阅读说明：本技术 用于合成乙二醇的催化剂及其制备方法和应用 (Catalyst for synthesizing ethylene glycol and preparation method and application thereof ) 是由 贾玉庆 缪长喜 孙清 卢媛娇 张磊 张新玉 于 2019-09-24 设计创作，主要内容包括：本发明公开了一种用于合成乙二醇的催化剂及其制备方法和应用。本发明的合成乙二醇的催化剂包含：a)金属组分,所述金属组分选自VIII族和IB族中的至少一种；b)三氧化钨；c)多元过渡金属氧化物固体酸。本发明中利用M-N-O固体酸负载的金属和三氧化钨催化剂应用于合成乙二醇的反应中,高效地催化了生物质原料向乙二醇的转化。(The invention discloses a catalyst for synthesizing ethylene glycol and a preparation method and application thereof. The catalyst for synthesizing ethylene glycol of the present invention comprises: a) a metal component selected from at least one of group VIII and group IB; b) tungsten trioxide; c) solid acid of multi-transition metal oxide. The invention utilizes M-N-O solid acid loaded metal and tungsten trioxide catalyst to be applied to the reaction of synthesizing ethylene glycol, and efficiently catalyzes the conversion of biomass raw materials to ethylene glycol.)

1. A catalyst for the synthesis of ethylene glycol comprising:

a) a metal component selected from at least one of group VIII and group IB, preferably a metal component selected from at least one of Ru, Pt, Pd, Ni, Cu and Au;

b) tungsten trioxide;

c) solid acid of multi-transition metal oxide.

2. The catalyst according to claim 1, wherein the transition metal oxide polybasic solid acid is an M-N-O oxide, wherein M is selected from at least one of Ti and Zr, and N is selected from at least one of Nb and Ta.

3. The catalyst according to claim 1 or 2, characterized in that the metal component is present in an amount of 0.03 to 40 parts, preferably 0.05 to 30 parts, based on 100 parts by weight of the total catalyst; the tungsten trioxide is 3-50 parts, preferably 5-40 parts; the part of the polybasic transition metal oxide solid acid is 10 to 96.97 parts, preferably 30 to 94.95 parts.

4. The catalyst according to any one of claims 1 to 3, wherein M to N in the M-N-O oxide solid acid in the catalyst is (0.01-99):1, preferably (0.05-19):1, more preferably (0.10-9):1, in terms of molar ratio.

5. The catalyst composition according to any of claims 1-4, characterized in that M is Ti and Zr, N is Nb and Ta, preferably the molar ratio of Ti and Zr is 1 (0.1-10), preferably 1 (0.5-2); the molar ratio of Nb to Ta is 1 (0.1-10), preferably 1 (0.5-2).

6. The method for preparing a catalyst according to any one of claims 1 to 5, comprising the steps of:

the preparation method comprises the steps of immersing multi-transition metal oxide solid acid in a solution containing a metal component precursor and a tungsten salt precursor, and then drying, roasting and reducing to obtain the catalyst for synthesizing the ethylene glycol, wherein preferably, the drying temperature is 60-150 ℃, the drying time is 6-72 hours, the roasting temperature is 200-900 ℃, the roasting time is 1-24 hours, the reducing temperature is 150-900 ℃, and the reducing time is 1-24 hours.

7. The method according to claim 6, wherein the method for producing the transition metal oxide solid acid comprises: a) adding alkali liquor into an aqueous solution containing M soluble salt and N soluble salt for precipitation; b) and aging the precipitate, filtering, washing, drying and roasting to obtain the multi-element transition metal oxide solid acid.

8. The method according to claim 7, wherein the alkali solution in a) is at least one selected from the group consisting of aqueous ammonia, sodium hydroxide, potassium hydroxide, and aqueous sodium carbonate; and/or b), the pH value in the precipitation process is 9.0-11.0, the drying temperature is 90-150 ℃, the drying time is 1-48 hours, the roasting temperature is 200-900 ℃, and the roasting time is 1-24 hours.

9. Use of the catalyst according to any one of claims 1-5 or the catalyst prepared according to any one of claims 6-8 in the preparation of ethylene glycol using a biomass feedstock, preferably the biomass feedstock is selected from at least one of cellulose, starch, hemicellulose and sugars; cellulose includes cellulose from microcrystalline cellulose and lignocellulosic biomass.

10. A process for the preparation of bio-based ethylene glycol comprising converting a biomass feedstock into ethylene glycol in the presence of a catalyst according to any one of claims 1 to 5 or a catalyst prepared according to any one of claims 6 to 8 in an atmosphere comprising a mixed gas of hydrogen and an inert gas, using water as a solvent, preferably at an initial reaction gas pressure of 4 to 15MPa, a reaction temperature of 120-280 ℃ and a biomass feedstock to solvent ratio of (0.001-0.15):1, preferably (0.005-0.10): 1.

Technical Field

The invention relates to the field of ethylene glycol synthesis, and mainly relates to a catalyst for synthesizing ethylene glycol, and a preparation method and application thereof.

Background

The current technical routes adopted by the ethylene glycol industrial production are mainly an ethylene oxide hydration method and a coal-to-ethylene glycol method. The ethylene glycol production capacity of the current ethylene oxide method is about 56 percent, and the ethylene glycol production capacity of the current ethylene oxide method is about 35 percent. Meanwhile, both routes depend on fossil resources, but the storage amount of the fossil resources is limited and the fossil resources are not renewable. With the reduction of fossil resources and the highlighting of environmental problems, it is urgently needed to develop a sustainable route for producing ethylene glycol as a supplement to the existing route, increase the yield of ethylene glycol and reduce the dependence on fossil resources to a certain extent. Biomass is the only renewable organic carbon source that can provide chemicals to humans. The biomass is used for producing the ethylene glycol, and the method has the advantages of rich raw material resources, flexible process route, energy conservation, emission reduction, greenness, low carbon and the like. Therefore, the development of a catalytic system capable of efficiently catalyzing the biomass raw material to be converted into the ethylene glycol is of great significance.

The method for preparing the ethylene glycol by using the biomass raw material mainly comprises three routes; in the first route, biomass is fermented to prepare bioethanol, ethanol is dehydrated to prepare ethylene, and the ethylene is epoxidized and hydrated to prepare ethylene glycol; the second route is that the biomass raw material is firstly prepared into saccharides, the saccharides are hydrogenated into sugar alcohol, and the sugar alcohol is then hydrogenated and cracked to prepare glycol; the third route is that the biomass raw material is treated to obtain cellulose/hemicellulose, starch or saccharides and the like, and then the cellulose/hemicellulose, the starch or the saccharides and the like are directly hydrocracked to prepare the ethylene glycol. The first route mainly links up the existing petrochemical technology and is the route which is popularized and applied most at present. Compared with the second route, the third route has fewer steps for preparing the ethylene glycol by direct catalytic hydrocracking without a sugar alcohol intermediate, and simultaneously the selectivity of the target product ethylene glycol is higher, and the method is more efficient and energy-saving and receives more attention. The conversion of non-edible biomass raw materials such as cellulose to prepare the ethylene glycol has the advantages of rich sources, low utilization cost and no influence on the food safety of human beings, and is the focus of current research. In 2008, researchers at the institute of chemical and physical sciences reported that tungsten carbide promoted with metallic nickel could be used to directly catalyze the conversion of cellulose to ethylene glycol (Direct catalytic conversion of cellulose into ethylene glycol-catalyzed transition carbonate, Angew. chem. int. Ed.2008,47, 8510-channels 8513). CN106573860A discloses a process for the selective conversion of a saccharide-containing feedstock to ethylene glycol by contacting a feedstock comprising at least one saccharide with a catalyst system in the presence of hydrogen and a reaction medium, the reaction being carried out at a pH of from 2.0 to 6.5, ethylene glycol being obtainable from the reaction mixture; wherein the catalyst system comprises tungsten, molybdenum, or a combination thereof and one or more transition metals selected from IUPAC groups 8, 9, and 10 and combinations thereof. CN109843839A discloses a sugar glycol catalyst acid treatment process by conditioning a heterogeneous hydrogenation catalyst by treatment with a protic acid to obtain an acid-conditioned heterogeneous hydrogenation catalyst, and then in a reactor containing hydrogen gas, a carbohydrate feed may be contacted with a dual-function catalyst system comprising the acid-conditioned heterogeneous hydrogenation catalyst and a soluble retro-aldol condensation catalyst to obtain a solution containing glycol. CN109485543A discloses a method for preparing ethylene glycol and 1, 2-propylene glycol from cellulose in one step and a catalyst thereof, which uses water, alkane, alcohol or a combination thereof as a solvent and hydrogen as a reaction atmosphere in the presence of a multi-catalyst composed of a metal oxide as a carrier and a hydrogenation metal loaded on the carrier to catalyze the conversion of cellulose into ethylene glycol and 1, 2-propylene glycol in a reactor.

