CN104772141B - A kind of preparation method and applications for the catalyst that low-carbon dihydric alcohol is prepared available for glucose hydrogenolysis - Google Patents

Abstract

The invention discloses a preparation method of a catalyst that can be used for glucose hydrogenolysis to prepare low-carbon dihydric alcohols; firstly, the catalyst carrier is pretreated, and then the pretreated catalyst carrier is impregnated with an auxiliary metal solution; The catalyst carrier of the auxiliary metal is impregnated with an active metal solution; finally, the hydrogen is reduced to obtain a catalyst that can be used for the hydrogenolysis of glucose to prepare low-carbon diols; the preparation method is simple to operate, low in cost, and high in efficiency. It can regulate the location and degree of glucose carbon chain disconnection and has high activity and high selectivity to low-carbon diols. The invention also discloses the application of the catalyst, which can be used to catalyze the hydrogenolysis reaction of glucose, especially can be used to catalyze the hydrogenolysis reaction of glucose in high-pressure continuous fixed bed, batch reactor and high-gravity rotary bed.

Description

A kind of preparation method of the catalyst that can be used for the hydrogenolysis of glucose to prepare low-carbon dihydric alcohol and its application

technical field

The invention belongs to the field of catalyst preparation, and in particular relates to a preparation method and application of a catalyst which can be used for hydrogenolysis of glucose to prepare low-carbon dihydric alcohols.

Background technique

With the depletion of petrochemical resources and the increasingly severe environmental pollution, the development and use of biomass energy has a profound impact on energy consumption, environmental protection and economic benefits. Catalysts currently used for biomass conversion are usually prepared by ordinary impregnation method. Although this preparation method is easy to operate, it has different particle sizes, uneven dispersion, and low metal surface utilization, resulting in high conversion efficiency and selectivity. Not high, the catalytic effect is not ideal. In addition, in order to improve the catalytic effect, most of them need to add acid/alkali as a promoter, which will cause corrosion to the equipment and increase the production cost. These drawbacks of catalysts limit their applications to a large extent. Especially in the field of glucose hydrogenolysis to prepare low-carbon diols, these disadvantages of the catalyst make it impossible to realize large-scale preparation of low-carbon diols by glucose hydrogenolysis.

The currently published patents on catalysts for biomass conversion mainly include:

1. A regular structure ruthenium catalyst and its preparation method, CN101850249A; by impregnating the regular structure nano-carbon fiber carrier with a solution containing ruthenium compound in equal amounts or excessively, aging at room temperature, then drying, and finally reducing to obtain the catalyst loaded on the regular structure Ruthenium catalyst on carbon nanofibers; the catalyst can be used to hydrogenolyze sorbitol to prepare ethylene glycol and propylene glycol; the conversion rate of sorbitol is about 50%, and the conversion rate is not high.

2. Plate-type carbon fiber-supported ruthenium catalyst and its preparation method and application, CN101347731; after purifying the plate-type nano-carbon fiber carrier, impregnating the plate-type nano-carbon fiber with a ruthenium-containing compound solution in equal amounts, aging at room temperature overnight, and then drying at 80-120°C Dry for 6 to 12 hours, and finally reduce to obtain a catalyst loaded with metal materials; this catalyst can also be used for the hydrogenolysis reaction of sorbitol to prepare ethylene glycol and propylene glycol; the conversion rate of sorbitol is about 50%, and the conversion rate is not high.

3. A nickel/copper catalyst and its preparation method and the method of using the catalyst to directly prepare 1,2-hexanediol from cellopolysaccharide, CN103055870A; first prepare carrier activated carbon and ethylenediamine nickel, ethylenediamine Copper, then by fully mixing the ethylenediamine copper solution, ethylenediamine nickel solution and activated carbon, and then adding NaBH ₄ solution ice bath reaction, to obtain the catalyst; or by ethylenediamine nickel, ethylenediamine copper through Equal volumes are impregnated on activated carbon, roasted and then reduced to obtain a catalyst; the catalyst can be used to catalyze the direct preparation of 1,2-hexanediol from cellopolysaccharide; the yield is 30-50%, and the conversion rate is not high.

