the zeolite are determined by the structure of the zeolite. The international zeolite association (IZA) assigns a three-letter structure code according to the skeleton. Zeolites can be classified into natural zeolites and synthetic zeolites depending on whether they are produced in nature or artificially synthesized. FAU and MOR zeolites are produced in nature, but can also be synthesized in the laboratory. There are 40 kinds of natural zeolites, which are very small compared to synthetic zeolites. When the zeolite is classified according to the pore size, typical zeolites of small pores include LTA, ERI, and CHA. The middle pores include MFI, MWW, and FER, and the large pores include FAU, BEA, MOR, LTL, MTW etc. are mentioned. In a preferred embodiment of the present invention, among these various zeolites, in particular, having a MFI, FAU, BEA, MOR structure may be preferable in terms of acidity, but is not limited thereto.

Meanwhile, the content of ruthenium in the supported catalyst of the present invention may be 0.1 to 5% by weight based on the total weight of the supported catalyst in consideration of the rate and economic efficiency of the hydrogenation reaction in the hydrogenation of saccharides.

An example of a method of manufacturing a supported catalyst carrying such ruthenium is as follows.

First, in step 1), the zeolite carrier is calcined at 200 to 600 ° C. for 1 to 15 hours.

Next, in step 2), the solid obtained in step 1) is treated with a solution of ruthenium compound and dried at 20 to 150 ° C.

In this case, the ruthenium compound corresponds to a ruthenium precursor, and may be selected from, for example, ruthenium (III) chloride, ruthenium (III) acetylacetonate, and ruthenium (III) nitrosyl acetate.

Next, in step 3), the dried product obtained in step 2) may be reduced with nitrogen gas containing hydrogen at 120 to 450 ° C. for 1 to 10 hours to obtain a supported catalyst carrying ruthenium. At this time, the nitrogen gas containing hydrogen may be preferable in that 1 to 10% of hydrogen can avoid rapid reduction.

Using the supported catalyst according to the above embodiments, the sugars may be prepared as the corresponding sugar alcohols by hydrogenation.

The sugar is not limited thereto, and for example, glucose, xylose, mannose, fructose, erythrose, galactose, sucrose, starch hydrolyzate, cellulose hydrolyzate and mixture of two or more selected from maltose Can be used.

Since sugars are generally in a solid state at room temperature, it is preferable to dissolve sugars in an appropriate solvent in order to improve reaction efficiency. In this case, as the solvent, sugars and sugar alcohols, which are products of a hydrogenation reaction, can be dissolved simultaneously, and any of them can be used. Generally, water or alcohol may be used alone or in combination. Examples of the alcohol may include methanol, ethanol, propanol, isopropanol or mixtures thereof. Preferably, water is used alone or in combination with water and ethanol.

Hydrogenation of sugars using the supported catalyst of the present invention may be preferably carried out at a reaction temperature of 60 to 200 ℃, if the reaction temperature is low, the reaction rate may be slow, if the reaction temperature is too high side reactions increase the desired reactant The problem of low selectivity may arise.

In addition, the hydrogenation reaction may be preferably performed under the conditions of the reaction pressure of 2 to 200 MPa in consideration of the reaction rate and the safety of the reactor.

The supported catalyst participating in such a hydrogenation reaction can be recovered without requiring a separate regeneration step, and can be repeatedly used for hydrogenation of saccharides, and catalyst components are not dissolved or deactivated even when repeatedly used. Therefore, sugar alcohols can be produced in high purity without generating by-products and waste and without complicated separation process.

The present invention as described above will be described in more detail based on the following examples, but the present invention is not limited by the following examples.

The evaluation method in a following example is as follows.

(1) The effective amount of ruthenium in the prepared catalyst was measured by chemical analysis, specifically, EDX (energy dispersive X-ray analysis).

(2) The crystal characteristic of the prepared catalyst was observed by X-ray diffraction (XRD).

(3) The amount of metal ions in the reactants after the hydrogenation reaction was determined by inductively coupled plasma mass spectrometry (ICP) (performed by Thermo Scientific ICAP 6500 duo inductively coupled plasma-atomic emission spectrometer (ICP-AES)).

(4) The characteristics (particle size) of the catalyst were observed by transmission electron microscopy (TEM, Maker FEI, Model Technai G ² ). To this end, catalyst samples were dissolved in 2-propanol, carefully dispersed in an ultrasonic bath and then deposited on a carbon-coated copper grid.

Example 1

(1) Preparation of Supported Catalyst

Beta-zeolite (β-Zeolite, BEA structure) was calcined at 500 ° C for 12 hours.

10.9 g of the calcined powder sample was placed in a 20 ml toluene solution in which 0.43 g of ruthenium acetylacetonate (RuC ₁₅ H ₂₁ O ₃ ) was dissolved, stirred for 1 hour, and dried in a vacuum oven at room temperature for 2 hours.