Disclosure of Invention

One of the technical problems to be solved by the invention is that the efficiency of preparing ethylene glycol by catalytic conversion of biomass is low in the prior art, and a catalyst for synthesizing ethylene glycol is provided. The second technical problem to be solved by the invention is to provide a preparation method of the catalyst for synthesizing the ethylene glycol. The invention provides a method for synthesizing ethylene glycol.

The inventor researches and discovers that the method utilizes the metal supported by the solid acid of the multi-transition metal oxide and the tungsten trioxide catalyst in the reaction for preparing the bio-based ethylene glycol, obtains higher raw material conversion efficiency and ethylene glycol yield even under the condition of not using liquid acid, has low requirement on equipment in the reaction process, can repeatedly use the catalyst, and is a novel green and environment-friendly method.

Accordingly, the present invention provides a catalyst for synthesizing ethylene glycol comprising:

a) a metal component selected from at least one of group VIII and group IB, preferably a metal component selected from at least one of Ru, Pt, Pd, Ni, Cu and Au;

b) tungsten trioxide;

c) solid acid of multi-transition metal oxide.

According to some embodiments of the catalyst of the present invention, the transition metal oxide solid acid is M-N-O oxide, wherein M is selected from at least one of Ti and Zr, and N is selected from at least one of Nb and Ta.

According to some embodiments of the catalyst of the present invention, M is Ti and Zr and N is Nb and Ta. The molar ratio of Ti to Zr may be 1 (0.1-10), preferably 1 (0.5-2). The molar ratio of Nb to Ta may be 1 (0.1-10), preferably 1 (0.5-2).

In the technical scheme of the invention, the M-N-O solid acid oxide M is Ti and Zr, the N is Nb and Ta, and the multifunctional catalyst is prepared by loading metal and tungsten trioxide, wherein each component respectively provides an acid center, a hydrogenation center and a C-C bond breaking center, and the conversion rate of raw materials and the yield of ethylene glycol are improved by the synergistic effect of each component on the catalyst in the reaction of preparing the bio-based ethylene glycol.

In the M-N-O oxide solid acid in the catalyst, the ratio of M to N can be (0.01-99):1, preferably (0.05-19):1, and more preferably (0.10-9): 1. According to some more preferred embodiments, M: N is (0.4-3): 1. Illustratively, M: N may be 1/9, 1/8, 1/7, 1/4, 2/7, 3/7, 1/1, 2/1, 3/1, and the like.

According to some embodiments of the catalyst of the present invention, the metal component is present in an amount of 0.03 to 40 parts, preferably 0.05 to 30 parts, based on 100 parts of the total weight of the catalyst.

According to some embodiments of the catalyst of the present invention, the tungsten trioxide is present in an amount of 3 to 50 parts, preferably 5 to 40 parts, such as 6 to 38 parts, 10 to 35 parts, 10 to 20 parts, 30 parts, etc., based on 100 parts total weight of the catalyst.

According to some embodiments of the catalyst of the present invention, the polybasic transition metal oxide solid acid is present in an amount of 10 to 96.97 parts, preferably 30 to 94.95 parts, based on 100 parts of the total weight of the catalyst.

The preparation method of the catalyst for synthesizing the ethylene glycol comprises the following steps:

the multi-transition metal oxide solid acid is impregnated in a solution containing a metal component precursor and a tungsten salt precursor, and then the catalyst for synthesizing the ethylene glycol is obtained through drying, roasting and reduction.

According to some embodiments of the preparation method of the present invention, in the above step, the drying temperature is preferably 60-150 ℃, the drying time is preferably 6-72 hours, the calcination temperature is preferably 200-900 ℃, the calcination time is preferably 1-24 hours, the reduction temperature is preferably 150-900 ℃, and the reduction time is preferably 1-24 hours.

According to some embodiments of the method of preparing of the present invention, the method of preparing a transition metal oxide solid acid comprises the steps of: a) adding alkali liquor into an aqueous solution containing M soluble salt and N soluble salt for precipitation; b) and aging the precipitate, filtering, washing, drying and roasting to obtain the multi-element transition metal oxide solid acid.

According to some embodiments of the preparation method of the present invention, the alkali solution in step a) is at least one selected from the group consisting of aqueous ammonia, sodium hydroxide, potassium hydroxide and aqueous sodium carbonate.

According to some embodiments of the preparation method of the present invention, in step b), the pH during precipitation is 9.0 to 11.0.

According to some embodiments of the preparation method of the present invention, in the step b), the drying temperature is 90 to 150 ℃ and the drying time is 1 to 48 hours.

According to some embodiments of the preparation method of the present invention, in step b), the calcination temperature is 200-900 ℃ and the calcination time is 1-24 hours.

The invention also provides the application of the catalyst for synthesizing the glycol or the catalyst prepared by the preparation method in preparing the glycol by using biomass raw materials, preferably, the biomass raw materials are selected from at least one of cellulose, starch, hemicellulose and sugar. Cellulose may include cellulose from microcrystalline cellulose and lignocellulosic biomass.

The invention also provides a method for synthesizing ethylene glycol, which comprises the step of converting a biomass raw material into ethylene glycol by using water as a solvent in the presence of the catalyst or the catalyst prepared by the preparation method in the invention and in an atmosphere of a mixed gas containing hydrogen and inert gas.

According to some embodiments, the biomass feedstock is selected from at least one of cellulose, starch, hemicellulose, and sugars. Cellulose may include cellulose from microcrystalline cellulose and lignocellulosic biomass.

According to some embodiments, the initial reaction gas pressure is 4-15MPa and the reaction temperature is 120-280 ℃.

According to some embodiments, the ratio of biomass feedstock to solvent water is (0.001-0.15):1, preferably (0.005-0.10): 1.

According to some embodiments, the inert gas is selected from at least one of nitrogen, helium, and argon.

According to some embodiments, the proportion of hydrogen in the gas mixture is between 10% and 100%, preferably between 50% and 100%, by volume.

According to some embodiments, the method for synthesizing ethylene glycol comprises the steps of putting a biomass raw material, the catalyst and water into a high-pressure reaction kettle, filling inert gas into the high-pressure reaction kettle for replacement after sealing, filling a mixed gas containing hydrogen and other inert gases at a certain pressure, wherein the initial reaction gas pressure is 4-15MPa, the reaction temperature is 120-280 ℃, and ethylene glycol is synthesized under the action of the catalyst.

In this application, room temperature generally refers to a temperature in the range of 20-30 ℃, e.g. 22-26 ℃.

