KR20120123189A - Preparing method from sugar to sugar alcohols by catalytic hydrogenation - Google Patents

Abstract

PURPOSE: A manufacturing method of sugar alcohols is provided to continuously manufacture sugar alcohols with high yield through a repeated catalytic hydrogenation of sugars without regeneration of a catalyst. CONSTITUTION: A manufacturing method of sugar alcohols comprises a step of preparing sugar alcohols through a hydrogenation of sugars by using a supported catalyst. The supported catalyst is that ruthenium is supported into a single support or a mixture support selected from silica, alumina, and titania. The support has a coating consisting of nickel metal oxide. The hydrogenation is conducted at the reaction temperature 60-200 °C and reaction pressure of 2-200 MPa. The comprised amount of the ruthenium is 0.2-15 weight% based on the total weight.

Description

Preparation method of sugar alcohols by catalytic hydrogenation of sugars {Preparing method from sugar to sugar alcohols by catalytic hydrogenation}

The present invention relates to a method for continuously producing sugar alcohols by catalytic hydrogenation of sugars.

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 method for continuously producing sugar alcohols in high yield by catalytic hydrogenation of sugars.

The present invention is to provide a method for continuously producing a corresponding sugar alcohols in high yield by repeatedly catalytic hydrogenation of sugars without regeneration of the catalyst.

According to one aspect of the present invention, ruthenium is supported on a single or mixture carrier selected from silica, alumina and titania, wherein the carrier has a film made of nickel metal oxide, and the sugars are subjected to hydrogenation reaction. By the corresponding sugar alcohols are 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.

In one embodiment of the present invention, the ruthenium may be supported by 0.2 to 15% by weight based on the total weight of the supported catalyst.

In one embodiment of the present invention, the film of the nickel metal oxide may be formed in an amount of 0.5 to 15% by weight based on the total amount of the supported catalyst.

In one embodiment of the present invention, the ruthenium may be nanoparticles having a particle diameter of 1 to 10 nm.

The method for producing sugar alcohols by catalytic hydrogenation of sugars according to the present invention is a by-product by preparing high purity sugar alcohols without dissolving or deactivating catalyst components during repeated use of ruthenium-supported catalysts in the hydrogenation reaction of sugars. And little waste is generated, there is an effect that can be produced sugar alcohols without complex separation process.

1 is an XRD profile (a: TiO ₂ , b: NiO-TiO ₂ , c: Ru / NiO-TiO ₂ ) of a ruthenium-supported nickel oxide film-titania catalyst (Preparation Example 1, Ru / NiO-TiO ₂ ) .
2 is a transmission electron microscope image of a ruthenium-supported nickel oxide film-titania catalyst (Preparation Example 1 Ru / NiO-TiO ₂ ).
FIG. 3 shows hydrogen TPR analysis results of a ruthenium-supported nickel oxide film-titania catalyst (Preparation Example 1, Ru / NiO-TiO ₂ ) and a ruthenium-supported titania catalyst (Comparative Example 1, Ru / TiO ₂ ) (a: TiO ₂ , b: Ru / TiO ₂ , c: NiO-TiO ₂ , d: Ru / NiO-TiO ₂ ).

Hereinafter, the present invention will be described in detail.

A method of continuously preparing the corresponding sugar alcohols by the catalytic hydrogenation of sugars according to the present invention comprises coating an oxide film with nickel metal on a single or mixture carrier selected from silica, alumina and titania, and ruthenium nanoparticles thereon. Use the supported catalyst.

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.

Silica, alumina, titania, etc. used as the carrier of the supported catalyst are not particularly limited, and may be of natural origin or synthesized.

In forming the nickel metal oxide film of the supported catalyst, it is possible to obtain a high activity even if a small amount of catalyst is used because the ruthenium is supported by nanoparticles so that the film is formed at 0.5 to 15% by weight based on the total weight of the supported catalyst. .

The particle diameter of the ruthenium nanoparticles supported on the supported catalyst is 1 to 10 nm, preferably 1.5 to 5 nm.

The content of ruthenium in the supported catalyst may be 0.2 to 15% 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.