4. A ruthenium catalyst, its preparation method and its application in the synthesis of tetrahydrofurfuryl alcohol, CN102489315A; first add carrier TiO 2 to the aqueous solution containing ruthenium salt or to the aqueous solution containing ruthenium salt and metal promoter salt, and then add the carrier TiO ₂ to the mixed Potassium borohydride or hydrazine hydrate solution is added to the solution to obtain a catalyst; the catalyst is used in the one-step hydrogenation of furfural to synthesize tetrahydrofurfuryl alcohol; the yield can be greater than 99%; but in the preparation process, sodium sulfate needs to be added as a solvent for hydrothermal treatment. The introduction of ions will affect the catalyst performance.

6. A preparation method of activated carbon-supported noble metal catalyst, CN102658133A; by treating activated carbon in ethylenediaminetetraacetic acid disodium salt solution, and then stirring in nitrate solution or chloride solution solution containing noble metal, adding alkaline Adjust the pH value of the aqueous solution and continue to stir, and finally reduce it with hydrazine hydrate or hydrogen to obtain a catalyst; this catalyst can be used to catalyze hydrogenation to synthesize DSD acid; And the use of alkaline solutions such as sodium hydroxide and potassium hydroxide to adjust the pH value of the reaction, the metal ions introduced will affect the performance of the catalyst.

7. Nickel/ruthenium catalyst and its method for water phase reaction, CN1246077; the catalyst is a particle formed from a porous carrier on which a certain amount of reduced nickel metal catalytic phase providing catalyst activity is deposited as the first dispersed phase , the particles also have a ruthenium metal added to the porous carrier as the second dispersed phase, the amount of which can effectively make the nickel metal catalyst phase anti-agglomeration or sintering, prolonging the life of the catalyst in the hydrogenation reaction; but The adopted reaction conditions are 350° C. and 340 atm, and the reaction temperature is slightly higher and the pressure is higher, resulting in energy consumption and potential safety hazards.

8. Tungsten carbide catalyst supported on mesoporous carbon, preparation and application therefore, EP2495042A1.

Currently published patents on the preparation of dihydric alcohols from sugars mainly include:

1, the preparation method of dibasic alcohol, CN101781166; Under alkaline conditions, use Raney nickel, ruthenium/carbon, nickel/ruthenium or copper oxide-zinc oxide as hydrogenolysis catalyst to hydrogenolyze glucose; Corrosion equipment, reaction at 10MPa ~ 13MPa will cause potential safety hazards.

2. The preparation method of dihydric alcohol, CN101781171; under alkaline conditions, use nickel-molybdenum-copper doped with chromium or iron, tin, and zinc as a hydrogenolysis catalyst to hydrogenolyze glucose; easy-to-corrosion equipment under alkaline conditions , Reacting under 10MPa ~ 13MPa will cause potential safety hazards.

3. A method for preparing low-carbon polyols, CN102020531; it uses non-precious metal Ni-W ₂ C/CNFs as a hydrogenolysis catalyst to hydrogenolyze sugars; the total yield of low-carbon diols does not exceed 30%, and the selectivity not tall.

4. A method for preparing small-molecule polyols by hydrolyzing sugar liquid from straw, CN102898278; first, using Raney nickel as a catalyst to hydrogenate soluble sugar liquid into a sugar-alcohol solution, and then heating up and hydrogenating to produce small-molecule polyols; low-carbon The total yield of dihydric alcohols is not more than 32%, and the selectivity is not high.

5, the preparation method of dibasic alcohol, CN101781170; use the mixture of sorbitol and mannitol as raw material, the nickel-molybdenum-copper doped with chromium or iron, tin, zinc is used as hydrogenolysis catalyst to hydrogenolyze mixed sugar alcohol; catalyst amount is 3% to 10% of the total weight of the water phase, if the amount used is too large, it will easily cause waste of resources and water pollution.

6. The synthesis method of dihydric alcohols and polyols, CN101781168; using sucrose as raw material, nickel-molybdenum-copper doped with chromium or iron, tin, zinc as a hydrogenolysis catalyst to hydrogenolyze sucrose; the amount of catalyst is 15% of the mass of sucrose ~30%, excessive usage will easily cause resource waste and water pollution.