For example, the reaction for synthesizing ethylene glycol comprises the following steps: adding a certain amount of reactants and a multifunctional catalyst into a 100mL high-pressure reaction kettle, adding a required amount of water, sealing the kettle, introducing inert gas for replacement, and filling gas containing hydrogen to a target pressure; heating to the target temperature, reacting for a certain time, and cooling after the reaction is finished. After the temperature is reduced to room temperature, the catalyst and the product are separated by vacuum filtration, the catalyst is washed for a plurality of times, and the filtrate is subjected to constant volume and then quantified. The liquid phase reaction product quantification was determined by high performance liquid chromatography (Waters Alliance e2695) and signal detection was done by differential Refractometer (RID). The chromatographic column used was a Phenomenex Rezex RCM-Monosaccharide column with water as the mobile phase, a flow rate of 0.6mL/min and a column temperature of 80 ℃.

In the invention, M-N-O solid acid loaded metal and tungsten trioxide catalyst are applied to the reaction for preparing the bio-based ethylene glycol, so that the conversion of the biomass raw material to the ethylene glycol is efficiently catalyzed. The M-N-O solid acid oxide used as a carrier in the invention has abundant B acid and L acid sites, and can increase the acidity of a solution and accelerate the conversion of reactants in the reaction process, so that the concentration of the reactants can be properly increased, or the reaction temperature can be reduced, or the reaction time can be shortened, and the conversion efficiency of the reaction can be improved. 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 novel green and environment-friendly process. The supported tungsten trioxide provides an active site for the trans-aldol condensation to break sugar and an intermediate C-C bond, and is an important component in the preparation of the ethylene glycol catalyst. Meanwhile, the supported multifunctional catalyst has high hydrothermal stability, good cyclic reaction performance, good economy and wide application prospect. When the multifunctional catalyst provided by the invention is used in the reaction of preparing ethylene glycol from cellulose, the conversion rate of the cellulose reaches 70.9% and the selectivity of the ethylene glycol is 39.5% under a higher cellulose concentration. The catalyst has good performance and stable circular reaction performance, and obtains good technical effect.

Detailed Description

The invention is further illustrated by the following examples, without restricting the inventive content to these examples.

Unless otherwise specified, each operation in examples and comparative examples was performed at room temperature.

The conversion of biomass and the selectivity and yield of ethylene glycol were calculated according to the following formula:

yield of ethylene glycol-biomass conversion x ethylene glycol selectivity

[ example 1 ]

Preparing Zr-Nb-O oxide solid acid by adopting a coprecipitation method, wherein Zr/Nb is 1/1 and is recorded as ZrO₂-Nb₂O₅(Zr/Nb ═ 1/1) (the same applies below):

5.345g of zirconyl nitrate dihydrate (ZrO (NO) was weighed out₃)₂·2h₂O) and 10.761g of niobium oxalate are dissolved in 50mL of deionized water, the mixture is uniformly mixed, ammonia water is added dropwise under vigorous stirring until the pH value is 10.0, and then the mixture is aged for 24 hours at room temperature; filtering the generated precipitate, washing with water to neutrality, drying at 120 deg.C for 12 hr, and calcining at 400 deg.C for 3 hr in air atmosphere to obtain ZrO₂-Nb₂O₅(Zr/Nb ═ 1/1) oxide solid acid.

Preparation of ZrO by dipping method₂-Nb₂O₅(Zr/Nb ═ 1/1) oxide-supported multifunctional catalyst, where the parts of Ni were 8.0 parts, tungsten trioxide were 30.0 parts, active carrier was 62.0 parts, and reported as catalyst a:

0.793g of nickel nitrate hexahydrate and 0.698g of ammonium metatungstate are dissolved in 3.0g of deionized water, the mixture is completely dissolved and uniformly mixed, 1.24g of the prepared active carrier is weighed, the mixture is shaken until the mixture is uniformly mixed, the mixture is dried at room temperature until most of water is evaporated, the mixture is continuously dried in an oven at 110 ℃ overnight, the mixture is roasted at 400 ℃ in the air atmosphere for 2 hours, and finally the mixture is reduced by hydrogen at 400 ℃ for 3 hours.

The reaction for preparing the glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle, 0.6g of catalyst is weighed to carry out the test of the reaction for preparing the glycol by the microcrystalline cellulose, wherein different H are considered₂Volume concentration, H₂The reaction performance was influenced by conditions such as pressure, temperature and cellulose amount, the reaction solution separated after the reaction was subjected to constant volume and the product was quantified by high performance liquid chromatography, and the conversion of cellulose and the selectivity and yield of ethylene glycol were calculated according to the above formula, and the results are shown in table 1.

TABLE 1

Wherein the reaction conditions were 40mL of water and 0.6g of catalyst A, and the reaction was carried out for 30 min.

[ example 2 ]

ZrO₂-Nb₂O₅The (Zr/Nb ═ 1/1) oxide solid acid was prepared in the same manner as in example 1.

ZrO₂-Nb₂O₅(Zr/Nb ═ 1/1) oxide-supported multifunctional catalyst, where the parts of Ni were 8.0 parts, tungsten trioxide were 5.0 parts, the parts of active carrier were 87.0 parts, and reported as catalyst B: the preparation method comprises the following steps: dissolving 0.793g of nickel nitrate hexahydrate and 0.116g of ammonium metatungstate in 3.0g of deionized water, mixing uniformly after completely dissolving, weighing 1.74g of the prepared active carrier, shaking until uniformly mixing,drying at room temperature until most of water is evaporated, continuing to dry in an oven at 110 ℃ overnight, then roasting at 400 ℃ for 2h in an air atmosphere, and finally reducing with hydrogen at 400 ℃ for 3 h.

The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle, 2.0g of microcrystalline cellulose and 0.6g of catalyst B are weighed and added into a high-pressure reaction kettle (100mL) filled with 40mL of water, the reaction kettle is closed, then nitrogen is introduced for replacement for three times, and H is filled₂/N₂(80/20) the mixed gas is heated to 240 ℃ to 8MPa, and the reaction is carried out for 30 min.

After the reaction, the temperature was decreased, and the solid and the reaction solution (reaction product) were separated by filtration, and the quantitative method of the reaction was the same as in example 1, and the results are shown in Table 2.

[ example 3 ]

ZrO₂-Nb₂O₅The (Zr/Nb ═ 1/1) oxide solid acid was prepared in the same manner as in example 1.

ZrO₂-Nb₂O₅(Zr/Nb ═ 1/1) oxide supported multifunctional catalyst, where the parts of Ni were 8.0 parts, tungsten trioxide 15.0 parts, active support 77.0 parts, noted catalyst C, prepared by impregnation: 0.793g of nickel nitrate hexahydrate and 0.349g of ammonium metatungstate are dissolved in 3.0g of deionized water, the mixture is completely dissolved and uniformly mixed, 1.54g of the prepared active carrier is weighed, the mixture is shaken until the mixture is uniformly mixed, the mixture is dried at room temperature until most of water is evaporated, the mixture is continuously dried in an oven at 110 ℃ overnight, the mixture is roasted at 400 ℃ for 2 hours in an air atmosphere, and finally the mixture is reduced by hydrogen at 400 ℃ for 3 hours.

The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle, 2.0g of microcrystalline cellulose and 0.6g of catalyst C are weighed and added into a high-pressure reaction kettle (100mL) filled with 40mL of water, the reaction kettle is closed, then nitrogen is introduced for replacement for three times, and H is filled₂/N₂(80/20) the mixed gas is heated to 240 ℃ to 8MPa, and the reaction is carried out for 30 min.