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 Preparation Examples and Examples, but the present invention is not limited to the following Preparation Examples and Examples.

Evaluation methods in the following Production Examples and Examples are as follows.

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

(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.

Preparation Example 1 Preparation of Supported Catalyst

0.55 g of nickel dichloride (NiCl ₂ ) was dissolved in 10 ml of distilled water. 4.75 g of titania (specific surface area 51 m 2 / g) powder was added to the solution, stirred well, and then dried in an oven at 110 ° C. overnight. The obtained solid was baked at 500 degreeC for 12 hours, and the nickel oxide film was formed in titania.

In the aqueous solution of the ruthenium compound in which 0.04 g of ruthenium trichloride (RuCl ₃ xH ₂ O) was dissolved in 10 ml of distilled water, the obtained nickel oxide film was obtained. 1.98 g of titania powder was added thereto, stirred well, and dried in an oven at 110 ° C. overnight.

The dried powder sample was reduced by nitrogen gas containing 5% hydrogen at 170 ° C. for 2 hours to obtain a ruthenium-supported nickel oxide film-titania catalyst (hereinafter referred to as Ru / NiO-TiO ₂ ).

The XRD profile evaluated by the above-described method for the obtained supported catalyst is shown in FIG. 1, and a TEM photograph thereof is shown in FIG. 2.

According to the XRD profile of FIG. 1, the diffraction pattern of the supported catalyst can confirm peaks due to NiO, and also Ru particles (particle diameter of 2 nm) are dispersed on the flakes (gray portion) of the nickel oxide film-titania in the TEM image of FIG. 2. It can be confirmed.

Meanwhile, as a result of EDX analysis, the content of ruthenium in the supported catalyst was 1.1% by weight, and the content of nickel was 5.4% by weight.

In addition, as shown in the hydrogen TPR analysis result of FIG. 3, it was confirmed that the reduction temperature of the Ru particles (particle size 2 nm) on the flakes of the nickel oxide film-titania was lowered to 170 ° C.

Example 1 Preparation of Sorbitol

Hydrogenation reaction to continuously prepare the corresponding sugar alcohols from sugars using the supported catalyst (Ru / NiO-TiO ₂ ) obtained in Preparation Example 1 was carried out in a fixed bed reactor made of SUS314.

₂ g of ruthenium / nickel oxide / titania catalyst (Ru / NiO-TiO ₂ ) obtained from Preparation Example 1 was added to a fixed bed reactor, and the temperature of the reactor was raised to 170 ° C., followed by reduction of the catalyst for 3 hours while purging the reactor with hydrogen. It was. Initially, the temperature of the reactor was lowered to 120 ° C., the pressure was increased to 5.5 MPa, and 20% aqueous glucose solution was injected at a rate of 0.04 ml / min to prepare sorbitol continuously for 100 hours. Next, the reaction temperature was 100 ℃ and sorbitol was continuously prepared for 150 hours under the same conditions as described above. Thereafter, 20% aqueous glucose solution was injected at a rate of 0.1 ml per minute, and sorbitol was continuously prepared for 150 hours under the same conditions as described above. Subsequently, the reaction temperature was 80 ° C. and 20% glucose aqueous solution was injected at a rate of 0.04 ml / min under the same conditions as described above to continuously prepare sorbitol for 150 hours. Thereafter, 20% aqueous glucose solution was injected at a rate of 0.1 ml per minute, and sorbitol was continuously prepared for 150 hours under the same conditions as described above.

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 glucose and selectivity of sorbitol after the reaction are shown in Table 1, and it was found that the catalytic activity was maintained even after the reaction continued for 700 hours or more.

Sorbitol was prepared by continuous reaction using a ruthenium / nickel oxide-titania catalyst (Preparation Example 1, Ru / NiO-TiO ₂ ) from glucose. reaction
Temperature
(℃) Glucose
Injection speed
(ml / min) continuity
Reaction time
(h) Glucose
Conversion rate
(%) Sorbitol
Selectivity
(%) Mannitol
Selectivity
(%) Etc
Selectivity
(%) 120 0.04 100 99.5 94.5 1.6 3.9 100 0.04 150 99.8 98.8 0.3 0.9 100 0.1 150 98.8 98.6 0.1 1.3 80 0.04 150 99.8 99.8 0.1 0.1 80 0.1 150 99.2 99.0 0.3 0.7

As a result of the metal detection after the hydrogenation reaction as described above, ruthenium, nickel and titanium were not detected at all in the solution after the hydrogenation reaction. In the above reaction, the content of ruthenium in the supported catalyst showed high conversion of glucose and selectivity of sorbitol even using a small amount of 1% by weight.

