CN111054342B - Catalyst for preparing glycol from carbohydrate and preparation method thereof - Google Patents

Catalyst for preparing glycol from carbohydrate and preparation method thereof Download PDF

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CN111054342B
CN111054342B CN201811201447.XA CN201811201447A CN111054342B CN 111054342 B CN111054342 B CN 111054342B CN 201811201447 A CN201811201447 A CN 201811201447A CN 111054342 B CN111054342 B CN 111054342B
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CN111054342A (en
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贾玉庆
孙清
缪长喜
张磊
张新玉
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/468—Iridium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/892—Nickel and noble metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention relates to a catalyst for preparing glycol from carbohydrate and a preparation method thereof, which mainly solve the problem of low efficiency of the catalyst for preparing glycol from carbohydrate in the prior art. The invention adopts a combined catalyst, which comprises a metal catalyst I and a multi-element transition metal oxide (M-N-W-O oxide) catalyst II containing M, N and W elements, wherein M is at least one of IVB elements, and N is at least one of VB elements. The combined catalyst used in the invention can better solve the problem and can be applied to the field of preparing ethylene glycol from carbohydrate.

Description

Catalyst for preparing glycol from carbohydrate and preparation method thereof
Technical Field
The invention relates to the field of biomass utilization, and mainly relates to a catalyst for preparing ethylene glycol from carbohydrate and a preparation method thereof.
Background
Ethylene glycol is used as an important bulk chemical and has very wide application, and is mainly used for producing polyethylene terephthalate, polyethylene naphthalate, motor vehicle antifreeze, unsaturated polyester resin, nonionic surfactant, plasticizer and the like. .
Technical routes adopted in the current ethylene glycol industrial production include petroleum raw material routes and coal ethylene glycol routes. Both of these routes rely on fossil resources, but fossil resources are limited in storage and are not renewable. With the exhaustion of fossil resources, there is an urgent need to find a sustainable route to produce ethylene glycol as a complement to existing routes. Biomass is the only renewable organic carbon source that can provide chemicals to humans as compared to other renewable energy sources such as solar, wind, nuclear, etc. The biomass is utilized to produce the glycol, the yield of the glycol can be increased, the dependence on the outside is reduced, meanwhile, the method has the advantages of rich raw material resources, flexible process route, energy conservation, emission reduction and the like. Therefore, developing a high-efficiency catalytic system to realize the conversion of biomass raw materials to ethylene glycol has important economic and social benefits, and is favored by more and more scientific researchers.
Three routes are mainly used for preparing ethylene glycol from biomass raw materials; biomass is fermented to prepare bioethanol by a first route, ethylene is prepared by ethanol dehydration, and ethylene is prepared into ethylene glycol by epoxidation and hydration; the second route is that the biomass raw material firstly prepares sugar, the sugar is hydrogenated into sugar alcohol, and the sugar alcohol is hydrocracked to prepare glycol; the third route is to treat biomass raw materials to obtain cellulose/hemicellulose, starch or saccharides and the like, and then directly hydrocracke to prepare ethylene glycol. The first route is mainly connected with the existing petrochemical technology, and is the most popularized and applied route at present. Compared with the second route, the third route has fewer steps for preparing the ethylene glycol by directly catalyzing and hydrocracking without passing through the sugar alcohol intermediate, and meanwhile, the target product ethylene glycol has higher selectivity, higher efficiency and energy conservation, and is receiving more and more attention. The conversion of non-edible biomass raw materials such as cellulose and the like to prepare ethylene glycol is the focus of research at present because the ethylene glycol does not fight against human grains. In 2008, researchers in Dalian institute of chemical and physical science reported for the first time that tungsten carbide promoted with metallic nickel directly catalyzed the conversion of cellulose into ethylene glycol (Direct catalytic conversion of cellulose into ethylene glycol using nickel-promoted tungsten carbide catalysts, angel. Chem. Int. Ed.2008,47, 8510-8513). CN102190562a discloses a method for preparing ethylene glycol from polyhydroxy compounds, which takes polyhydroxy compounds such as cellulose, starch, hemicellulose, sucrose, glucose, fructose, levan and the like as reaction raw materials, takes VIII group transition metals such as iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, oxides of platinum and tungsten, tungstic acid, tungstate containing and heteropolyacid containing tungsten as catalytic active components to form a composite catalyst, and carries out one-step catalytic conversion process under the hydrothermal condition of 120-300 ℃ and hydrogen pressure of 1-13MPa, thus realizing the efficient, high-selectivity and high-yield preparation of ethylene glycol from polyhydroxy compounds. CN 104119207a discloses a method for preparing ethylene glycol by catalytic conversion of carbohydrate, the method uses carbohydrate as a reaction raw material, water as a solvent, and a catalyst formed by a simple substance or compound of lanthanum and one or more than two of transition metals of iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium and platinum as a composite catalyst, and the method realizes the efficient, high-selectivity and high-yield preparation of ethylene glycol by one-step catalytic conversion process of cellulose under the hydrothermal condition of 120-300 ℃ and hydrogen pressure of 1-13 MPa.
The research shows that in the process of preparing the ethylene glycol from the carbohydrate, the metal catalyst and the M-N-W-O oxide catalyst are used, so that higher efficiency of preparing the ethylene glycol from the carbohydrate can be obtained, and meanwhile, the catalyst has higher hydrothermal stability, can be recycled and has good economic benefit; meanwhile, the catalyst has low requirements on reaction equipment, and is a new environment-friendly catalytic system.
Disclosure of Invention
One of the technical problems to be solved by the invention is that the efficiency of preparing ethylene glycol by using carbohydrate is lower in the prior art, and a combined catalyst for preparing ethylene glycol by using carbohydrate is provided. The second technical problem to be solved by the invention is to provide a preparation method of a catalyst corresponding to one of the technical problems. The third technical problem to be solved by the invention is a method for preparing ethylene glycol from carbohydrate by adopting a catalyst corresponding to one of the technical problems.
In order to solve the technical problems, the invention adopts the following technical scheme: a catalyst for the preparation of ethylene glycol from a carbohydrate comprising a metal catalyst I and a multi-element transition metal oxide (M-N-W-O oxide) catalyst II comprising M, N and W elements, wherein M is selected from at least one of the elements of group IVB and N is selected from at least one of the elements of group VB.
In the above technical scheme, the catalyst for preparing ethylene glycol from a carbohydrate, wherein the carbohydrate is at least one selected from cellulose, starch, hemicellulose and saccharides, but is not limited thereto; wherein the cellulose comprises microcrystalline cellulose and cellulose in lignocellulosic biomass.
In the above technical scheme, the metal component of the catalyst I is at least one selected from VIII groups, and the preferable metal component is at least one selected from Ni, ru and Ir.
In the above technical scheme, in the catalyst I, other components besides the metal component are selected from at least one of carbon materials or oxides, and exist as a carrier of the metal component or mixed with the metal component.
In the above technical scheme, the content of the metal component is 0.03% -95%, preferably 0.08% -90%, more preferably 0.1% -70% of the weight of the catalyst I.
In the technical scheme, M in the M-N-W-O oxide catalyst II is at least one selected from Ti, zr and Hf in the IVB group.
In a preferred embodiment, M in the catalyst II is selected from Ti and Zr.
In the above technical scheme, N in the M-N-W-O oxide catalyst II is at least one selected from group VB element V, nb and Ta.
In a preferred technical scheme, N in the catalyst II is selected from Nb and Ta.
In the technical scheme, the catalyst II is prepared from the IVB element, the N is prepared from the VB element and the W, and further, the catalyst II is prepared from the Ti and the Zr, the N is prepared from the Nb and the Ta and is prepared from the W element, so that unexpected synergistic effect is achieved on improving the yield of the target product glycol in the reaction of preparing the glycol.
In the above embodiment, the molar ratio of W (M+N) in the M-N-W-O oxide catalyst II is (0.01-199): 1, preferably (0.10-49): 1, more preferably (0.20-9): 1.
In the above technical scheme, the molar ratio of M to N in the M-N-W-O oxide catalyst II is (0.01-99): 1, preferably (0.10-9): 1
In the above technical scheme, the ratio of the metal content in the catalyst I to the W content in the oxide catalyst II used in the reaction process is in the range of 0.0001-1500, preferably 0.001-500, by weight.