The dried powder sample was reduced for 6 hours at 300 ° C. with nitrogen gas containing 5% hydrogen to obtain a ruthenium-supported beta-zeolite catalyst (hereinafter referred to as Ru / β-Zeolite).

The TEM photograph evaluated by the above method about the obtained supported catalyst is shown in FIG.

In the TEM photograph of FIG. 1, it can be seen that Ru particles (black dots, particle diameter of about 1.0 nm) are dispersed in the flake phase (gray portion) of the beta-zeolite.

In addition, the XRD profile for the supported catalyst obtained is shown in FIG. According to the XRD profile of FIG. 2, it can be seen that the diffraction pattern of the supported catalyst is almost the same as that of the carrier (beta-zeolite), which may be because Ru particles are made of nanoparticles.

Meanwhile, the ruthenium content in the supported catalyst was 1.3% by weight as a result of EDX analysis.

(2) Production of sugar alcohols

Hydrogenation reaction to prepare the corresponding sugar alcohols from sugars using the supported catalyst obtained in (1) was carried out in a 300 ml Teflon container in a high pressure tank reactor made of SUS314.

0.45 g of the ruthenium / beta-zeolite catalyst obtained from the above (1) was added to a Teflon reactor and 200 ml of 20% glucose aqueous solution was added thereto. The reactor was purged with hydrogen and the pressure was raised to 5.5 MPa and reacted at 120 ° C. for 120 minutes while stirring at a speed of 1200 rpm.

The reaction product was analyzed by liquid chromatography with a refractive index detector as described above.

As a result of analysis, the conversion of glucose after the reaction was 99.5% and the selectivity of sorbitol was 99.5%, and thereafter, the activity was not decreased even if the reaction was performed 100 times or more continuously. As a result of the metal detection after the hydrogenation reaction as described above, ruthenium, aluminum and silicon were not detected at all in the solution after the hydrogenation reaction. In the above reaction, the content of ruthenium in the supported catalyst is 1.3% by weight, which shows high conversion of glucose and selectivity of sorbitol even when a small amount is used.

[Example 2]

(1) Preparation of Supported Catalyst

A catalyst was prepared in the same manner as in Example 1 (1), except that 10.9 g of HZSM-5 zeolite (MFI structure) was added instead of 10.9 g of beta-zeolite.

The TEM photograph evaluated by the above method about the obtained supported catalyst is shown in FIG.

In the TEM photograph of FIG. 3, it can be seen that Ru particles (black dots, particle diameter of about 1.0 nm) are dispersed in the flake phase (gray and black speckles) of the HZSM-5 zeolite.

In addition, the XRD profile for the supported catalyst obtained is shown in FIG. According to the XRD profile of FIG. 4, it can be seen that the diffraction pattern of the supported catalyst is almost the same as that of the carrier (HZSM-5 zeolite), since the Ru particles are made of nanoparticles.

In the EDX analysis, the content of ruthenium in the supported catalyst was 0.7% by weight.

(2) Production of sugar alcohols

Using the ruthenium / HZSM-5 zeolite supported catalyst obtained from (1), hydrogenation was carried out in the same manner as in (2) of Example 1.

The reaction product was analyzed by liquid chromatography with a refractive index detector as described above.

As a result of analysis, the conversion rate of glucose was 99.7% and the selectivity of sorbitol was 99.5%, and thereafter, no activity was lowered even after 100 or more consecutive reactions. As a result of the metal detection after the hydrogenation reaction as described above, ruthenium, aluminum and silicon were not detected at all in the solution after the hydrogenation reaction. In the above reaction, the content of ruthenium in the supported catalyst is 0.7% by weight, which shows high conversion of glucose and selectivity of sorbitol even when a small amount is used.

[Example 3]

(1) Preparation of Supported Catalyst

The supported catalyst was prepared in the same manner as in Example (1).

(2) Production of sugar alcohols

The hydrogenation reaction was carried out in the same manner as in Example (2), except that the catalyst obtained from (1) was used and the reactant was used with 20% xylose instead of 20% glucose.

 The reaction product was analyzed by liquid chromatography with a refractive index detector as described above.

As a result of the analysis, the conversion of xylose was 98.9% and the selectivity of xylitol was 99.5% after the reaction. As a result of the metal detection after the hydrogenation reaction as described above, ruthenium, aluminum and silicon were not detected at all in the solution after the hydrogenation reaction. In the above reaction, the content of ruthenium in the supported catalyst is 1.3% by weight, which shows high conversion of xylose and selectivity of xylitol even when a small amount is used.