Example 2 Preparation of Xylitol

The hydrogenation reaction was carried out in the same manner as in Example 1 except for using the supported catalyst (Ru / NiO-TiO ₂ ) obtained in Preparation Example 1 and using 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 rate of xylose and the selectivity of xylitol after the reaction are shown in Table 2, and it was found that the catalytic activity was maintained even after the reaction continued for 700 hours or more.

Xylitol was prepared from xylose by continuous reaction using a ruthenium / nickel oxide-titania catalyst (Preparation Example 1, Ru / NiO-TiO ₂ ). reaction
Temperature
(℃) Xylose
Injection speed
(ml / min) continuity
Reaction time
(h) Xylose
Conversion Rate (%) Xylitol
Selectivity (%) Arabitol
Selectivity (%) Etc
Selectivity
(%) 120 0.04 100 100 96.4 1.6 2.0 100 0.04 150 100 98.8 0.3 0.9 100 0.1 150 100 98.5 0.1 1.4 80 0.04 150 100 99.8 0.1 0.1 80 0.1 150 100 99.1 0.3 0.6

As a result of the metal detection after the hydrogenation reaction as described above, ruthenium, nickel and titanium were not detected at all in the solution after the hydrogenation reaction.

Example 3 Preparation of Mannitol

The hydrogenation reaction was carried out in the same manner as in Example 1 except for using the supported catalyst (Ru / NiO-TiO ₂ ) obtained in Preparation Example 1 and using 20% mannose 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 mannose and selectivity of mannitol are shown in Table 3, and the activity was maintained constant even after the reaction was continued for 700 hours or more.

Mannitol was prepared by continuous reaction using a ruthenium / nickel oxide-titania catalyst (Preparation Example 1, Ru / NiO-TiO ₂ ) from mannose. reaction
Temperature
(℃) Mannose
Injection speed
(ml / min) continuity
Reaction time
(h) Mannos
Conversion Rate (%) Mannitol
Selectivity (%) Etc
Selectivity (%) 120 0.04 100 99.5 96.4 3.6 100 0.04 150 99.7 98.6 1.4 100 0.1 150 98.7 98.5 1.5 80 0.04 150 99.7 99.6 0.4 80 0.1 150 99.2 99.1 0.9

As a result of the metal detection after the hydrogenation reaction as described above, ruthenium, nickel and titanium were not detected at all in the solution after the hydrogenation reaction.

[Comparative Preparation Example 1] Preparation of Supported Catalyst

1.98 g of titania (specific surface area 51 m 2 / g) powder was added to an aqueous solution of ruthenium compound in which 0.04 g of ruthenium trichloride (RuCl ₃ × xH ₂ O) was dissolved in 10 ml of distilled water, stirred well, and dried overnight at 110 ° C. in an oven.

The dried powder sample was reduced at 400 ° C. for 3 hours with nitrogen gas containing 5% hydrogen to obtain a ruthenium loaded titania catalyst (hereinafter referred to as Ru / TiO ₂ ).

As a result of the EDX analysis, the content of ruthenium in the supported catalyst was 1.1% by weight.

In addition, as shown in the hydrogen TPR analysis of FIG. 3, the reduction temperature of the Ru particles on the flakes of titania was confirmed at 400 ° C.

Comparative Example 1 Preparation of Sorbitol

The hydrogenation reaction was carried out in the same manner as in Example 1, except that the catalyst (Ru / TiO ₂ ) obtained from Comparative Preparation Example 1 was used.