In the technical scheme, the metal catalyst and the M-N-W-O oxide catalyst are used together to play an unexpected synergistic effect on improving the yield of the ethylene glycol in the reaction of preparing the ethylene glycol from the carbohydrate.
In order to solve the second technical problem, the technical scheme adopted by the invention comprises the following steps:
a) The preparation method of the catalyst I comprises an impregnation method, a precipitation method, an ion exchange method and a liquid phase reduction method;
b) The preparation method of the catalyst II mainly adopts a coprecipitation method.
In the technical scheme, the preparation of the catalyst II comprises the following steps of:
a) Weighing tungsten salt precursor with required content, dissolving in proper amount of deionized water, ensuring complete dissolution and uniform mixing of the precursor, and regulating pH of the solution by using ammonia water to obtain solution A;
b) Weighing the needed content of M, N soluble salt, dissolving in a proper amount of deionized water, and uniformly mixing to obtain a solution B;
c) Slowly dropwise adding the solution B into the solution A while stirring vigorously, and simultaneously dropwise adding ammonia water to adjust the pH of the solution, and aging the precipitate;
d) And washing, filtering, drying and roasting the obtained solid to obtain the catalyst II.
In the technical scheme, in the preparation process of the catalyst II, the pH value of the solution A is regulated to 9.0-11.0 in the step a, the pH value of the precipitate in the step c is regulated to 9.5-11.5, the ageing temperature of the precipitate is room temperature-240 ℃, the ageing time is 1-72 hours, the drying temperature is 80-150 ℃, the drying time is 1-48 hours, the roasting temperature is 300-900 ℃, and the roasting time is 1-12 hours.
In order to solve the third technical problem, the invention adopts the technical scheme that the catalyst I and the catalyst II in the scheme are adopted, water is used as a solvent, hydrogen is filled into a high-pressure reaction kettle before the reaction, and the initial hydrogen pressure is 1-10MPa, preferably 2-8MPa; the reaction temperature is 120-300 ℃, preferably 150-260 ℃, and the biomass raw material is catalyzed to be converted into ethylene glycol under the action of the combined catalyst.
In the technical scheme, the reaction for preparing the ethylene glycol by catalytic conversion of biomass comprises the following steps: adding a required catalyst and a certain amount of reactants into a 100mL high-pressure reaction kettle, adding a required amount of water, sealing the kettle, and introducing hydrogen for replacement to reach a target pressure; heating to the target temperature, reacting for a certain time, and cooling after the reaction is finished. After cooling to room temperature, the solid and the reaction solution were separated by filtration, and the filtrate was fixed in volume and then quantified. The reaction solution was subjected to gas chromatography after silylation, and each product was quantitatively analyzed by using an HP-1ms (30 m. Times.0.25 mm. Times.0.25 μm)) column and an FID detector, and an internal standard method.
The conversion of biomass and the selectivity to ethylene glycol and yield were calculated according to the following formula:
Figure BDA0001830101420000041
Figure BDA0001830101420000042
ethylene glycol yield = biomass conversion x ethylene glycol selectivity
The coupling metal catalyst and the M-N-W-O oxide catalyst are applied to the reaction of preparing the ethylene glycol from the carbohydrate, and efficiently catalyze the conversion of the carbohydrate to the ethylene glycol. The M-N-W-O oxide not only provides an active site for obtaining the glycol precursor by breaking the C-C bond of a catalytic reactant or a reaction intermediate, but also increases the acidity of a solution under the reaction condition by the acidic site contained in the oxide, accelerates the conversion of the reactant, reduces the reaction temperature, shortens the reaction time, improves the reaction efficiency, reduces the deep cracking of the glycol, and is beneficial to ensuring the selectivity of the glycol. Meanwhile, liquid acid is not required to be added in the method, so that the discharge of acid liquor and environmental pollution are avoided, and the method is a green and environment-friendly process; and the metal catalyst and the oxide catalyst have high hydrothermal stability and good cyclic reaction performance, so that the economy is improved, and the industrialization is realized more easily. The catalyst provided by the invention is used in the reaction of preparing ethylene glycol from cellulose, the conversion rate of cellulose reaches 58.7% at a lower temperature, and the selectivity of ethylene glycol is 38.6%; the catalyst has better performance and stable cyclic reaction performance, and obtains better technical effect.
The present invention is further illustrated by the following examples, but the present invention is not limited to these examples.
Detailed Description
[ example 1 ]
30％Ni-SiO 2 The catalyst is prepared by adopting a precipitation method: 29.726g of nickel nitrate hexahydrate is dissolved in deionized water to prepare 1mol/L nickel nitrate solution, 4mol/L NaOH solution is dropwise added under vigorous stirring for precipitation, 35g of 40% silica sol is dropwise added after the pH value is more than 11 to form gel, then the temperature is raised to 100 ℃ for aging for 4 hours, and the filtrate is filtered and washed until the filtrate is neutral. Oven-drying at 120deg.C overnight, calcining at 500deg.C under air atmosphere for 4 hr, and reducing with hydrogen.
Ternary transition metal oxide catalyst containing Zr, nb and W, where W/Zr/nb=0.2/0.6/0.4, noted WO 3 -ZrO 2 -Nb 2 O 5 (W/Zr/nb=0.2/0.6/0.4) (hereinafter the same applies). The preparation method adopts a coprecipitation method to prepare: 0.566g of ammonium metatungstate ((NH) 4 ) 6 W 7 O 24 ·6H 2 O) dissolving in 30mL of deionized water, and regulating the pH to about 10.0 by using ammonia water to obtain solution A; 1.684g of nitric acid dihydrate was weighed againZirconyl (ZrO (NO) 3 ) 2 ·2H 2 O) and 2.260g of niobium oxalate are dissolved in 50mL of deionized water and uniformly mixed to obtain a solution B; slowly dripping the solution B into the solution A under vigorous stirring, simultaneously dripping ammonia water to adjust the pH to about 10.0, and heating to 100 ℃ for reflux aging for 24 hours after the dripping of the solution B is completed; after cooling, the precipitate is filtered, washed to neutrality by water, dried at 120 ℃ for 12 hours, and finally baked at 500 ℃ for 4 hours in air atmosphere to prepare the WO 3 -ZrO 2 -Nb 2 O 5 (W/Zr/nb=0.2/0.6/0.4) oxide catalyst.
The reaction for preparing glycol by catalytic conversion of cellulose is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose and 0.5g of 30% Ni-SiO are weighed 2 And 0.6g WO 3 -ZrO 2 -Nb 2 O 5 (W/Zr/nb=0.2/0.6/0.4) the catalyst was added to a high-pressure reaction vessel (100 mL) containing 40mL of water, the reaction vessel was closed, then replaced three times by introducing hydrogen, then charging hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. Cooling after the reaction is finished, and filtering to separate solid and reaction liquid (reaction product).
Mixing a certain amount of reaction solution with an internal standard solution, derivatizing part of the mixed solution by using hexamethyldisilazane and trimethylchlorosilane, and quantitatively analyzing by using gas chromatography. The conversion of cellulose and the selectivity and yield of ethylene glycol were calculated according to the above formula. The evaluation results are shown in Table 1.
[ example 2 ]
30％Ni-SiO 2 The catalyst preparation was the same as in example 1.
WO 3 -ZrO 2 -Nb 2 O 5 (W/Zr/nb=1.0/0.6/0.4) catalyst was prepared by co-precipitation: 1.132g of ammonium metatungstate ((NH) 4 ) 6 W 7 O 24 ·6H 2 O) dissolving in 60mL of deionized water, and regulating the pH to about 10.0 by using ammonia water to obtain solution A; then, 0.673g of zirconyl nitrate dihydrate (ZrO (NO) 3 ) 2 ·2H 2 O) and 0.904g of niobium oxalate are dissolved in 20mL of deionized water and uniformly mixed to obtain solution B; solution B was slowly stirred vigorously Dropwise adding the solution A, simultaneously dropwise adding ammonia water to adjust the pH to about 10.0, and after the solution B is completely added, heating to 100 ℃, refluxing and aging for 24 hours; after cooling, the precipitate is filtered, washed to neutrality by water, dried at 120 ℃ for 12 hours, and finally baked at 500 ℃ for 4 hours in air atmosphere to prepare the WO 3 -ZrO 2 -Nb 2 O 5 (W/Zr/nb=1.0/0.6/0.4) oxide catalyst.