7. The synthesis method of dibasic alcohols and polyhydric alcohols, CN101781167; use sucrose as a raw material, and use Raney nickel, ruthenium/carbon, nickel/ruthenium or copper oxide-zinc oxide as a hydrogenolysis catalyst to hydrogenolyze sucrose; 15% to 30%, if the usage is too large, it will easily cause waste of resources.

Therefore, it is of great significance to explore the preparation method of new catalysts for the hydrogenolysis of glucose to low-carbon diols.

Contents of the invention

The first technical problem to be solved in the present invention is to provide a preparation method of a catalyst that can be used for the hydrogenolysis of glucose to prepare low-carbon dibasic alcohols; impregnated with an agent metal solution; then impregnated the catalyst carrier loaded with an auxiliary metal with an active metal solution; finally passed hydrogen reduction to obtain a catalyst that can be used for the hydrogenolysis of glucose to prepare low-carbon diols; the preparation method is simple in operation, low in cost, and efficient High, the catalyst can regulate the position and degree of glucose carbon chain disconnection when catalyzing glucose, has high activity, and has high selectivity to low-carbon diols.

The second technical problem to be solved by the present invention is to provide the application of a catalyst that can be used to prepare low-carbon diols by hydrogenolysis of glucose. The catalyst containing various metal components can be used to catalyze the hydrogenolysis reaction of glucose, especially for high-pressure Catalytic hydrogenolysis of glucose in continuous fixed bed, batch tank reactor and high gravity rotating bed.

The present invention provides a kind of preparation method that can be used in the preparation method of the catalyst of low-carbon dihydric alcohol by glucose hydrogenolysis, comprises the following steps:

1) Pretreatment of the catalyst carrier;

2) impregnating the pretreated catalyst carrier with an auxiliary metal solution;

3) impregnating the catalyst carrier loaded with the auxiliary metal with the active metal solution;

4) Reduction with hydrogen to obtain a catalyst that can be used for the hydrogenolysis of glucose to prepare low-carbon diols;

Wherein, the pretreatment is the pure solvent or aqueous solution of PEG-200, the pure solvent or aqueous solution of PEG-400, the pure solvent or aqueous solution of PEG-600, the pure solvent or aqueous solution of Triton X-100, the ammonia of EDTA One or more mixtures of aqueous solution and citric acid aqueous solution are used to treat the catalyst carrier.

Preferably, the auxiliary metal solution is an aqueous solution of one or more than two of W, Mo, Zr, Al and Co; the active metal solution is an aqueous solution of Ru and/or Ni. The pretreated catalyst carrier is impregnated with an equal volume or excess of an auxiliary metal solution, and the catalyst carrier loaded with an auxiliary metal is impregnated with an equal volume or an excess amount of an active metal solution.

Preferably, the mass ratio of the catalyst carrier to the promoter metal is 1:0.05-0.5. Too little promoter metal can not achieve the purpose of regulating the catalytic performance of active components; too much can easily cover the active sites and reduce the catalytic performance. The mass ratio of the catalyst carrier to the active metal is 1:0.005-0.2. Too little active metal will lead to insufficient active sites and reduce the catalytic performance; too much will easily agglomerate and also reduce the catalytic performance.

Preferably, the catalyst carrier is silica, activated carbon or carbon fiber.

More preferably, the catalyst carrier is 20-40 mesh silica, 20-40 mesh activated carbon or 50nm-15μm carbon fiber. Using 20-40 mesh silica and activated carbon as the carrier can avoid the adverse effects of bed pressure drop and internal diffusion; using 50nm-15μm carbon fiber as the carrier can form a larger specific surface area, compared with conventional carbon fiber as the carrier, It has significant structural advantages for industrial applications.

Preferably, in step 1), the pretreatment of the catalyst carrier is:

I purify the catalyst carrier;

II place the purified catalyst carrier in the pretreatment solution and heat to obtain a mixed solution;

III Suction filter the mixed solution, vacuumize, dry and calcinate to obtain the pretreated catalyst carrier.

It can be understood that there is no need to limit the amount and concentration of the pretreatment solution.

Preferably, the purification of the I catalyst carrier is:

Purification of silica: in air atmosphere, calcined silica at 150-250°C for 2-3 hours;

Purification of activated carbon: calcining activated carbon at 150-250°C for 2-3 hours in a nitrogen atmosphere;

Purification of carbon fiber: place carbon fiber in 50-120mL nitric acid, heat at 60-90°C for 2-3 hours, condense and reflux, and then dry the reflux.