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 and selectivity of sorbitol after the reaction are shown in Table 4, and the reaction products are by-products compared to the ruthenium / nickel oxide-titania catalyst (Ru / NiO-TiO ₂ ) used in Example 1 when the reaction is performed continuously for 700 hours or more. Phosphorous mannitol was formed and other impurities were generated, indicating that the conversion of glucose was somewhat inferior to the selectivity of sorbitol.

Sorbitol was prepared by continuous reaction using a ruthenium / titania catalyst (Ru / TiO ₂ ) from glucose. reaction
Temperature
(℃) Glucose
Injection speed
(ml / min) continuity
Reaction time
(h) Glucose
Conversion rate
(%) Sorbitol
Selectivity
(%) Mannitol
Selectivity
(%) Etc
Selectivity
(%) 120 0.04 100 99.4 79.5 5.6 14.9 100 0.04 150 99.8 96.8 0.9 2.3 100 0.1 150 98.8 96.6 0.8 2.6 80 0.04 150 99.7 98.4 0.8 0.8 80 0.1 150 98.2 98.0 0.6 1.4

As a result of the metal detection after the hydrogenation reaction as described above, ruthenium and titanium were not detected at all in the solution after the hydrogenation reaction.

Comparative Example 2 Preparation of Xylitol

The hydrogenation reaction was carried out in the same manner as in Example 1 except for using the catalyst (Ru / TiO ₂ ) obtained from Comparative Preparation Example 1 and using 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 analysis, the conversion rate of xylose and the selectivity of xylitol are shown in Table 5, and the reaction was performed continuously for 700 hours or more, compared to the ruthenium / nickel oxide-titania catalyst (Ru / NiO-TiO ₂ ) used in Example 1 As a by-product arabitol is produced and other impurities are generated, it was found that the conversion of xylose was somewhat inferior to the selectivity of xylitol.

Xylitol Preparation by Continuous Reaction Using Ruthenium / Titania Catalyst (Ru / TiO ₂ ) from Xylose reaction
Temperature
(℃) Xylose
Injection speed
(ml / min) continuity
Reaction time
(h) Xylose
Conversion Rate (%) Xylitol
Selectivity (%) Arabitol
Selectivity (%) Etc
Selectivity
(%) 120 0.04 100 99.8 81.5 4.6 13.9 100 0.04 150 99.8 96.8 0.9 2.3 100 0.1 150 98.8 95.6 1.3 3.1 80 0.04 150 99.7 98.4 0.8 0.8 80 0.1 150 98.6 97.0 1.1 1.9

As a result of the metal detection after the hydrogenation reaction as described above, ruthenium and titanium were not detected at all in the solution after the hydrogenation reaction.

Comparative Example 3 Preparation of Mannitol

The hydrogenation reaction was carried out in the same manner as in Example 1 except for using the catalyst (Ru / TiO ₂ ) obtained from Comparative Preparation Example 1 and using 20% mannose 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 mannose and selectivity of mannitol are shown in Table 6, and when the reaction was performed continuously for 700 hours or more, it was compared with the ruthenium / nickel oxide-titania catalyst (Ru / NiO-TiO ₂ ) used in Example 1 It was found that impurities were produced, resulting in somewhat lower mannose conversion and mannitol selectivity.

Mannitol was prepared by continuous reaction using a ruthenium / titania catalyst (Ru / TiO ₂ ) from mannose. reaction
Temperature
(℃) Mannose
Injection speed
(ml / min) continuity
Reaction time
(h) Mannos
Conversion Rate (%) Mannitol
Selectivity (%) Etc
Selectivity (%) 120 0.04 100 99.5 80.5 19.5 100 0.04 150 99.6 95.8 4.2 100 0.1 150 98.6 95.4 4.6 80 0.04 150 99.7 97.4 2.6 80 0.1 150 99.1 96.0 4.0

As a result of the metal detection after the hydrogenation reaction as described above, ruthenium and titanium were not detected at all in the solution after the hydrogenation reaction.

Comparative Example 4 Preparation of Sorbitol Using a Commercial 5% Ru / C Catalyst

Hydrogenation was carried out in the same manner as in Example 1 using a commercial 5% Ru / C catalyst, and after the reaction, the results of the liquid chromatography analysis showed that the conversion of glucose and the selectivity of sorbitol are as shown in Table 7, and more than 700 hours. When the reaction was continued, it was found that the by-product mannitol is produced in a large amount, other impurities are generated, and the selectivity of sorbitol is significantly lower than that of the ruthenium / nickel oxide-titania catalyst (Ru / NiO-TiO ₂ ) used in Example 1 .