The reaction for preparing glycol by catalytic conversion of cellulose is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose and 0.5g of 30% Ni-SiO are weighed 2 And 0.6g WO 3 -ZrO 2 -Nb 2 O 5 (W/Zr/nb=1.0/0.6/0.4) the catalyst was added to a high-pressure reaction vessel (100 mL) containing 40mL of water, the reaction vessel was closed, then replaced three times by introducing hydrogen, then charging hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. Cooling after the reaction is finished, and filtering to separate solid and reaction liquid (reaction product). The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 3 ]
30％Ni-SiO 2 The catalyst preparation was the same as in example 1.
WO 3 -ZrO 2 -Nb 2 O 5 (W/Zr/nb=9.0/0.6/0.4) catalyst was prepared by co-precipitation: 1.019g of ammonium metatungstate ((NH) 4 ) 6 W 7 O 24 ·6H 2 O) dissolving in 60mL of deionized water, and regulating the pH to about 10.0 by using ammonia water to obtain solution A; then, 0.067g of zirconyl nitrate dihydrate (ZrO (NO) 3 ) 2 ·2H 2 O) and 0.090g of niobium oxalate are dissolved in 20mL of deionized water and uniformly mixed to obtain a solution B; slowly dripping the solution B into the solution A under vigorous stirring, simultaneously dripping ammonia water to adjust the pH to about 10.0, and heating to 100 ℃ for reflux aging for 24 hours after the dripping of the solution B is completed; after cooling, the precipitate is filtered, washed to neutrality by water, dried at 120 ℃ for 12 hours, and finally baked at 500 ℃ for 4 hours in air atmosphere to prepare the WO 3 -ZrO 2 -Nb 2 O 5 (W/Zr/nb=9.0/0.6/0.4) oxide catalyst.
Catalytic conversion of cellulose to ethylene glycolThe reaction of the alcohol is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose and 0.5g of 30% Ni-SiO are weighed 2 And 0.6g WO 3 -ZrO 2 -Nb 2 O 5 (W/Zr/nb=9.0/0.6/0.4) the catalyst was added to a high-pressure reaction vessel (100 mL) containing 40mL of water, the reaction vessel was closed, then replaced three times by introducing hydrogen, then charging hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. Cooling after the reaction is finished, and filtering to separate solid and reaction liquid (reaction product). The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 4 ]
30％Ni-SiO 2 The catalyst preparation was the same as in example 1.
WO 3 -ZrO 2 -Nb 2 O 5 (W/Zr/nb=1.0/0.1/0.9) catalyst was prepared by co-precipitation: 1.132g of ammonium metatungstate ((NH) 4 ) 6 W 7 O 24 ·6H 2 O) dissolving in 60mL of deionized water, and regulating the pH to about 10.0 by using ammonia water to obtain solution A; then, 0.112g of zirconyl nitrate dihydrate (ZrO (NO) 3 ) 2 ·2H 2 O) and 2.034g of niobium oxalate are dissolved in 20mL of deionized water and uniformly mixed to obtain solution B; slowly dripping the solution B into the solution A under vigorous stirring, simultaneously dripping ammonia water to adjust the pH to about 10.0, and heating to 100 ℃ for reflux aging for 24 hours after the dripping of the solution B is completed; after cooling, the precipitate is filtered, washed to neutrality by water, dried at 120 ℃ for 12 hours, and finally baked at 500 ℃ for 4 hours in air atmosphere to prepare the WO 3 -ZrO 2 -Nb 2 O 5 (W/Zr/nb=1.0/0.1/0.9) oxide catalyst.
The reaction for preparing glycol by catalytic conversion of cellulose is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose and 0.5g of 30% Ni-SiO are weighed 2 And 0.6g WO 3 -ZrO 2 -Nb 2 O 5 (W/Zr/nb=1.0/0.1/0.9) the catalyst was added to a high-pressure reaction vessel (100 mL) containing 40mL of water, the reaction vessel was closed, and then replaced three times with hydrogen, and then charged with hydrogen to 6MPa, heated to 220 c, and reacted for 30 minutes. Cooling after the reaction is finished, and filtering to separate solid and reaction liquid (reaction product). ReactionThe quantitative method of (2) was the same as in example 1, and the results are shown in Table 1.
[ example 5 ]
30％Ni-SiO 2 The catalyst preparation was the same as in example 1.
WO 3 -ZrO 2 -Nb 2 O 5 (W/Zr/nb=1.0/0.9/0.1) the catalyst was prepared by co-precipitation: 1.132g of ammonium metatungstate ((NH) 4 ) 6 W 7 O 24 ·6H 2 O) dissolving in 60mL of deionized water, and regulating the pH to about 10.0 by using ammonia water to obtain solution A; 1.010g of zirconyl nitrate dihydrate (ZrO (NO) 3 ) 2 ·2H 2 O) and 0.226g of niobium oxalate are dissolved in 20mL of deionized water and uniformly mixed to obtain a solution B; slowly dripping the solution B into the solution A under vigorous stirring, simultaneously dripping ammonia water to adjust the pH to about 10.0, and heating to 100 ℃ for reflux aging for 24 hours after the dripping of the solution B is completed; after cooling, the precipitate is filtered, washed to neutrality by water, dried at 120 ℃ for 12 hours, and finally baked at 500 ℃ for 4 hours in air atmosphere to prepare the WO 3 -ZrO 2 -Nb 2 O 5 (W/Zr/nb=1.0/0.9/0.1) oxide catalyst.
The reaction for preparing glycol by catalytic conversion of cellulose is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose and 0.5g of 30% Ni-SiO are weighed 2 And 0.6g WO 3 -ZrO 2 -Nb 2 O 5 (W/Zr/nb=1.0/0.9/0.1) the catalyst was added to a high-pressure reaction vessel (100 mL) containing 40mL of water, the reaction vessel was closed, then replaced three times by introducing hydrogen, then charging hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. Cooling after the reaction is finished, and filtering to separate solid and reaction liquid (reaction product). The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 6 ]
30％Ni-SiO 2 The catalyst preparation was the same as in example 1.
WO 3 -TiO 2 -Nb 2 O 5 (W/Ti/nb=1.0/0.6/0.4) catalyst was prepared by co-precipitation: 1.132g of ammonium metatungstate ((NH) 4 ) 6 W 7 O 24 ·6H 2 O) dissolving in 60mL of deionized water, and regulating the pH to about 10.0 by using ammonia water to obtain solution A; then, 0.605g of titanium sulfate (Ti (SO) 4 ) 2 And 0.904g of niobium oxalate are dissolved in 20mL of deionized water and uniformly mixed to obtain solution B; slowly dripping the solution B into the solution A under vigorous stirring, simultaneously dripping ammonia water to adjust the pH to about 10.0, and heating to 100 ℃ for reflux aging for 24 hours after the dripping of the solution B is completed; after cooling, the precipitate is filtered, washed to neutrality by water, dried at 120 ℃ for 12 hours, and finally baked at 500 ℃ for 4 hours in air atmosphere to prepare the WO 3 -TiO 2 -Nb 2 O 5 (W/Ti/nb=1.0/0.6/0.4) oxide catalyst.
The reaction for preparing glycol by catalytic conversion of cellulose is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose and 0.5g of 30% Ni-SiO are weighed 2 And 0.6g WO 3 -TiO 2 -Nb 2 O 5 (W/Ti/nb=1.0/0.6/0.4) the catalyst was added to a high-pressure reaction vessel (100 mL) containing 40mL of water, the reaction vessel was closed, and after three replacements with hydrogen gas, the reaction vessel was heated to 220 ℃ to react for 30 minutes under 6 MPa. Cooling after the reaction is finished, and filtering to separate solid and reaction liquid (reaction product). The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 7 ]
30％Ni-SiO 2 The catalyst preparation was the same as in example 1.