After the reaction, the temperature was decreased, and the solid and the reaction solution (reaction product) were separated by filtration, and the quantitative method of the reaction was the same as in example 1, and the results are shown in Table 2.

[ example 4 ]

ZrO₂-Nb₂O₅The (Zr/Nb ═ 1/1) oxide solid acid was prepared in the same manner as in example 1.

ZrO₂-Nb₂O₅(Zr/Nb ═ 1/1) oxide supported multifunctional catalyst, where the parts of Ni was 8.0 parts, tungsten trioxide was 40.0 parts, active carrier was 52.0 parts, noted catalyst D, prepared by impregnation: 0.793g of nickel nitrate hexahydrate and 0.930g of ammonium metatungstate are dissolved in 3.0g of deionized water, the mixture is completely dissolved and uniformly mixed, 1.24g of the prepared active carrier is weighed, the mixture is shaken until the mixture is uniformly mixed, the mixture is dried at room temperature until most of water is evaporated, the mixture is continuously dried in an oven at 110 ℃ overnight, then the mixture is roasted at 400 ℃ for 2 hours in an air atmosphere, and finally the mixture is reduced by hydrogen at 400 ℃ for 3 hours.

The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle, 2.0g of microcrystalline cellulose and 0.6g of catalyst D are weighed and added into a high-pressure reaction kettle (100mL) filled with 40mL of water, the reaction kettle is closed, then nitrogen is introduced for replacement for three times, and H is filled₂/N₂(80/20) the mixed gas is heated to 240 ℃ to 8MPa, and the reaction is carried out for 30 min.

After the reaction, the temperature was decreased, and the solid and the reaction solution (reaction product) were separated by filtration, and the quantitative method of the reaction was the same as in example 1, and the results are shown in Table 2.

[ example 5 ]

ZrO₂-Nb₂O₅The (Zr/Nb ═ 1/9) oxide solid acid was prepared by a coprecipitation method: 1.069g zirconyl nitrate dihydrate (ZrO (NO) was weighed out₃)₂·2h₂O) and 19.369g of niobium oxalate are dissolved in 50mL of deionized water, the mixture is uniformly mixed, ammonia water is added dropwise under vigorous stirring until the pH value is 10.0, and then the mixture is aged for 24 hours at room temperature; filtering the generated precipitate, washing with water to neutrality, drying at 120 deg.C for 12 hr, and calcining at 400 deg.C for 3 hr in air atmosphere to obtain ZrO₂-Nb₂O₅(Zr/Nb ═ 1/9) oxide solid acid.

ZrO₂-Nb₂O₅(Zr/Nb. 1/9) oxide supported multifunctional catalyst wherein8.0 parts of Ni, 30.0 parts of tungsten trioxide and 62.0 parts of active carrier, and is marked as catalyst E, and the catalyst is prepared by an impregnation method: 0.793g of nickel nitrate hexahydrate and 0.698g of ammonium metatungstate are dissolved in 3.0g of deionized water, the mixture is completely dissolved and uniformly mixed, 1.24g of the prepared active carrier is weighed, the mixture is shaken until the mixture is uniformly mixed, the mixture is dried at room temperature until most of water is evaporated, the mixture is continuously dried in an oven at 110 ℃ overnight, the mixture is roasted at 400 ℃ in the air atmosphere for 2 hours, and finally the mixture is reduced by hydrogen at 400 ℃ for 3 hours.

The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle, 2.0g of microcrystalline cellulose and 0.6g of catalyst E are weighed and added into a high-pressure reaction kettle (100mL) filled with 40mL of water, the reaction kettle is closed, then nitrogen is introduced for replacement for three times, and H is filled₂/N₂(80/20) the mixed gas is heated to 240 ℃ to 8MPa, and the reaction is carried out for 30 min.

After the reaction, the temperature was decreased, and the solid and the reaction solution (reaction product) were separated by filtration, and the quantitative method of the reaction was the same as in example 1, and the results are shown in Table 2.

[ example 6 ]

ZrO₂-Nb₂O₅The (Zr/Nb ═ 3/7) oxide solid acid was prepared by a coprecipitation method: 3.207g of zirconyl nitrate dihydrate (ZrO (NO) was weighed out₃)₂·2h₂O) and 15.065g of niobium oxalate are dissolved in 50mL of deionized water, the mixture is uniformly mixed, ammonia water is added dropwise under vigorous stirring until the pH value is 10.0, and then the mixture is aged for 24 hours at room temperature; filtering the generated precipitate, washing with water to neutrality, drying at 120 deg.C for 12 hr, and calcining at 400 deg.C for 3 hr in air atmosphere to obtain ZrO₂-Nb₂O₅(Zr/Nb ═ 3/7) oxide solid acid.

ZrO₂-Nb₂O₅(Zr/Nb ═ 3/7) oxide supported multifunctional catalyst, where the parts of Ni was 8.0 parts, tungsten trioxide was 30.0 parts, and the parts of active carrier was 62.0 parts, noted catalyst F, prepared by impregnation: dissolving 0.793g of nickel nitrate hexahydrate and 0.698g of ammonium metatungstate in 3.0g of deionized water, mixing uniformly after completely dissolving, weighing 1.24g of the prepared active carrier, and shaking until mixingAnd (3) homogenizing, drying at room temperature until most of water is evaporated, continuing to dry in an oven at 110 ℃ overnight, then roasting at 400 ℃ for 2h in an air atmosphere, and finally reducing with hydrogen at 400 ℃ for 3 h.

The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle, 2.0g of microcrystalline cellulose and 0.6g of catalyst F are weighed and added into a high-pressure reaction kettle (100mL) filled with 40mL of water, the reaction kettle is closed, then nitrogen is introduced for replacement for three times, and H is filled₂/N₂(80/20) the mixed gas is heated to 240 ℃ to 8MPa, and the reaction is carried out for 30 min.

After the reaction, the temperature was decreased, and the solid and the reaction solution (reaction product) were separated by filtration, and the quantitative method of the reaction was the same as in example 1, and the results are shown in Table 2.

[ example 7 ]

ZrO₂-Nb₂O₅The (Zr/Nb ═ 7/3) oxide solid acid was prepared by a coprecipitation method: 7.483g of zirconyl nitrate dihydrate (ZrO (NO) was weighed out₃)₂·2h₂O) and 6.456g niobium oxalate are dissolved in 50mL deionized water, the mixture is uniformly mixed, ammonia water is added dropwise under vigorous stirring until the pH value is 10.0, and then the mixture is aged for 24 hours at room temperature; filtering the generated precipitate, washing with water to neutrality, drying at 120 deg.C for 12 hr, and calcining at 400 deg.C for 3 hr in air atmosphere to obtain ZrO₂-Nb₂O₅(Zr/Nb ═ 7/3) oxide solid acid.

ZrO₂-Nb₂O₅(Zr/Nb ═ 7/3) oxide supported multifunctional catalyst, where the parts of Ni was 8.0 parts, tungsten trioxide was 30.0 parts, and the parts of active carrier was 62.0 parts, noted as catalyst G, prepared by impregnation: 0.793g of nickel nitrate hexahydrate and 0.698g of ammonium metatungstate are dissolved in 3.0g of deionized water, the mixture is completely dissolved and uniformly mixed, 1.24g of the prepared active carrier is weighed, the mixture is shaken until the mixture is uniformly mixed, the mixture is dried at room temperature until most of water is evaporated, the mixture is continuously dried in an oven at 110 ℃ overnight, the mixture is roasted at 400 ℃ in the air atmosphere for 2 hours, and finally the mixture is reduced by hydrogen at 400 ℃ for 3 hours.