Preferably, in the purification of carbon fibers, drying the reflux liquid is drying the reflux liquid at 100-150° C. for 6-12 hours in an air or nitrogen atmosphere. If the temperature is too low and the time is too short, the drying effect cannot be achieved; if the temperature is too high and the time is too long, the solvent removal rate will be too fast, which will adversely affect the structure and stability of the catalyst.

Preferably, in the above II, the heating is: heating at 80-120°C for 1-10 hours. If the temperature is too low and the time is too short, the pretreatment effect cannot be achieved; if the temperature is too high and the time is too long, the pretreatment solution will generate carbon substances in the catalyst pores, which will have an adverse effect on metal impregnation and dispersion.

Preferably, in said III:

Filtration and vacuuming are:

Suction filter the mixture at room temperature for 1 to 3 hours, take out the filter residue, and vacuum for 1 to 2 hours; if the suction filtration time is too short, the suction filtration effect cannot be achieved, and if the suction filtration time is too long, it is easy to extract the pretreatment solvent that enters the carrier channel, affecting Pretreatment effect: Vacuuming for 1-2 hours can drive out the gas in the carrier pores as much as possible to ensure the metal loading capacity;

Dry as:

Vacuum dry at 100-150°C for 6-15 hours; if the temperature is too low and the time is too short, the drying effect cannot be achieved; if the temperature is too high and the time is too long, the rate of solvent removal will be too fast, which will adversely affect the structure and stability of the catalyst ;

Roasted as:

Silica: in air atmosphere, roasted at 300-500°C for 2-6 hours;

Activated carbon: nitrogen atmosphere, roasting at 300-500°C for 2-6 hours;

Carbon fiber: in a nitrogen atmosphere, calcined at 300-500°C for 2-6 hours; if the temperature is too low and the time is too short, the calcining effect cannot be achieved (that is, the final catalyst has stable catalytic performance and a certain crystal form, grain size, and voids can be obtained. Structure and specific surface, improve the mechanical strength of the catalyst); if the temperature is too high and the time is too long, it is easy to sinter, so that the surface area of the carrier does not increase but decreases.

Preferably, in step 2), after impregnating the catalyst support with the metal solution of the auxiliary agent, vacuumize, dry, and roast; wherein,

Drying is: drying at 100-150°C for 6-15 hours; too low temperature and too short time will not achieve the drying effect; too high temperature and too long time will make the rate of solvent removal too fast, which will affect the structure and stability of the catalyst. Adverse effects; drying in air is sufficient.

Roasted as:

Silica: in air atmosphere, roasted at 300-500°C for 2-6 hours;

Activated carbon: nitrogen atmosphere, roasting at 300-500°C for 2-6 hours;

Carbon fiber: in a nitrogen atmosphere, roast at 300-500°C for 2-6 hours; the temperature is too low and the time is too short to achieve the roasting effect (that is, to make the final catalyst have stable catalytic performance and obtain a certain crystal form, grain size, and void structure. and specific surface, improve the mechanical strength of the catalyst); if the temperature is too high and the time is too long, the catalyst is easy to sinter, so that the surface area does not increase but decreases.

Preferably, in step 3), after impregnating the catalyst support supporting the auxiliary metal with the active metal solution, vacuumize, dry, and roast; wherein,

Drying is: drying at 100-150°C for 6-15 hours; too low temperature and too short time will not achieve the drying effect; too high temperature and too long time will make the rate of solvent removal too fast, which will affect the structure and stability of the catalyst. Adverse effects; drying in air is sufficient.

Roasted as:

Silica: in air atmosphere, roasted at 300-500°C for 2-6 hours;

Activated carbon: nitrogen atmosphere, roasting at 300-500°C for 2-6 hours;

Carbon fiber: in a nitrogen atmosphere, calcined at 300-500°C for 2-6 hours; if the temperature is too low and the time is too short, the calcining effect cannot be achieved (that is, the final catalyst has stable catalytic performance and a certain crystal form, grain size, and voids can be obtained. Structure and specific surface, improve the mechanical strength of the catalyst); if the temperature is too high and the time is too long, the catalyst is easy to sinter, so that the surface area does not increase but decreases.