WO 3 -HfO 2 -Nb 2 O 5 (W/Hf/nb=1.0/0.6/0.4) catalyst was prepared by co-precipitation: 1.132g of ammonium metatungstate ((NH) 4 ) 6 W 7 O 24 ·6H 2 O) dissolving in 60mL of deionized water, and regulating the pH to about 10.0 by using ammonia water to obtain solution A; 1.032g of hafnium oxychloride (HfOCl) was then weighed out 2 ·8H 2 O) and 0.904g of niobium oxalate are dissolved in 20mL of deionized water and uniformly mixed to obtain solution B; slowly dripping the solution B into the solution A under vigorous stirring, simultaneously dripping ammonia water to adjust the pH to about 10.0, and heating to 100 ℃ for reflux aging for 24 hours after the dripping of the solution B is completed; after cooling, the precipitate is filtered, washed to neutrality by water and is cooled to 120 DEG CDrying for 12 hr, and roasting at 500 deg.C for 4 hr in air atmosphere to obtain WO 3 -HfO 2 -Nb 2 O 5 (W/Hf/nb=1.0/0.6/0.4) oxide catalyst.
The reaction for preparing glycol by catalytic conversion of cellulose is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose and 0.5g of 30% Ni-SiO are weighed 2 And 0.6g WO 3 -HfO 2 -Nb 2 O 5 (W/Hf/nb=1.0/0.6/0.4) the catalyst was added to a high-pressure reaction vessel (100 mL) containing 40mL of water, the reaction vessel was closed, and after three replacements with hydrogen gas, the reaction vessel was heated to 220 ℃ to react for 30 minutes under 6 MPa. Cooling after the reaction is finished, and filtering to separate solid and reaction liquid (reaction product). The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 8 ]
30％Ni-SiO 2 The catalyst preparation was the same as in example 1.
WO 3 -ZrO 2 -TiO 2 -Nb 2 O 5 (W/Zr/Ti/nb=1.0/0.3/0.3/0.4) catalyst was prepared by co-precipitation: 1.132g of ammonium metatungstate ((NH) 4 ) 6 W 7 O 24 ·6H 2 O) dissolving in 60mL of deionized water, and regulating the pH to about 10.0 by using ammonia water to obtain solution A; then, 0.337g of zirconyl nitrate dihydrate (ZrO (NO) 3 ) 2 ·2H 2 O), 0.302g of titanium sulfate (Ti (SO) 4 ) 2 And 0.904g of niobium oxalate are dissolved in 20mL of deionized water and uniformly mixed to obtain solution B; slowly dripping the solution B into the solution A under vigorous stirring, simultaneously dripping ammonia water to adjust the pH to about 10.0, and heating to 100 ℃ for reflux aging for 24 hours after the dripping of the solution B is completed; after cooling, the precipitate is filtered, washed to neutrality by water, dried at 120 ℃ for 12 hours, and finally baked at 500 ℃ for 4 hours in air atmosphere to prepare the WO 3 -ZrO 2 -TiO 2 -Nb 2 O 5 (W/Zr/Ti/nb=1.0/0.3/0.3/0.4) oxide catalyst.
The reaction for preparing glycol by catalytic conversion of cellulose is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose and 0.5g of 30% Ni-SiO are weighed 2 And 0.6g WO 3 -ZrO 2 -TiO 2 -Nb 2 O 5 (W/Zr/Ti/nb=1.0/0.3/0.3/0.4) the catalyst was added to a high-pressure reaction vessel (100 mL) containing 40mL of water, the reaction vessel was closed, then replaced three times by introducing hydrogen, then charging hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. Cooling after the reaction is finished, and filtering to separate solid and reaction liquid (reaction product). The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 9 ]
30％Ni-SiO 2 The catalyst preparation was the same as in example 1.
WO 3 -ZrO 2 -HfO 2 -Nb 2 O 5 (W/Zr/Hf/nb=1.0/0.3/0.3/0.4) catalyst was prepared by co-precipitation: 1.132g of ammonium metatungstate ((NH) 4 ) 6 W 7 O 24 ·6H 2 O) dissolving in 60mL of deionized water, and regulating the pH to about 10.0 by using ammonia water to obtain solution A; then, 0.337g of zirconyl nitrate dihydrate (ZrO (NO) 3 ) 2 ·2H 2 O)、0.516g HfOCl 2 ·8H 2 O and 0.904g of niobium oxalate are dissolved in 20mL of deionized water and uniformly mixed to obtain solution B; slowly dripping the solution B into the solution A under vigorous stirring, simultaneously dripping ammonia water to adjust the pH to about 10.0, and heating to 100 ℃ for reflux aging for 24 hours after the dripping of the solution B is completed; after cooling, the precipitate is filtered, washed to neutrality by water, dried at 120 ℃ for 12 hours, and finally baked at 500 ℃ for 4 hours in air atmosphere to prepare the WO 3 -ZrO 2 -HfO 2 -Nb 2 O 5 (W/Zr/Hf/nb=1.0/0.3/0.3/0.4) oxide catalyst.
The reaction for preparing glycol by catalytic conversion of cellulose is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose and 0.5g of 30% Ni-SiO are weighed 2 And 0.6g WO 3 -ZrO 2 -HfO 2 -Nb 2 O 5 (W/Zr/Hf/nb=1.0/0.3/0.3/0.4) the catalyst was added to a high pressure reactor (100 mL) containing 40mL of water, the reactor was closed, then replaced three times by introducing hydrogen, then charging hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. Cooling after the reaction is finished, filtering and separating solid and reacting Liquid (reaction product). The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 10 ]
30％Ni-SiO 2 The catalyst preparation was the same as in example 1.
WO 3 -TiO 2 -HfO 2 -Nb 2 O 5 (W/Ti/Hf/nb=1.0/0.3/0.3/0.4) catalyst was prepared by co-precipitation: 1.132g of ammonium metatungstate ((NH) 4 ) 6 W 7 O 24 ·6H 2 O) dissolving in 60mL of deionized water, and regulating the pH to about 10.0 by using ammonia water to obtain solution A; then, 0.302g of titanium sulfate (Ti (SO) 4 ) 2 、0.516g HfOCl 2 ·8H 2 O and 0.904g of niobium oxalate are dissolved in 20mL of deionized water and uniformly mixed to obtain solution B; slowly dripping the solution B into the solution A under vigorous stirring, simultaneously dripping ammonia water to adjust the pH to about 10.0, and heating to 100 ℃ for reflux aging for 24 hours after the dripping of the solution B is completed; after cooling, the precipitate is filtered, washed to neutrality by water, dried at 120 ℃ for 12 hours, and finally baked at 500 ℃ for 4 hours in air atmosphere to prepare the WO 3 -TiO 2 -HfO 2 -Nb 2 O 5 (W/Ti/Hf/nb=1.0/0.3/0.3/0.4) oxide catalyst.
The reaction for preparing glycol by catalytic conversion of cellulose is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose and 0.5g of 30% Ni-SiO are weighed 2 And 0.6g WO 3 -TiO 2 -HfO 2 -Nb 2 O 5 (W/Ti/Hf/nb=1.0/0.3/0.3/0.4) the catalyst was added to a high pressure reactor (100 mL) containing 40mL of water, the reactor was closed, then replaced three times by introducing hydrogen, then charging hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. Cooling after the reaction is finished, and filtering to separate solid and reaction liquid (reaction product). The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 11 ]
30％Ni-SiO 2 The catalyst preparation was the same as in example 1.
WO 3 -ZrO 2 -V 2 O 5 (W/Zr/v=1.0/0.6/0.4) catalyst employs co-catalystPreparation by a precipitation method: 1.132g of ammonium metatungstate ((NH) 4 ) 6 W 7 O 24 ·6H 2 O) dissolving in 60mL of deionized water, and regulating the pH to about 10.0 by using ammonia water to obtain solution A; then, 0.673g of zirconyl nitrate dihydrate (ZrO (NO) 3 ) 2 ·2H 2 O) and 0.205g of sodium metavanadate are dissolved in 20mL of deionized water, and uniformly mixed to obtain a solution B; slowly dripping the solution B into the solution A under vigorous stirring, simultaneously dripping ammonia water to adjust the pH to about 10.0, and heating to 100 ℃ for reflux aging for 24 hours after the dripping of the solution B is completed; after cooling, the precipitate is filtered, washed to neutrality by water, dried at 120 ℃ for 12 hours, and finally baked at 500 ℃ for 4 hours in air atmosphere to prepare the WO 3 -ZrO 2 -V 2 O 5 (W/Zr/v=1.0/0.6/0.4) oxide catalyst.