The reaction for preparing the glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle and is calledAdding 2.0G microcrystalline cellulose and 0.6G catalyst G into a high-pressure reaction kettle (100mL) filled with 40mL water, sealing the reaction kettle, introducing nitrogen for three times for replacement, and filling H₂/N₂(80/20) the mixed gas is heated to 240 ℃ to 8MPa, and the reaction is carried out for 30 min.

After the reaction, the temperature was decreased, and the solid and the reaction solution (reaction product) were separated by filtration, and the quantitative method of the reaction was the same as in example 1, and the results are shown in Table 2.

[ example 8 ]

ZrO₂-Nb₂O₅The (Zr/Nb ═ 9/1) oxide solid acid was prepared by a coprecipitation method: 9.621g of zirconyl nitrate dihydrate (ZrO (NO) was weighed out₃)₂·2h₂O) and 2.152g of niobium oxalate are dissolved in 50mL of deionized water, the mixture is uniformly mixed, ammonia water is added dropwise under vigorous stirring until the pH value is 10.0, and then the mixture is aged for 24 hours at room temperature; filtering the generated precipitate, washing with water to neutrality, drying at 120 deg.C for 12 hr, and calcining at 400 deg.C for 3 hr in air atmosphere to obtain ZrO₂-Nb₂O₅(Zr/Nb ═ 9/1) oxide solid acid.

ZrO₂-Nb₂O₅(Zr/Nb ═ 9/1) oxide supported multifunctional catalyst, where the parts of Ni was 8.0 parts, tungsten trioxide was 30.0 parts, and the parts of active carrier was 62.0 parts, noted as catalyst H, prepared by impregnation: 0.793g of nickel nitrate hexahydrate and 0.698g of ammonium metatungstate are dissolved in 3.0g of deionized water, the mixture is completely dissolved and uniformly mixed, 1.24g of the prepared active carrier is weighed, the mixture is shaken until the mixture is uniformly mixed, the mixture is dried at room temperature until most of water is evaporated, the mixture is continuously dried in an oven at 110 ℃ overnight, the mixture is roasted at 400 ℃ in the air atmosphere for 2 hours, and finally the mixture is reduced by hydrogen at 400 ℃ for 3 hours.

The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle, 2.0g of microcrystalline cellulose and 0.6g of catalyst H are weighed and added into a high-pressure reaction kettle (100mL) filled with 40mL of water, the reaction kettle is closed, then nitrogen is introduced for replacement for three times, and H is filled₂/N₂(80/20) the mixed gas is heated to 240 ℃ to 8MPa, and the reaction is carried out for 30 min.

After the reaction, the temperature was decreased, and the solid and the reaction solution (reaction product) were separated by filtration, and the quantitative method of the reaction was the same as in example 1, and the results are shown in Table 2.

[ example 9 ]

TiO₂-Nb₂O₅(Ti/Nb ═ 1/1) oxide solid acid was prepared by coprecipitation method: 4.800g of titanium sulfate and 10.761g of niobium oxalate are weighed and dissolved in 50mL of deionized water, the mixture is uniformly mixed, ammonia water is added dropwise under vigorous stirring until the pH value is 10.0, and then the mixture is aged for 24 hours at room temperature; filtering the generated precipitate, washing with water to neutrality, drying at 120 deg.C for 12 hr, and calcining at 400 deg.C in air atmosphere for 3 hr to obtain TiO₂-Nb₂O₅(Ti/Nb 1/1) oxide solid acid.

TiO₂-Nb₂O₅(Ti/Nb 1/1) oxide supported multifunctional catalyst, where the parts of Ni is 8.0 parts, tungsten trioxide is 30.0 parts, active carrier is 62.0 parts, noted as catalyst I, prepared by impregnation: 0.793g of nickel nitrate hexahydrate and 0.698g of ammonium metatungstate are dissolved in 3.0g of deionized water, the mixture is completely dissolved and uniformly mixed, 1.24g of the prepared active carrier is weighed, the mixture is shaken until the mixture is uniformly mixed, the mixture is dried at room temperature until most of water is evaporated, the mixture is continuously dried in an oven at 110 ℃ overnight, the mixture is roasted at 400 ℃ in the air atmosphere for 2 hours, and finally the mixture is reduced by hydrogen at 400 ℃ for 3 hours.

The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle, 2.0g of microcrystalline cellulose and 0.6g of catalyst I are weighed and added into a high-pressure reaction kettle (100mL) filled with 40mL of water, the reaction kettle is closed, then nitrogen is introduced for replacement for three times, and H is filled₂/N₂(80/20) the mixed gas is heated to 240 ℃ to 8MPa, and the reaction is carried out for 30 min.

After the reaction, the temperature was decreased, and the solid and the reaction solution (reaction product) were separated by filtration, and the quantitative method of the reaction was the same as in example 1, and the results are shown in Table 2.

[ example 10 ]

ZrO₂-TiO₂-Nb₂O₅(Zr/Ti/Nb ═ 0.5/0.5/1) oxide solid acid was prepared by a coprecipitation method: 2.673g of zirconyl nitrate dihydrate, 2.400g of titanium sulfate and10.761g of niobium oxalate is dissolved in 50mL of deionized water, the mixture is uniformly mixed, ammonia water is added dropwise under vigorous stirring until the pH value is 10.0, and then the mixture is aged for 24 hours at room temperature; filtering the generated precipitate, washing with water to neutrality, drying at 120 deg.C for 12 hr, and calcining at 400 deg.C for 3 hr in air atmosphere to obtain ZrO₂-TiO₂-Nb₂O₅(Zr/Ti/Nb ═ 0.5/0.5/1) oxide solid acid.

ZrO₂-TiO₂-Nb₂O₅(Zr/Ti/Nb ═ 0.5/0.5/1) oxide supported multifunctional catalyst, where the parts of Ni 8.0 parts, tungsten trioxide 30.0 parts, active support 62.0 parts, noted catalyst J, prepared by impregnation: 0.793g of nickel nitrate hexahydrate and 0.698g of ammonium metatungstate are dissolved in 3.0g of deionized water, the mixture is completely dissolved and uniformly mixed, 1.24g of the prepared active carrier is weighed, the mixture is shaken until the mixture is uniformly mixed, the mixture is dried at room temperature until most of water is evaporated, the mixture is continuously dried in an oven at 110 ℃ overnight, the mixture is roasted at 400 ℃ in the air atmosphere for 2 hours, and finally the mixture is reduced by hydrogen at 400 ℃ for 3 hours.

The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle, 2.0g of microcrystalline cellulose and 0.6g of catalyst J are weighed and added into a high-pressure reaction kettle (100mL) filled with 40mL of water, the reaction kettle is closed, then nitrogen is introduced for replacement for three times, and H is filled₂/N₂(80/20) the mixed gas is heated to 240 ℃ to 8MPa, and the reaction is carried out for 30 min.

After the reaction, the temperature was decreased, and the solid and the reaction solution (reaction product) were separated by filtration, and the quantitative method of the reaction was the same as in example 1, and the results are shown in Table 2.

[ example 11 ]

ZrO₂-Ta₂O₅The (Zr/Ta ═ 1/1) oxide solid acid was prepared by a coprecipitation method: weighing 5.345g of zirconyl nitrate dihydrate and 12.521g of tantalum oxalate, dissolving the zirconyl nitrate dihydrate and the 12.521g of tantalum oxalate in 50mL of deionized water, uniformly mixing, dropwise adding ammonia water under vigorous stirring until the pH value is 10.0, and then aging for 24 hours at room temperature; filtering the generated precipitate, washing with water to neutrality, drying at 120 deg.C for 12 hr, and calcining at 400 deg.C for 3 hr in air atmosphere to obtain ZrO₂-Ta₂O₅(Zr/Ta ═ 1/1) oxide solid acid.