Sorbitol was prepared by continuous reaction using a commercial 5% Ru / C catalyst from glucose. reaction
Temperature
(℃) Glucose
Injection speed
(ml / min) continuity
Reaction time
(h) Glucose
Conversion rate
(%) Sorbitol
Selectivity
(%) Mannitol
Selectivity
(%) Etc
Selectivity
(%) 120 0.04 100 100 59.5 19.4 21.1 100 0.04 150 100 83.8 5.4 10.8 100 0.1 150 100 78.6 5.4 16.0 80 0.04 150 100 96.0 1.8 2.2 80 0.1 150 100 94.0 1.6 4.4

Comparative Example 5 Preparation of Xylitol Using Commercial 5% Ru / C Catalyst

Hydrogenation was carried out in the same manner as in Example 1 using a commercial 5% Ru / C catalyst, and after the reaction, the liquid chromatography analysis showed the conversion of xylose and the selectivity of xylitol are shown in Table 8, and 700 hours. When the reaction was continuously performed, it was found that a large amount of by-product arabitol was produced, other impurities were generated, and the selectivity of xylitol was greatly decreased compared to the ruthenium / nickel oxide-titania catalyst (Ru / NiO-TiO ₂ ) used in Example 1. Could.

Xylitol Preparation by Continuous Reaction from Xylose Using Commercial 5% Ru / C Catalyst reaction
Temperature
(℃) Xylose
Injection speed
(ml / min) continuity
Reaction time
(h) Xylose
Conversion Rate (%) Xylitol
Selectivity (%) Arabitol
Selectivity (%) Etc
Selectivity
(%) 120 0.04 100 99.8 61.5 18.4 20.1 100 0.04 150 99.8 84.8 6.4 10.8 100 0.1 150 98.8 77.6 6.4 16.0 80 0.04 150 99.7 95.0 2.8 2.2 80 0.1 150 98.6 93.0 2.6 4.4

Comparative Example 6 Preparation of Mannitol Using a Commercial 5% Ru / C Catalyst

Hydrogenation was carried out in the same manner as in Example 1 using a commercial 5% Ru / C catalyst, and after the reaction, the result of liquid chromatography analysis showed that mannose conversion and mannitol selectivity are shown in Table 9, and were performed for 700 hours or longer. When the reaction was continued, it was found that the ruthenium / nickel oxide-titania catalyst (Ru / NiO-TiO ₂ ) used in Example 1 produced a large amount of other impurities and greatly decreased the selectivity of mannitol.

Mannitol was prepared by continuous reaction using a commercial 5% Ru / C catalyst from mannose reaction
Temperature
(℃) Mannose
Injection speed
(ml / min) continuity
Reaction time
(h) Mannos
Conversion Rate (%) Mannitol
Selectivity (%) Etc
Selectivity (%) 120 0.04 100 99.5 80.5 19.5 100 0.04 150 99.6 95.8 4.2 100 0.1 150 98.6 95.4 4.6 80 0.04 150 99.7 97.4 2.6 80 0.1 150 99.1 96.0 4.0

Claims (7)

Ruthenium is supported on a carrier alone or in a mixture selected from silica, alumina and titania, and the carrier has a coating of nickel metal oxide, and the sugars are converted into the corresponding sugar alcohols by hydrogenation. How to manufacture.
The method of claim 1,
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.
The method of claim 1,
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 3, wherein
The saccharide is dissolved in a solvent and used, and the solvent is selected from water, alcohol or a mixture thereof.
The method of claim 1,
The ruthenium is supported by 0.2 to 15% by weight based on the total weight of the supported catalyst. The method of claim 1,
Wherein the coating of the nickel metal oxide is formed in an amount of 0.5 to 15% by weight based on the total amount of the supported catalyst.
The method of claim 1,
The ruthenium is a nanoparticle having a particle diameter of 1 to 10 nm.

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