Further, in step 4), reduction is carried out at 300-500° C. for 6-12 hours in a hydrogen atmosphere. If the temperature is too low and the time is too short, the activation effect cannot be achieved; if the temperature is too high and the time is too long, the structure and stability of the catalyst will be easily affected.

The invention provides the application of a catalyst that can be used for the hydrogenolysis of glucose to prepare low-carbon dihydric alcohols, and the catalyst can be used to catalyze the hydrogenolysis of glucose.

Preferably, when catalyzing the hydrogenolysis reaction of glucose, the concentration of the aqueous glucose solution is 2-50wt%.

Preferably, it can be used for catalytic hydrogenolysis of glucose in high-pressure continuous fixed bed, batch reactor and high-gravity rotating bed; more preferably, it can be used for catalytic hydrogenolysis of glucose in high-pressure continuous fixed bed and high-gravity rotating bed .

Preferably, when the catalyst is used in a high-pressure continuous fixed-bed catalytic hydrogenolysis reaction of glucose, the process conditions are: temperature 175-215°C, pressure 3-5MPa, liquid space velocity 1-300h ^-1 ;

When the catalyst is used in a batch reactor to catalyze the hydrogenolysis of glucose, the process conditions are: temperature 195-215°C, pressure 3-5MPa, liquid space velocity 1-300h ^-1 , rotation speed 1400-1800r/min;

When the catalyst is used in a high-gravity rotating bed to catalyze the hydrogenolysis of glucose, the process conditions are: temperature 195-215°C, pressure 3-5MPa, liquid space velocity 1-500h ^-1 , rotation speed 200-1500r/min.

Traditional biomass hydrogenation is carried out in a batch reactor, and the reaction is a slurry bed mode. Hydrogen, glucose solution and catalyst are put into the reactor at one time. Due to the influence of catalyst performance, most catalysts need to add acid / Alkaline promoter to promote the hydrogenation reaction.

In the fixed bed reaction, the reaction is a trickle bed mode, and the raw material solution is slowly passed through the catalyst bed by gravity, and the product is also separated from the catalyst bed by gravity. The solid catalyst is fixed with quartz wool. Since the residence time is controllable, the purpose of regulating product distribution can be achieved by regulating the degree of hydrogenolysis chain scission of raw materials. Compared with the batch reaction, this method has better continuity and operability.

In the high-gravity rotating bed reaction, the raw material enters the reactor and rotates into finer droplets, thereby increasing the contact effect with the catalyst bed, and it is separated from the catalyst by centrifugal force, which greatly increases the mass transfer efficiency. During the operation of the high-gravity reactor, the residence time of the reaction is reduced by an order of magnitude, but at the same time, the proportion of hydrogen dissolved in the liquid phase of the reaction is greatly increased, thereby promoting the hydrogenation chain scission reaction. And by adjusting the rotational speed, there can be an optimal choice between residence time and mass transfer rate. There are two types of high-gravity reactors: vertical and horizontal.

The beneficial effects of the present invention are as follows:

1. By controlling specific operating conditions, pretreat the surface of the carrier with polyethylene glycol, triton X-100, EDTA, citric acid and other pretreatment solutions to change the type and quantity of functional groups on the surface of the carrier (mainly produced carboxyl groups , acid anhydride, carbonyl and other oxygen-containing groups), so as to improve the dispersion of metal particles, increase the utilization rate of metal particles, and finally achieve the purpose of regulating the distribution of reaction products (that is, the degree of hydrogenation chain scission);

2. Adding promoter metals in the catalyst preparation process can adjust the acid properties of the catalyst, regulate the number of acid centers, and finally achieve the purpose of regulating the chain scission degree of glucose hydrogenation when it is used to catalyze glucose;

3. Simple operation, low cost, high efficiency, suitable for large-scale production, using environmentally friendly pretreatment solution to avoid environmental pollution;

4. When using the catalyst of the present invention to catalyze glucose, it is only necessary to dissolve the raw material glucose in water. Compared with dissolving glucose in solvents such as dimethyl sulfoxide and valerolactone, it can save costs and have high solubility; the mass concentration is selected at 50 %, it can avoid coking of glucose raw materials in the reactor and other problems; and it has high activity and high selectivity to low-carbon dihydric alcohols;