ZrO₂-Ta₂O₅(Zr/Ta-1/1) oxide supported multifunctional catalyst, where the parts of Ni is 8.0 parts, tungsten trioxide is 30.0 parts, active carrier is 62.0 parts, and it is denoted as catalyst K, prepared by impregnation: 0.793g of nickel nitrate hexahydrate and 0.698g of ammonium metatungstate are dissolved in 3.0g of deionized water, the mixture is completely dissolved and uniformly mixed, 1.24g of the prepared active carrier is weighed, the mixture is shaken until the mixture is uniformly mixed, the mixture is dried at room temperature until most of water is evaporated, the mixture is continuously dried in an oven at 110 ℃ overnight, the mixture is roasted at 400 ℃ in the air atmosphere for 2 hours, and finally the mixture is reduced by hydrogen at 400 ℃ for 3 hours.

The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle, 2.0g of microcrystalline cellulose and 0.6g of catalyst K are weighed and added into a high-pressure reaction kettle (100mL) filled with 40mL of water, the reaction kettle is closed, then nitrogen is introduced for replacement for three times, and H is filled₂/N₂(80/20) the mixed gas is heated to 240 ℃ to 8MPa, and the reaction is carried out for 30 min.

After the reaction, the temperature was decreased, and the solid and the reaction solution (reaction product) were separated by filtration, and the quantitative method of the reaction was the same as in example 1, and the results are shown in Table 2.

[ example 12 ]

ZrO₂-Nb₂O₅-Ta₂O₅The (Zr/Nb/Ta 1/0.5/0.5) oxide solid acid is prepared by adopting a coprecipitation method: weighing 5.345g of zirconyl nitrate dihydrate, 5.380g of niobium oxalate and 6.260g of tantalum oxalate, dissolving in 50mL of deionized water, uniformly mixing, dropwise adding ammonia water under vigorous stirring until the pH value is 10.0, and then aging for 24h at room temperature; filtering the generated precipitate, washing with water to neutrality, drying at 120 deg.C for 12 hr, and calcining at 400 deg.C for 3 hr in air atmosphere to obtain ZrO₂-Nb₂O₅-Ta₂O₅(Zr/Nb/Ta ═ 1/0.5/0.5) oxide solid acid.

ZrO₂-Nb₂O₅-Ta₂O₅(Zr/Nb/Ta 1/0.5/0.5) oxide-supported multifunctional catalyst, wherein the part of Ni is 8.0 parts, and the part of tungsten trioxide is 30 parts0 parts, 62.0 parts of active carrier, denoted as catalyst L, prepared by impregnation: 0.793g of nickel nitrate hexahydrate and 0.698g of ammonium metatungstate are dissolved in 3.0g of deionized water, the mixture is completely dissolved and uniformly mixed, 1.24g of the prepared active carrier is weighed, the mixture is shaken until the mixture is uniformly mixed, the mixture is dried at room temperature until most of water is evaporated, the mixture is continuously dried in an oven at 110 ℃ overnight, the mixture is roasted at 400 ℃ in the air atmosphere for 2 hours, and finally the mixture is reduced by hydrogen at 400 ℃ for 3 hours.

The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle, 2.0g of microcrystalline cellulose and 0.6g of catalyst L are weighed and added into a high-pressure reaction kettle (100mL) filled with 40mL of water, the reaction kettle is closed, then nitrogen is introduced for replacement for three times, and H is filled₂/N₂(80/20) the mixed gas is heated to 240 ℃ to 8MPa, and the reaction is carried out for 30 min.

After the reaction, the temperature was decreased, and the solid and the reaction solution (reaction product) were separated by filtration, and the quantitative method of the reaction was the same as in example 1, and the results are shown in Table 2.

[ example 13 ]

ZrO₂-TiO₂-Nb₂O₅-Ta₂O₅(Zr/Ti/Nb/Ta ═ 0.5/0.5/0.5/0.5) oxide solid acid was prepared by coprecipitation method: 2.673g of zirconyl nitrate dihydrate, 2.400g of titanium sulfate, 5.380g of niobium oxalate and 6.260g of tantalum oxalate are weighed and dissolved in 50mL of deionized water, the mixture is uniformly mixed, ammonia water is added dropwise under vigorous stirring until the pH value is 10.0, and then the mixture is aged for 24 hours at room temperature; filtering the generated precipitate, washing with water to neutrality, drying at 120 deg.C for 12 hr, and calcining at 400 deg.C for 3 hr in air atmosphere to obtain ZrO₂-TiO₂-Nb₂O₅-Ta₂O₅(Zr/Ti/Nb/Ta ═ 0.5/0.5/0.5/0.5) oxide solid acid.

ZrO₂-TiO₂-Nb₂O₅-Ta₂O₅(Zr/Ti/Nb/Ta ═ 0.5/0.5/0.5/0.5) oxide supported multifunctional catalyst, where the parts of Ni 8.0, tungsten trioxide 30.0, active carrier 62.0, noted as catalyst M, prepared by impregnation: 0.793g of nickel nitrate hexahydrate and 0.698g of metatungstenDissolving ammonium sulfate in 3.0g of deionized water, completely dissolving, uniformly mixing, weighing 1.24g of the prepared active carrier, shaking until the mixture is uniformly mixed, drying at room temperature until most of water is evaporated, continuously drying in an oven at 110 ℃ overnight, roasting at 400 ℃ in an air atmosphere for 2 hours, and finally reducing with hydrogen at 400 ℃ for 3 hours.

The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle, 2.0g of microcrystalline cellulose and 0.6g of catalyst M are weighed and added into a high-pressure reaction kettle (100mL) filled with 40mL of water, the reaction kettle is closed, then nitrogen is introduced for replacement for three times, and H is filled₂/N₂(80/20) the mixed gas is heated to 240 ℃ to 8MPa, and the reaction is carried out for 30 min.

After the reaction, the temperature was decreased, and the solid and the reaction solution (reaction product) were separated by filtration, and the quantitative method of the reaction was the same as in example 1, and the results are shown in Table 2.

[ example 14 ]

ZrO₂-TiO₂-Nb₂O₅-Ta₂O₅(Zr/Ti/Nb/Ta 0.5/0.5/0.5/0.5) oxide solid acid preparation method same as example 13.

ZrO₂-TiO₂-Nb₂O₅-Ta₂O₅(Zr/Ti/Nb/Ta ═ 0.5/0.5/0.5/0.5) oxide supported multifunctional catalyst, where the parts of Ni 30.0, tungsten trioxide 30.0, active carrier 40.0, noted as catalyst N, prepared by impregnation: dissolving 2.973g of nickel nitrate hexahydrate and 0.698g of ammonium metatungstate in 1.0g of deionized water, completely dissolving and uniformly mixing, weighing 0.8g of the prepared active carrier, shaking until the active carrier is uniformly mixed, drying at room temperature until most of water is evaporated, continuously drying in an oven at 110 ℃ overnight, then roasting at 400 ℃ in an air atmosphere for 2 hours, and finally reducing with hydrogen at 400 ℃ for 3 hours.

The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle, 2.0g of microcrystalline cellulose and 0.6g of catalyst N are weighed and added into a high-pressure reaction kettle (100mL) filled with 40mL of water, the reaction kettle is closed, then nitrogen is introduced for replacement for three times, and H is filled₂/N₂(80/20) the mixed gas is heated to 240 ℃ to 8MPa, and the reaction is carried out for 30 min.

After the reaction, the temperature was decreased, and the solid and the reaction solution (reaction product) were separated by filtration, and the quantitative method of the reaction was the same as in example 1, and the results are shown in Table 2.

[ example 15 ]

ZrO₂-TiO₂-Nb₂O₅-Ta₂O₅(Zr/Ti/Nb/Ta 0.5/0.5/0.5/0.5) oxide solid acid preparation method same as example 13.