Example 4

(1) Preparation of Supported Catalyst

Beta zeolite (β-Zeolite, BEA structure) is calcined at 500 ° C for 12 hours.

9.95 g of the calcined powder sample was added to 10 ml of an aqueous solution of ruthenium compound in which 0.1 g of ruthenium trichloride (RuCl ₃ .xH ₂ O) was dissolved, stirred well, and dried overnight in an oven at 80 ° C.

The dried powder sample was reduced for 6 hours at 300 ° C. with nitrogen gas containing 5% hydrogen to obtain a ruthenium-supported beta zeolite catalyst (hereinafter referred to as Ru / β-Zeolite).

EDX analysis showed that the content of ruthenium in the supported catalyst was 0.8% by weight.

(2) Production of sugar alcohols

Using the catalyst obtained in the above (1), hydrogenation was carried out in the same manner as in (2) of Example 1, and the liquid chromatography analysis showed that the conversion of glucose was 98.9% and the selectivity of sorbitol was 98.7%. There was no activity deterioration even after the reaction was performed 100 times or more continuously. As a result of the metal detection after the hydrogenation reaction as described above, ruthenium, aluminum and silicon were not detected at all in the solution after the hydrogenation reaction. In the above reaction, the content of ruthenium in the supported catalyst is 0.8% by weight, which shows high conversion of glucose and selectivity of sorbitol even when a small amount is used.

[Example 5]

(1) Preparation of Supported Catalyst

The catalyst was prepared in the same manner as in Example 4 (1), except that 9.95 g of HZSM-5 zeolite (MFI structure) was added instead of 9.95 g of beta-zeolite.

EDX analysis showed that the content of ruthenium in the supported catalyst was 1.2% by weight.

(2) Production of sugar alcohols

Using the catalyst obtained in the above (1), hydrogenation was carried out in the same manner as in (2) of Example 1, and the liquid chromatography analysis showed that the conversion of glucose was 98.7% and the selectivity of sorbitol was 98.7%. There was no activity deterioration even after the reaction was performed 100 times or more continuously. As a result of the metal detection after the hydrogenation reaction as described above, ruthenium, aluminum and silicon were not detected at all in the solution after the hydrogenation reaction. In the above reaction, the content of ruthenium in the supported catalyst was 1.2% by weight, which shows high conversion of glucose and selectivity of sorbitol even though a small amount was used.

Claims (10)

Ruthenium is supported on the zeolite carrier,
A supported catalyst for producing sugar alcohols by catalytic hydrogenation of sugars.
The method of claim 1,
A supported catalyst for preparing sugar alcohols by catalytic hydrogenation of saccharides in which the ruthenium is supported at 0.1 to 5% by weight based on the total weight of the supported catalyst.
1) calcining the zeolite carrier;
2) treating the solid obtained in the step 1) with a solution of the ruthenium compound and then drying it; And
3) reducing the dried product obtained in step 2) with nitrogen gas containing hydrogen to obtain a supported catalyst carrying ruthenium;
Method of producing a supported catalyst for producing sugar alcohols by catalytic hydrogenation of sugars comprising a.
The method of claim 3, wherein
The preparation method of the supported catalyst is
1) calcining the zeolite carrier at 200 to 600 ° C. for 1 to 15 hours;
2) treating the solid obtained in step 1) with a solution of ruthenium compound and drying at 20 to 150 ° C; And
3) reducing the dried product obtained in step 2) with nitrogen gas containing hydrogen at 120 to 450 ° C. for 1 to 10 hours to obtain a supported catalyst carrying ruthenium;
Method of producing a supported catalyst for producing sugar alcohols by catalytic hydrogenation of sugars comprising a.
The method of claim 4, wherein
The ruthenium compound is a ruthenium (III) chloride, ruthenium (III) acetylacetonate and ruthenium (III) The production method of the supported catalyst for producing sugar alcohols by the catalytic hydrogenation of sugars.
The method of claim 4, wherein
The hydrogen-containing nitrogen gas is a method for producing a supported catalyst for producing sugar alcohols by catalytic hydrogenation of saccharides, which are nitrogen gas containing 1 to 10% hydrogen.
Using the supported catalyst according to claim 1 or 2, a method for producing a sugar alcohol to the corresponding sugar alcohols by hydrogenation reaction.
8. The method of claim 7,
The hydrogenation reaction is carried out under the conditions of the reaction temperature of 60 to 200 ℃ and the reaction pressure of 2 to 200MPa.
8. The method of claim 7,
The saccharide is a single or a mixture of two or more selected from glucose, xylose, mannose, fructose, erythrose, galactose, sucrose, starch hydrolyzate, cellulose hydrolyzate and maltose.
The method of claim 9,
The saccharide is dissolved in a solvent and used, and the solvent is selected from water, alcohol or a mixture thereof.

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