The reaction for preparing glycol by catalytic conversion of cellulose is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose and 0.5g of 30% Ni-SiO are weighed 2 And 0.6g WO 3 -ZrO 2 -V 2 O 5 (W/Zr/v=1.0/0.6/0.4) the catalyst was added to a high-pressure reaction vessel (100 mL) containing 40mL of water, the reaction vessel was closed, then replaced three times by introducing hydrogen, then charging hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. Cooling after the reaction is finished, and filtering to separate solid and reaction liquid (reaction product). The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 12 ]
30％Ni-SiO 2 The catalyst preparation was the same as in example 1.
WO 3 -ZrO 2 -Ta 2 O 5 (W/Zr/ta=1.0/0.6/0.4) catalyst was prepared by co-precipitation: 1.132g of ammonium metatungstate ((NH) 4 ) 6 W 7 O 24 ·6H 2 O) dissolving in 60mL of deionized water, and regulating the pH to about 10.0 by using ammonia water to obtain solution A; then, 0.673g of zirconyl nitrate dihydrate (ZrO (NO) 3 ) 2 ·2H 2 O) and 1.052g of tantalum oxalate are dissolved in 20mL of deionized water and uniformly mixed to obtain solution B; slowly dripping the solution B into the solution A under vigorous stirring, and simultaneously dripping ammonia waterAdjusting the pH to about 10.0, and after the solution B is added dropwise, heating to 100 ℃, refluxing and aging for 24 hours; after cooling, the precipitate is filtered, washed to neutrality by water, dried at 120 ℃ for 12 hours, and finally baked at 500 ℃ for 4 hours in air atmosphere to prepare the WO 3 -ZrO 2 -Ta 2 O 5 (W/Zr/ta=1.0/0.6/0.4) oxide catalyst.
The reaction for preparing glycol by catalytic conversion of cellulose is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose and 0.5g of 30% Ni-SiO are weighed 2 And 0.6g WO 3 -ZrO 2 -Ta 2 O 5 (W/Zr/ta=1.0/0.6/0.4) the catalyst was added to a high-pressure reaction vessel (100 mL) containing 40mL of water, the reaction vessel was closed, then replaced three times by introducing hydrogen, then charging hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. Cooling after the reaction is finished, and filtering to separate solid and reaction liquid (reaction product). The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 13 ]
30％Ni-SiO 2 The catalyst preparation was the same as in example 1.
WO 3 -ZrO 2 -Nb 2 O 5 -Ta 2 O 5 (W/Zr/Nb/ta=1.0/0.6/0.2/0.2) the catalyst was prepared by co-precipitation: 1.132g of ammonium metatungstate ((NH) 4 ) 6 W 7 O 24 ·6H 2 O) dissolving in 60mL of deionized water, and regulating the pH to about 10.0 by using ammonia water to obtain solution A; then, 0.673g of zirconyl nitrate dihydrate (ZrO (NO) 3 ) 2 ·2H 2 O), 0.452g of niobium oxalate and 0.526g of tantalum oxalate are dissolved in 20mL of deionized water and uniformly mixed to obtain a solution B; slowly dripping the solution B into the solution A under vigorous stirring, simultaneously dripping ammonia water to adjust the pH to about 10.0, and heating to 100 ℃ for reflux aging for 24 hours after the dripping of the solution B is completed; after cooling, the precipitate is filtered, washed to neutrality by water, dried at 120 ℃ for 12 hours, and finally baked at 500 ℃ for 4 hours in air atmosphere to prepare the WO 3 -ZrO 2 -Nb 2 O 5 -Ta 2 O 5 (W/Zr/Nb/ta=1.0/0.6/0.2/0.2) oxide catalyst.
The reaction for preparing glycol by catalytic conversion of cellulose is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose and 0.5g of 30% Ni-SiO are weighed 2 And 0.6g WO 3 -ZrO 2 -Nb 2 O 5 -Ta 2 O 5 (W/Zr/Nb/ta=1.0/0.6/0.2/0.2) the catalyst was added to a high-pressure reaction vessel (100 mL) containing 40mL of water, the reaction vessel was closed, then replaced three times by introducing hydrogen, charging hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. Cooling after the reaction is finished, and filtering to separate solid and reaction liquid (reaction product). The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 14 ]
30％Ni-SiO 2 The catalyst preparation was the same as in example 1.
WO 3 -ZrO 2 -Nb 2 O 5 -V 2 O 5 (W/Zr/Nb/v=1.0/0.6/0.2/0.2) catalyst was prepared by co-precipitation: 1.132g of ammonium metatungstate ((NH) 4 ) 6 W 7 O 24 ·6H 2 O) dissolving in 60mL of deionized water, and regulating the pH to about 10.0 by using ammonia water to obtain solution A; then, 0.673g of zirconyl nitrate dihydrate (ZrO (NO) 3 ) 2 ·2H 2 O), 0.452g of niobium oxalate and 0.102g of sodium metavanadate are dissolved in 20mL of deionized water, and uniformly mixed to obtain a solution B; slowly dripping the solution B into the solution A under vigorous stirring, simultaneously dripping ammonia water to adjust the pH to about 10.0, and heating to 100 ℃ for reflux aging for 24 hours after the dripping of the solution B is completed; after cooling, the precipitate is filtered, washed to neutrality by water, dried at 120 ℃ for 12 hours, and finally baked at 500 ℃ for 4 hours in air atmosphere to prepare the WO 3 -ZrO 2 -Nb 2 O 5 -V 2 O 5 (W/Zr/Nb/v=1.0/0.6/0.2/0.2) oxide catalyst.
The reaction for preparing glycol by catalytic conversion of cellulose is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose and 0.5g of 30% Ni-SiO are weighed 2 And 0.6g WO 3 -ZrO 2 -Nb 2 O 5 -V 2 O 5 (W/Zr/Nb/v=1.0/0.6/0.2/0.2) catalyst was added to a high pressure reaction with 40mL of waterIn a kettle (100 mL), the reaction kettle is closed, then hydrogen is introduced for three times for replacement, the hydrogen is filled to 6MPa, the temperature is raised to 220 ℃, and the reaction is carried out for 30 minutes. Cooling after the reaction is finished, and filtering to separate solid and reaction liquid (reaction product). The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 15 ]
30％Ni-SiO 2 The catalyst preparation was the same as in example 1.
WO 3 -ZrO 2 -Ta 2 O 5 -V 2 O 5 (W/Zr/Ta/v=1.0/0.6/0.2/0.2) catalyst was prepared by co-precipitation: 1.132g of ammonium metatungstate ((NH) 4 ) 6 W 7 O 24 ·6H 2 O) dissolving in 60mL of deionized water, and regulating the pH to about 10.0 by using ammonia water to obtain solution A; then, 0.673g of zirconyl nitrate dihydrate (ZrO (NO) 3 ) 2 ·2H 2 O), 0.526g of tantalum oxalate and 0.102g of sodium metavanadate are dissolved in 20mL of deionized water, and uniformly mixed to obtain a solution B; slowly dripping the solution B into the solution A under vigorous stirring, simultaneously dripping ammonia water to adjust the pH to about 10.0, and heating to 100 ℃ for reflux aging for 24 hours after the dripping of the solution B is completed; after cooling, the precipitate is filtered, washed to neutrality by water, dried at 120 ℃ for 12 hours, and finally baked at 500 ℃ for 4 hours in air atmosphere to prepare the WO 3 -ZrO 2 -Ta 2 O 5 -V 2 O 5 (W/Zr/Ta/v=1.0/0.6/0.2/0.2) oxide catalyst.
The reaction for preparing glycol by catalytic conversion of cellulose is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose and 0.5g of 30% Ni-SiO are weighed 2 And 0.6g WO 3 -ZrO 2 -Ta 2 O 5 -V 2 O 5 (W/Zr/Ta/v=1.0/0.6/0.2/0.2) the catalyst was added to a high-pressure reaction vessel (100 mL) containing 40mL of water, the reaction vessel was closed, then replaced three times by introducing hydrogen, charging hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. Cooling after the reaction is finished, and filtering to separate solid and reaction liquid (reaction product). The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 16 ]
30％Ni-SiO 2 The catalyst preparation was the same as in example 1.