ZrO₂-TiO₂-Nb₂O₅-Ta₂O₅(Zr/Ti/Nb/Ta ═ 0.5/0.5/0.5/0.5) oxide supported multifunctional catalyst, where Ru is 0.1 parts, tungsten trioxide is 30.0 parts, active carrier is 69.9 parts, noted as catalyst O, prepared by impregnation: 0.40mL of 0.0732mol/L RuCl was taken₃The aqueous solution and 1.033g of ammonium metatungstate, then 3.5g of deionized water are added, the mixture is vibrated evenly, 2.070g of the prepared active carrier is weighed, the mixture is vibrated till the mixture is mixed evenly, the mixture is dried at room temperature until most of water is evaporated, the mixture is continuously dried in an oven at 110 ℃ overnight, then the mixture is roasted for 2 hours at 400 ℃ in the air atmosphere, and finally the mixture is reduced for 3 hours at 400 ℃ by hydrogen.

The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle, 2.0g of microcrystalline cellulose and 0.6g of catalyst O are weighed and added into a high-pressure reaction kettle (100mL) filled with 40mL of water, the reaction kettle is closed, then nitrogen is introduced for replacement for three times, and H is filled₂/N₂(80/20) the mixed gas is heated to 240 ℃ to 8MPa, and the reaction is carried out for 30 min.

After the reaction, the temperature was decreased, and the solid and the reaction solution (reaction product) were separated by filtration, and the quantitative method of the reaction was the same as in example 1, and the results are shown in Table 2.

[ example 16 ]

ZrO₂-TiO₂-Nb₂O₅-Ta₂O₅(Zr/Ti/Nb/Ta 0.5/0.5/0.5/0.5) oxide solid acid preparation method same as example 13.

ZrO₂-TiO₂-Nb₂O₅-Ta₂O₅(Zr/Ti/Nb/Ta ═ 0.5/0.5/0.5/0.5) oxide supported multifunctional catalyst, where Pt parts are 0.4 parts, tungsten trioxide parts are 30.0 parts, active carrier parts are 69.6 parts, noted as catalyst P, prepared by impregnation: taking 1.60mL of 0.0386mol/L H₂PtCl₆The aqueous solution and 1.051g ammonium metatungstate are added with 2.5g deionized water, the mixture is mixed evenly, 2.096g of the active carrier prepared above is weighed, the mixture is shaken until the mixture is mixed evenly, the mixture is dried at room temperature until most of water is evaporated, the mixture is continuously dried in an oven at 110 ℃ overnight, then the mixture is roasted for 2h at 400 ℃ in air atmosphere, and finally the mixture is reduced for 3h with hydrogen at 400 ℃.

The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle, 2.0g of microcrystalline cellulose and 0.6g of catalyst P are weighed and added into a high-pressure reaction kettle (100mL) filled with 40mL of water, the reaction kettle is closed, then nitrogen is introduced for replacement for three times, and H is filled₂/N₂(80/20) the mixed gas is heated to 240 ℃ to 8MPa, and the reaction is carried out for 30 min.

After the reaction, the temperature was decreased, and the solid and the reaction solution (reaction product) were separated by filtration, and the quantitative method of the reaction was the same as in example 1, and the results are shown in Table 2.

[ example 17 ]

ZrO₂-TiO₂-Nb₂O₅-Ta₂O₅(Zr/Ti/Nb/Ta 0.5/0.5/0.5/0.5) oxide solid acid preparation method same as example 13.

ZrO₂-TiO₂-Nb₂O₅-Ta₂O₅(Zr/Ti/Nb/Ta ═ 0.5/0.5/0.5/0.5) oxide supported multifunctional catalyst, where Pd parts are 0.4 parts, Au parts are 0.6 parts, tungsten trioxide parts are 30.0 parts, active carrier parts are 69 parts, and it is prepared by impregnation: 0.020g of PdCl was taken₂Is dissolved in 1.5g of aqueous hydrochloric acid, and 3.65mL of 0.0249mol/L HAuCl is taken₄Dissolving and mixing the aqueous solution and 1.047g of ammonium metatungstate uniformly, weighing 2.07g of the active carrier prepared above, shaking until the mixture is uniformly mixed, drying at room temperature until most of water is evaporated, continuing to dry in an oven at 110 ℃ overnight, and then drying in airRoasting at 400 deg.C for 2h under atmosphere, and reducing with hydrogen at 400 deg.C for 3 h.

The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle, 2.0g of microcrystalline cellulose and 0.6g of catalyst Q are weighed and added into a high-pressure reaction kettle (100mL) filled with 40mL of water, the reaction kettle is closed, then nitrogen is introduced for replacement for three times, and H is filled₂/N₂(80/20) the mixed gas is heated to 240 ℃ to 8MPa, and the reaction is carried out for 30 min.

After the reaction, the temperature was decreased, and the solid and the reaction solution (reaction product) were separated by filtration, and the quantitative method of the reaction was the same as in example 1, and the results are shown in Table 2.

[ example 18 ]

ZrO₂-TiO₂-Nb₂O₅-Ta₂O₅(Zr/Ti/Nb/Ta 0.5/0.5/0.5/0.5) oxide solid acid preparation method same as example 13.

ZrO₂-TiO₂-Nb₂O₅-Ta₂O₅(Zr/Ti/Nb/Ta is 0.5/0.5/0.5/0.5) oxide-supported multifunctional catalyst, wherein the weight part of Cu is 8.0 parts, the weight part of tungsten trioxide is 30.0 parts, the weight part of active carrier is 62 parts, and the catalyst is marked as catalyst R and is prepared by adopting an impregnation method: dissolving 0.608g of copper nitrate trihydrate and 0.698g of ammonium metatungstate in 3.0g of deionized water, completely dissolving, dissolving and uniformly mixing, weighing 1.24g of the prepared active carrier, shaking until the active carrier is uniformly mixed, drying at room temperature until most of water is evaporated, continuing to dry in an oven at 110 ℃ overnight, then roasting at 400 ℃ in an air atmosphere for 2 hours, and finally reducing with hydrogen at 400 ℃ for 3 hours.

The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle, 2.0g of microcrystalline cellulose and 0.6g of catalyst R are weighed and added into a high-pressure reaction kettle (100mL) filled with 40mL of water, the reaction kettle is closed, then nitrogen is introduced for replacement for three times, and H is filled₂/N₂(80/20) the mixed gas is heated to 240 ℃ to 8MPa, and the reaction is carried out for 30 min.

After the reaction, the temperature was decreased, and the solid and the reaction solution (reaction product) were separated by filtration, and the quantitative method of the reaction was the same as in example 1, and the results are shown in Table 2.

[ example 19 ]

ZrO₂-TiO₂-Nb₂O₅-Ta₂O₅(Zr/Ti/Nb/Ta 0.5/0.5/0.5/0.5) oxide solid acid preparation method same as example 13.

ZrO₂-TiO₂-Nb₂O₅-Ta₂O₅(Zr/Ti/Nb/Ta ═ 0.5/0.5/0.5/0.5) oxide-supported multifunctional catalyst, where Ru is 0.025 parts, Ni is 6.0 parts, tungsten trioxide is 30.0 parts, active carrier is 63.975 parts, and it is prepared by impregnation: 0.10mL of 0.0732mol/L RuCl was taken₃Adding 3.5g of deionized water, uniformly shaking, weighing 1.893g of the prepared active carrier, uniformly shaking, drying at room temperature until most of water is evaporated, continuously drying in an oven at 110 ℃ overnight, roasting at 400 ℃ in an air atmosphere for 2 hours, and finally reducing with hydrogen at 400 ℃ for 3 hours.