WO 3 -(Zr,Ti)O 2 -(Nb,Ta) 2 O 5 (W/Zr/Ti/Nb/ta=1.0/0.3/0.3/0.2/0.2) the catalyst was prepared by co-precipitation: 1.132g of ammonium metatungstate ((NH) 4 ) 6 W 7 O 24 ·6H 2 O) dissolving in 60mL of deionized water, and regulating the pH to about 10.0 by using ammonia water to obtain solution A; then, 0.337g of zirconyl nitrate dihydrate (ZrO (NO) 3 ) 2 ·2H 2 O), 0.302g of titanium sulfate (Ti (SO) 4 ) 2 0.452g of niobium oxalate and 0.526g of tantalum oxalate are dissolved in 20mL of deionized water and uniformly mixed to obtain a solution B; slowly dripping the solution B into the solution A under vigorous stirring, simultaneously dripping ammonia water to adjust the pH to about 10.0, and heating to 100 ℃ for reflux aging for 24 hours after the dripping of the solution B is completed; after cooling, the precipitate is filtered, washed to neutrality by water, dried at 120 ℃ for 12 hours, and finally baked at 500 ℃ for 4 hours in air atmosphere to prepare the WO 3 -(Zr,Ti)O 2 -(Nb,Ta) 2 O 5 (W/Zr/Ti/Nb/ta=1.0/0.3/0.3/0.2/0.2) oxide catalyst.
The reaction for preparing glycol by catalytic conversion of cellulose is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose and 0.5g of 30% Ni-SiO are weighed 2 And 0.6g WO 3 -(Zr,Ti)O 2 -(Nb,Ta) 2 O 5 (W/Zr/Ti/Nb/ta=1.0/0.3/0.3/0.2/0.2) the catalyst was added to a high-pressure reaction vessel (100 mL) containing 40mL of water, the reaction vessel was closed, then replaced three times by introducing hydrogen, then, the temperature was raised to 220 ℃ to react for 30 minutes under 6 MPa. Cooling after the reaction is finished, and filtering to separate solid and reaction liquid (reaction product). The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 17 ]
10％Ni-SiO 2 The catalyst is prepared by adopting a precipitation method: 14.863g of nickel nitrate hexahydrate is dissolved in deionized water to prepare 1mol/L nickel nitrate solution, 4mol/L NaOH solution is dripped under vigorous stirring to precipitate, 67.5g of 40% silica sol is dripped after the pH value is more than 11 to form gel, and then the temperature is raised to 10 DEG CAging at 0deg.C for 4 hr, filtering, and washing until the filtrate is neutral. Oven-drying at 120deg.C overnight, calcining at 500deg.C under air atmosphere for 4 hr, and reducing with hydrogen.
WO 3 -(Zr,Ti)O 2 -(Nb,Ta) 2 O 5 (W/Zr/Ti/Nb/ta=1.0/0.3/0.3/0.2/0.2) the catalyst was prepared in the same manner as in example 16.
The reaction for preparing glycol by catalytic conversion of cellulose is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose and 1.5g of 10% Ni-SiO are weighed 2 And 0.6g WO 3 -(Zr,Ti)O 2 -(Nb,Ta) 2 O 5 (W/Zr/Ti/Nb/ta=1.0/0.3/0.3/0.2/0.2) the catalyst was added to a high-pressure reaction vessel (100 mL) containing 40mL of water, the reaction vessel was closed, then replaced three times by introducing hydrogen, then, the temperature was raised to 220 ℃ to react for 30 minutes under 6 MPa. Cooling after the reaction is finished, and filtering to separate solid and reaction liquid (reaction product). The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
Example 18
70％Ni-SiO 2 The catalyst is prepared by adopting a precipitation method: 27.745g of nickel nitrate hexahydrate is dissolved in deionized water to prepare 1mol/L nickel nitrate solution, 4mol/L NaOH solution is dropwise added under vigorous stirring for precipitation, 6g of 40% silica sol is dropwise added after the pH value is more than 11 to form gel, then the temperature is raised to 100 ℃ for aging for 4 hours, and the filtrate is filtered and washed until the filtrate is neutral. Oven-drying at 120deg.C overnight, calcining at 500deg.C under air atmosphere for 4 hr, and reducing with hydrogen.
WO 3 -(Zr,Ti)O 2 -(Nb,Ta) 2 O 5 (W/Zr/Ti/Nb/ta=1.0/0.3/0.3/0.2/0.2) the catalyst was prepared in the same manner as in example 16.
The reaction for preparing glycol by catalytic conversion of cellulose is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose and 0.25g of 70% Ni-SiO were weighed 2 And 0.6g WO 3 -(Zr,Ti)O 2 -(Nb,Ta) 2 O 5 (W/Zr/Ti/Nb/ta=1.0/0.3/0.3/0.2/0.2) the catalyst was added to a high-pressure reaction vessel (100 mL) containing 40mL of water, the reaction vessel was closed, then replaced three times by introducing hydrogen, then, the temperature was raised to 220 ℃ to react for 30 minutes under 6 MPa. Cooling after the reaction is finished, filtering and separatingSolid and reaction liquid (reaction product). The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 19 ]
30％Ni-Al 2 O 3 The catalyst is prepared by adopting a precipitation method: 29.726g of nickel nitrate hexahydrate is dissolved in deionized water to prepare 1mol/L nickel nitrate solution, 4mol/L NaOH solution is added dropwise for precipitation under vigorous stirring until the pH is more than 11, and 14g of Al is added 2 O 3 A gel formed, then aged at room temperature for 4h, and filtered and washed until the filtrate was neutral. Oven-drying at 120deg.C overnight, calcining at 500deg.C under air atmosphere for 4 hr, and reducing with hydrogen.
WO 3 -(Zr,Ti)O 2 -(Nb,Ta) 2 O 5 (W/Zr/Ti/Nb/ta=1.0/0.3/0.3/0.2/0.2) the catalyst was prepared in the same manner as in example 16.
The reaction for preparing glycol by catalytic conversion of cellulose is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose and 0.5g of 30% Ni-Al are weighed 2 O 3 And 0.6g WO 3 -(Zr,Ti)O 2 -(Nb,Ta) 2 O 5 (W/Zr/Ti/Nb/ta=1.0/0.3/0.3/0.2/0.2) the catalyst was added to a high-pressure reaction vessel (100 mL) containing 40mL of water, the reaction vessel was closed, then replaced three times by introducing hydrogen, then, the temperature was raised to 220 ℃ to react for 30 minutes under 6 MPa. Cooling after the reaction is finished, and filtering to separate solid and reaction liquid (reaction product). The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 20 ]
The 1% Ru/C catalyst is prepared by an isovolumetric impregnation method: 1.35mL of RuCl 0.0732mol/L was taken 3 Adding 2g deionized water, shaking uniformly, adding 0.99 active carbon, shaking uniformly, drying at room temperature until most of water is evaporated, drying in a 110 ℃ oven overnight, and reducing with hydrogen.
WO 3 -(Zr,Ti)O 2 -(Nb,Ta) 2 O 5 (W/Zr/Ti/Nb/ta=1.0/0.3/0.3/0.2/0.2) the catalyst was prepared in the same manner as in example 16.
The reaction for preparing glycol by catalytic conversion of cellulose is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose, 0.2g of 1% Ru/C and 0.6g of WO are weighed out 3 -(Zr,Ti)O 2 -(Nb,Ta) 2 O 5 (W/Zr/Ti/Nb/ta=1.0/0.3/0.3/0.2/0.2) the catalyst was added to a high-pressure reaction vessel (100 mL) containing 40mL of water, the reaction vessel was closed, then replaced three times by introducing hydrogen, then, the temperature was raised to 220 ℃ to react for 30 minutes under 6 MPa. Cooling after the reaction is finished, and filtering to separate solid and reaction liquid (reaction product). The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 21 ]
0.1％Ir/SiO 2 The catalyst is prepared by adopting an isovolumetric impregnation method: take 0.4mL of 0.0375mol/L H 2 IrCl 6 Adding 11.5g deionized water, shaking uniformly, adding 2.880g SiO 2 Shaking until the mixture is uniform, drying at room temperature until most of water is evaporated, drying in an oven at 110 ℃ for overnight, and finally roasting in the air and reducing with hydrogen.