The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle, 2.0g of microcrystalline cellulose and 0.6g of catalyst S are weighed and added into a high-pressure reaction kettle (100mL) filled with 40mL of water, the reaction kettle is closed, then nitrogen is introduced for replacement for three times, and H is filled₂/N₂(80/20) the mixed gas is heated to 240 ℃ to 8MPa, and the reaction is carried out for 30 min.

After the reaction, the temperature was decreased, and the solid and the reaction solution (reaction product) were separated by filtration, and the quantitative method of the reaction was the same as in example 1, and the results are shown in Table 2.

Comparative example 1

ZrO₂-TiO₂-Nb₂O₅-Ta₂O₅(Zr/Ti/Nb/Ta 0.5/0.5/0.5/0.5) oxide solid acid preparation method same as example 13.

The reaction for preparing the glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle, and 2.0g of microcrystalline cellulose and 0.6g of ZrO are weighed₂-TiO₂-Nb₂O₅-Ta₂O₅(Zr/Nb/Ta 0.5/0.5/0.5) oxide solid acid was added to a solution containing 40mL of waterThe autoclave (100mL) was sealed, then purged with nitrogen three times, and then charged with H₂/N₂(80/20) the mixed gas is heated to 240 ℃ to 8MPa, and the reaction is carried out for 30 min.

After the reaction, the temperature was decreased, and the solid and the reaction solution (reaction product) were separated by filtration, and the quantitative method of the reaction was the same as in example 1, and the results are shown in Table 2.

Comparative example 2

ZrO₂-TiO₂-Nb₂O₅-Ta₂O₅(Zr/Ti/Nb/Ta 0.5/0.5/0.5/0.5) oxide solid acid preparation method same as example 13.

ZrO₂-TiO₂-Nb₂O₅-Ta₂O₅(Zr/Ti/Nb/Ta ═ 0.5/0.5/0.5/0.5) tungsten trioxide catalyst supported by solid acid oxide, where the parts of tungsten trioxide is 30.0 parts and the parts of active carrier is 70.0 parts, and is denoted as catalyst T, and it is prepared by impregnation method: dissolving 0.698g of ammonium metatungstate in 3.0g of deionized water, completely dissolving, uniformly mixing, weighing 1.4g of the active carrier, shaking until the active carrier is uniformly mixed, drying at room temperature until most of water is evaporated, continuously drying in an oven at 110 ℃ overnight, roasting at 400 ℃ in an air atmosphere for 2 hours, and finally reducing with hydrogen at 400 ℃ for 3 hours.

The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle, 2.0g of microcrystalline cellulose and 0.6g of catalyst T are weighed and added into a high-pressure reaction kettle (100mL) filled with 40mL of water, the reaction kettle is closed, then nitrogen is introduced for replacement for three times, and H is filled₂/N₂(80/20) the mixed gas is heated to 240 ℃ to 8MPa, and the reaction is carried out for 30 min.

After the reaction, the temperature was decreased, and the solid and the reaction solution (reaction product) were separated by filtration, and the quantitative method of the reaction was the same as in example 1, and the results are shown in Table 2.

Comparative example 3

ZrO₂The preparation method comprises the following steps: weighing 10.690g of zirconyl nitrate dihydrate, dissolving in 50mL of deionized water, uniformly mixing, dropwise adding ammonia water under vigorous stirring until the pH value is 10.0, and then aging for 24h at room temperature; the precipitate formedFiltering, washing with water to neutrality, drying at 120 deg.C for 12 hr, and calcining at 400 deg.C in air atmosphere for 3 hr to obtain ZrO₂An oxide.

ZrO₂The multifunctional catalyst is oxide supported catalyst with Ni in 8.0 weight portions, tungsten trioxide in 30.0 weight portions and carrier ZrO₂The part of oxide is 62.0 parts, and is marked as catalyst U, and the catalyst is prepared by an impregnation method: 0.793g of nickel nitrate hexahydrate and 0.698g of ammonium metatungstate are dissolved in 3.0g of deionized water, the mixture is completely dissolved and uniformly mixed, 1.24g of the prepared carrier is weighed, the carrier is shaken until the mixture is uniformly mixed, the carrier is dried at room temperature until most of water is evaporated, the carrier is continuously dried in an oven at 110 ℃ overnight, the carrier is roasted at 400 ℃ in the air atmosphere for 2 hours, and finally the carrier is reduced by hydrogen at 400 ℃ for 3 hours.

The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle, 2.0g of microcrystalline cellulose and 0.6g of catalyst U are weighed and added into a high-pressure reaction kettle (100mL) filled with 40mL of water, the reaction kettle is closed, then nitrogen is introduced for replacement for three times, and H is filled₂/N₂(80/20) the mixed gas is heated to 240 ℃ to 8MPa, and the reaction is carried out for 30 min.

After the reaction, the temperature was decreased, and the solid and the reaction solution (reaction product) were separated by filtration, and the quantitative method of the reaction was the same as in example 1, and the results are shown in Table 2.

Comparative example 4

Nb₂O₅The preparation method comprises the following steps: weighing 20.522g of niobium oxalate, dissolving the niobium oxalate in 50mL of deionized water, uniformly mixing, dropwise adding ammonia water under vigorous stirring until the pH value is 10.0, and then aging for 24 hours at room temperature; filtering the generated precipitate, washing with water to neutrality, drying at 120 deg.C for 12 hr, and calcining at 400 deg.C in air atmosphere for 3 hr to obtain Nb₂O₅An oxide.

Nb₂O₅The multifunctional catalyst is carried by oxide, wherein the parts of Ni and tungsten trioxide are respectively 8.0 and 30.0, and the carrier is Nb₂O₅The part of oxide is 62.0 parts, and is marked as catalyst V, and the catalyst is prepared by an impregnation method: 0.793g of nickel nitrate hexahydrate and 0.698g of ammonium metatungstate were dissolved in 3.0g of deionized water until completely dissolvedAnd uniformly mixing, weighing 1.24g of the prepared carrier, shaking until the carrier is uniformly mixed, drying at room temperature until most of water is evaporated, continuing to dry in an oven at 110 ℃ overnight, then roasting at 400 ℃ for 2h in an air atmosphere, and finally reducing with hydrogen at 400 ℃ for 3 h.

The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle, 2.0g of microcrystalline cellulose and 0.6g of catalyst V are weighed and added into a high-pressure reaction kettle (100mL) filled with 40mL of water, the reaction kettle is closed, then nitrogen is introduced for replacement for three times, and H is filled₂/N₂(80/20) the mixed gas is heated to 240 ℃ to 8MPa, and the reaction is carried out for 30 min.

After the reaction, the temperature was decreased, and the solid and the reaction solution (reaction product) were separated by filtration, and the quantitative method of the reaction was the same as in example 1, and the results are shown in Table 2.

TABLE 2

Wherein the reaction conditions are 2.0g of microcrystalline cellulose, 40mL of water, 0.6g of catalyst and 8MPa of H₂/N₂(80/20), reaction at 240 ℃ for 30 min.

[ example 20 ]

The catalyst after the reaction of example 19 was recovered, and the catalyst was subjected to cyclic reaction 1 to 5 times under the same reaction conditions, and the reaction results were measured for different numbers of cycles, and the comparative cases are shown in Table 3.

TABLE 3

Wherein the reaction conditions are 2.0g of cellulose, 40mL of water, 0.6g of catalyst S and 8MPa of H₂/N₂(80/20), reaction at 240 ℃ for 30 min.

What has been described above is merely a preferred example of the present invention. It should be noted that other equivalent variations and modifications can be made by those skilled in the art based on the technical teaching provided by the present invention, and the protection scope of the present invention should be considered.