WO 3 -(Zr,Ti)O 2 -(Nb,Ta) 2 O 5 (W/Zr/Ti/Nb/ta=1.0/0.3/0.3/0.2/0.2) the catalyst was prepared in the same manner as in example 16.
The reaction for preparing glycol by catalytic conversion of cellulose is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose, 2.0g of 0.1% Ir/SiO are weighed out 2 And 0.6g WO 3 -(Zr,Ti)O 2 -(Nb,Ta) 2 O 5 (W/Zr/Ti/Nb/ta=1.0/0.3/0.3/0.2/0.2) the catalyst was added to a high-pressure reaction vessel (100 mL) containing 40mL of water, the reaction vessel was closed, then replaced three times by introducing hydrogen, then, the temperature was raised to 220 ℃ to react for 30 minutes under 6 MPa. Cooling after the reaction is finished, and filtering to separate solid and reaction liquid (reaction product). The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 22 ]
0.1％Ir-30％Ni-SiO 2 The catalyst is prepared by the following method: firstly, 29.726g of nickel nitrate hexahydrate is dissolved in deionized water to prepare 1mol/L nickel nitrate solution, 4mol/L NaOH solution is dripped under vigorous stirring to precipitate, 35g of 40% silica sol is dripped to form gel after the pH value is more than 11, and then the temperature is raised Aging at 100deg.C for 4 hr, filtering, and washing until the filtrate is neutral. Drying overnight at 120deg.C, calcining at 500deg.C for 4 hr in air atmosphere to obtain NiO-SiO 2 . 0.40mL of 0.0375mol/L H is taken 2 IrCl 6 8.6g of deionized water is added, the mixture is vibrated uniformly, and 3.116g of NiO-SiO is added 2 Shaking until the mixture is uniform, drying at room temperature until most of water is evaporated, drying in an oven at 110deg.C for overnight, and reducing with hydrogen to obtain 0.1% Ir-30% Ni-SiO 2 A catalyst.
WO 3 -(Zr,Ti)O 2 -(Nb,Ta) 2 O 5 (W/Zr/Ti/Nb/ta=1.0/0.3/0.3/0.2/0.2) the catalyst was prepared in the same manner as in example 16.
The reaction for preparing glycol by catalytic conversion of cellulose is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose, 0.4g of 0.1% Ir-30% Ni-SiO are weighed 2 And 0.6g WO 3 -ZrO 2 -TiO 2 (W/Zr/ti=1/0.5/0.5) the catalyst was added to a high-pressure reaction vessel (100 mL) containing 40mL of water, the reaction vessel was closed, then replaced three times by introducing hydrogen, then charging hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. Cooling after the reaction is finished, and filtering to separate solid and reaction liquid (reaction product). The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
Comparative example 1
30％Ni-SiO 2 The catalyst preparation was the same as in example 1.
The reaction for preparing glycol by catalytic conversion of cellulose is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose and 0.5g of 30% Ni-SiO were weighed out 2 The catalyst was added to a high pressure reactor (100 mL) containing 40mL of water, the reactor was closed, and then replaced three times with hydrogen, then charged with hydrogen to 6MPa, heated to 220℃and reacted for 30 minutes. Cooling after the reaction is finished, and filtering to separate solid and reaction liquid (reaction product). The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
Comparative example 2
30％Ni-SiO 2 The catalyst preparation was the same as in example 1.
WO 3 The catalyst is prepared by adopting a direct calcination method:2.0g of ammonium metatungstate is taken and roasted for 4 hours at 500 ℃ under the air atmosphere to prepare WO 3 。
The reaction for preparing glycol by catalytic conversion of cellulose is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose and 0.5g of 30% Ni-SiO are weighed 2 And 0.6g WO 3 The catalyst was added to a high pressure reactor (100 mL) containing 40mL of water, the reactor was closed, and then replaced three times with hydrogen, then charged with hydrogen to 6MPa, heated to 220℃and reacted for 30 minutes. Cooling after the reaction is finished, and filtering to separate solid and reaction liquid (reaction product). The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ comparative example 3 ]
30％Ni-SiO 2 The catalyst preparation was the same as in example 1.
WO 3 -ZrO 2 (W/zr=1.0/1.0) the catalyst was prepared by precipitation: 1.132g of ammonium metatungstate ((NH) 4 ) 6 W 7 O 24 ·6H 2 O) dissolving in 60mL of deionized water, and regulating the pH to about 10.0 by using ammonia water to obtain solution A; 1.122g of zirconyl nitrate dihydrate (ZrO (NO) 3 ) 2 ·2H 2 O) dissolving in 20mL of deionized water, and uniformly mixing to obtain solution B; slowly dropwise adding the solution B into the solution A under vigorous stirring, simultaneously dropwise adding ammonia water to adjust the pH to about 10.0, and heating to 100 ℃ after the solution B is completely dropwise added, refluxing and aging for 24 hours; after cooling, the precipitate is filtered, washed to neutrality by water, dried at 120 ℃ for 12 hours, and finally baked at 500 ℃ for 4 hours in air atmosphere to prepare the WO 3 -ZrO 2 (W/zr=1.0/1.0) oxide.
The reaction for preparing glycol by catalytic conversion of cellulose is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose and 0.5g of 30% Ni-SiO are weighed 2 And 0.6g WO 3 -ZrO 2 (W/zr=1.0/1.0) the catalyst was added to a high-pressure reaction vessel (100 mL) containing 40mL of water, the reaction vessel was closed, then replaced three times by introducing hydrogen, charging hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. Cooling after the reaction is finished, and filtering to separate solid and reaction liquid (reaction product). The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ comparative example 4 ]
30％Ni-SiO 2 The catalyst preparation was the same as in example 1.
WO 3 -Nb 2 O 5 (W/nb=1.0/1.0) the catalyst was prepared by precipitation: 1.132g of ammonium metatungstate ((NH) 4 ) 6 W 7 O 24 ·6H 2 O) dissolving in 60mL of deionized water, and regulating the pH to about 10.0 by using ammonia water to obtain solution A; then weighing 2.260g of niobium oxalate, dissolving in 20mL of deionized water, and uniformly mixing to obtain a solution B; slowly dropwise adding the solution B into the solution A under vigorous stirring, simultaneously dropwise adding ammonia water to adjust the pH to about 10.0, and heating to 100 ℃ after the solution B is completely dropwise added, refluxing and aging for 24 hours; after cooling, the precipitate is filtered, washed to neutrality by water, dried at 120 ℃ for 12 hours, and finally baked at 500 ℃ for 4 hours in air atmosphere to prepare the WO 3 -Nb 2 O 5 (W/nb=1.0/1.0) oxide.
The reaction for preparing glycol by catalytic conversion of cellulose is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose and 0.5g of 30% Ni-SiO are weighed 2 And 0.6g WO 3 -Nb 2 O 5 (W/nb=1.0/1.0) the catalyst was charged into a high-pressure reaction vessel (100 mL) containing 40mL of water, the reaction vessel was closed, and then replaced three times with hydrogen, and after charging hydrogen to 6MPa, the temperature was raised to 220 ℃ and the reaction was carried out for 30 minutes. Cooling after the reaction is finished, and filtering to separate solid and reaction liquid (reaction product). The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
Comparative example 5
30％Ni-SiO 2 The catalyst preparation was the same as in example 1.
WO 3 The catalyst preparation was the same as in comparative example 2.
ZrO 2 The catalyst is prepared by adopting a precipitation method: 1.122g of zirconyl nitrate dihydrate (ZrO (NO) 3 ) 2 ·2H 2 O) dissolving in 80mL of deionized water, and uniformly mixing; dropwise adding ammonia water into the zirconyl nitrate aqueous solution under vigorous stirring to adjust the pH to about 10.0, and after the dropwise adding is finished, heating to 100 ℃, refluxing and aging for 24 hours; after the cooling-down of the material, the material is cooled,filtering the precipitate, washing with water to neutrality, drying at 120deg.C for 12 hr, and calcining at 500deg.C in air atmosphere for 4 hr to obtain ZrO 2 。
Nb 2 O 5 The catalyst is prepared by adopting a precipitation method: weighing 2.260g of niobium oxalate, dissolving in 80mL of deionized water, and uniformly mixing; dropwise adding ammonia water into the niobium oxalate aqueous solution under vigorous stirring to adjust the pH to about 10.0, and after the dropwise adding is finished, heating to 100 ℃, refluxing and aging for 24 hours; after cooling, the generated precipitate is filtered, washed to be neutral by water, dried for 12 hours at 120 ℃, and finally roasted for 4 hours at 500 ℃ under the air atmosphere to prepare Nb 2 O 5 。
TiO 2 The catalyst is prepared by adopting a precipitation method: 1.008g of titanium sulfate (Ti (SO) 4 ) 2 ) Dissolving in 80mL deionized water, and uniformly mixing; dropwise adding ammonia water into the titanium sulfate aqueous solution under vigorous stirring to adjust the pH to about 10.0, and after the dropwise adding is finished, heating to 100 ℃, refluxing and aging for 24 hours; after cooling, the generated precipitate is filtered, washed to be neutral by water, dried for 12 hours at 120 ℃, and finally baked for 4 hours at 500 ℃ under the air atmosphere to prepare the TiO 2 。
Ta 2 O 5 The catalyst is prepared by adopting a precipitation method: 2.630g of tantalum oxalate is weighed and dissolved in 80mL of deionized water, and the mixture is uniformly mixed; dropwise adding ammonia water into the tantalum oxalate aqueous solution under vigorous stirring to adjust the pH to about 10.0, and after the dropwise adding is finished, heating to 100 ℃, refluxing and aging for 24 hours; after cooling, the precipitate is filtered, washed to be neutral by water, dried for 12 hours at 120 ℃, and finally baked for 4 hours at 500 ℃ in air atmosphere to prepare Ta 2 O 5 。
The reaction for preparing glycol by catalytic conversion of cellulose is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose and 0.5g of 30% Ni-SiO are weighed 2 、0.383g WO 3 、0.061g ZrO 2 、0.040g TiO 2 、0.044g Nb 2 O 5 And 0.072g Ta 2 O 5 The catalyst is added into a high-pressure reaction kettle (100 mL) filled with 40mL of water, the reaction kettle is closed, then hydrogen is introduced for three times for replacement, the hydrogen is filled to 6MPa, the temperature is raised to 220 ℃, The reaction was carried out for 30 minutes. Cooling after the reaction is finished, and filtering to separate solid and reaction liquid (reaction product). The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ comparative example 6 ]
WO 3 -(Zr,Ti)O 2 -(Nb,Ta) 2 O 5 (W/Zr/Ti/Nb/ta=1.0/0.3/0.3/0.2/0.2) the catalyst was prepared in the same manner as in example 16.
The reaction for preparing glycol by catalytic conversion of cellulose is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose and 0.6g of WO were weighed out 3 -(Zr,Ti)O 2 -(Nb,Ta) 2 O 5 (W/Zr/Ti/Nb/ta=1.0/0.3/0.3/0.2/0.2) the catalyst was added to a high-pressure reaction vessel (100 mL) containing 40mL of water, the reaction vessel was closed, then replaced three times by introducing hydrogen, then, the temperature was raised to 220 ℃ to react for 30 minutes under 6 MPa. Cooling after the reaction is finished, and filtering to separate solid and reaction liquid (reaction product). The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
TABLE 1
Figure BDA0001830101420000191
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Figure BDA0001830101420000201
Figure BDA0001830101420000211
Reaction conditions: 1.0g microcrystalline cellulose, 40mL water, 6MPa H 2 ，220℃，30min。
Examples 23 to 27
The catalyst after the reaction of example 16 was recovered and subjected to a catalyst recycling reaction 5 times to obtain examples 23 to 27, and the results are shown in Table 2.
TABLE 2
Number of cycles Conversion/% Ethylene glycol selectivity/% Ethylene glycol yield/%
Example 16 - 58.7 38.6 22.7
Example 23 1 time 58.3 38.4 22.4
Example 24 2 times 58.0 38.2 22.2
Example 25 3 times 57.6 38.2 22.0
Example 26 4 times 57.5 37.9 21.8
Example 27 5 times 57.7 37.6 21.7
Reaction conditions: 1.0g of cellulose, 40mL of water, 6MPa H 2 The reaction is carried out for 30min at 220 ℃.
Examples 28 to 32
The combined catalyst prepared in example 16 was used in the reaction of other biomass raw materials to prepare ethylene glycol, and the results are shown in table 3.
TABLE 3 Table 3
Figure BDA0001830101420000212
Figure BDA0001830101420000221
Reaction conditions: 1.0g of raw material, 40mL of water and 6MPa of H 2 The reaction is carried out for 30min at 220 ℃.

Claims (11)

1. A catalyst for preparing glycol from carbohydrate, the catalyst comprising a metal catalyst I and an M-N-W-O oxide catalyst II containing M, N and W elements, wherein M is selected from at least one of the elements of group IVB and N is selected from at least one of the elements of group VB;
the metal component in the catalyst I is at least one of VIII groups, and is specifically selected from at least one of Ni, ru and Ir;
in the catalyst I, other components besides the metal component are selected from at least one of carbon materials or oxides, and are formed by a carrier of the metal component or mixed with the metal component;
in the catalyst II, W (M+N) is (0.2-199) 1; the preparation method of the catalyst II is a coprecipitation method.
2. The catalyst according to claim 1, characterized in that the carbohydrate is selected from at least one of cellulose, starch and hemicellulose.
3. Catalyst I according to claim 1, characterized in that the metal component content is 0.03% -95% by weight of the catalyst I.
4. The catalyst according to claim 1, wherein M in the M-N-W-O oxide catalyst II is selected from at least one of group IVB elements Ti, zr and Hf.
5. The catalyst according to claim 1, wherein N in the M-N-W-O oxide catalyst II is at least one selected from group VB elements V, nb and Ta.
6. The catalyst according to claim 1, wherein the ratio of the metal content of catalyst I to the W content of catalyst II used in the reaction is between 0.0001 and 1500 by weight.
7. Catalyst according to claim 1, characterized in that the molar ratio of M to N in catalyst II is (0.01-99) 1.
8. A process for preparing ethylene glycol using the catalyst for carbohydrate production according to any one of claims 1 to 7, characterized in that:
a) The preparation method of the catalyst I is an impregnation method, a precipitation method, an ion exchange method or a liquid phase reduction method;
b) The preparation method of the catalyst II is a coprecipitation method.
9. The method for preparing a catalyst for preparing ethylene glycol from a carbohydrate as set forth in claim 8, wherein the b) the method for preparing catalyst II comprises the steps of:
a) Weighing tungsten salt precursor with required content, dissolving in proper amount of deionized water, ensuring complete dissolution and uniform mixing of the precursor, and regulating pH of the solution by using ammonia water to obtain solution A;
b) Weighing the needed content of M, N soluble salt, dissolving in a proper amount of deionized water, and uniformly mixing to obtain a solution B;
c) Slowly dropwise adding the solution B into the solution A while maintaining vigorous stirring, simultaneously dropwise adding ammonia water to adjust the pH of the solution, and aging the precipitate under certain conditions;
d) And washing, filtering, drying and roasting the obtained solid to obtain the catalyst II.
10. The method for preparing a catalyst for preparing ethylene glycol from a carbohydrate as claimed in claim 9, wherein the pH of the solution a is adjusted to 9.0-11.0 in step a, the pH of the precipitate in step c is adjusted to 9.5-11.5, the aging temperature of the precipitate is room temperature-240 ℃, the aging time is 1-72 hours, the drying temperature is 80-150 ℃, the drying time is 1-48 hours, the roasting temperature is 300-900 ℃ and the roasting time is 1-12 hours in the preparation process.
11. A method for preparing ethylene glycol from carbohydrate, which is characterized in that the catalyst as claimed in any one of claims 1-7 is adopted, water is used as solvent, hydrogen is filled into a high-pressure reaction kettle before the reaction, the initial hydrogen pressure is 1-10 MPa, the reaction temperature is 120-300 ℃, and biomass is converted into ethylene glycol under the action of the catalyst.
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