5. When catalyzing the hydrogenolysis reaction of glucose in the three reactors of fixed bed, batch kettle and rotating bed, no need to add any alkaline accelerator, and the damage to the equipment is also minimized;

6. When using the catalyst of the present invention to catalyze glucose, not only industrial glucose can be used as a raw material, but also the by-products and even waste materials rich in polyols, aldehydes, and acids in the fermentation industry, such as wine making, etc., can be used as raw materials. Compared with fossil resources such as petroleum and natural gas, the raw materials in the preparation of polyols can effectively use biomass and greatly improve economic benefits.

detailed description

In order to better understand the present invention, the solution of the present invention will be further described through specific examples below, and the protection scope of the present invention should include the entire content of the claims, but is not limited thereto.

Glucose conversion rate (%) = (1-the number of carbon moles of glucose in the product/the number of carbon moles in the raw material)×100

Ethylene glycol selectivity (%) = (carbon moles of ethylene glycol in the product/carbon moles of glucose participating in the reaction) × 100

Propylene glycol selectivity (%) = (carbon moles of propylene glycol in the product/carbon moles of glucose participating in the reaction) × 100

Butanediol selectivity (%) = (carbon moles of butanediol in the product/carbon moles of glucose participating in the reaction) × 100

Ethylene glycol yield (%) = (the number of carbon moles of ethylene glycol in the product/the number of carbon moles in the raw material) × 100

Propylene glycol yield (%) = (the number of carbon moles of propylene glycol in the product/the number of carbon moles in the raw material) × 100

Butanediol yield (%) = (the number of carbon moles of butanediol in the product/the number of carbon moles in the raw material) × 100

Example 1

A method for preparing a catalyst that can be used for hydrogenolysis of glucose to prepare low-carbon dihydric alcohols, comprising the following steps:

1. Pretreatment of silica carrier

1 takes by weighing 5g of silicon dioxide, and at 200°C, it is placed in an air atmosphere and roasted for 2h, taken out after cooling to room temperature, and transferred to a three-necked flask;

II Add 80mL of PEG-200 pure solution to the flask, use an electric heating mantle to raise the temperature to 120°C, heat for 2h and then cool to room temperature;

III Use a Buchner funnel to filter at room temperature for 1 hour, take out the filter residue, vacuumize for 1 hour, then place it in a vacuum oven, dry it in vacuum at 120°C for 10 hours, and finally bake it in an air atmosphere at 500°C for 2 hours, and cool to Packaged after room temperature for use.

2. Loading auxiliary metals on silica

① Dissolve a certain amount of ammonium metatungstate precursor in deionized water to prepare an ammonium metatungstate aqueous solution, and impregnate the treated _SiO2 carrier in equal amounts at a loading rate of 10wt%W;

②After impregnation, vacuumize for 1h, then dry in the air atmosphere at 120°C for 10h, and then bake in the air atmosphere at 500°C for 2h, that is, the auxiliary metal W is successfully loaded on the PEG-200 pretreated _SiO2 carrier .

3. Supporting active metals on silica

1) A certain amount of RuCl ₃ ·nH2O precursor was dissolved in deionized water to prepare a RuCl ₃ aqueous solution, which was impregnated on the above-mentioned SiO ₂ carrier loaded with W at a loading rate of 1wt% Ru;

2) Same as 2②, get Ru-W/SiO ₂ (PEG-200) catalyst (1wt%Ru-10wt%W).

4. Activate the catalyst

The catalyst was reduced at 500°C for 10 h in a hydrogen atmosphere to obtain an activated catalyst (1wt%Ru-10wt%W).

The activated catalyst was characterized and analyzed, the average particle size was 2nm, the dispersion was uniform, and there was no agglomeration.

Comparative example 1

With embodiment 1, change is:

Without any preprocessing steps.

Finally, the activated catalyst (1wt%Ru-10wt%W) was obtained.

Characterization and analysis of the activated catalyst showed that the average particle size was 10nm, and there was agglomeration phenomenon.

Example 2

A method for preparing a catalyst that can be used for hydrogenolysis of glucose to prepare low-carbon dihydric alcohols, comprising the following steps:

1. Pretreatment of activated carbon AC

1 takes by weighing 5g gac, at 200 ℃, it is placed in the roasting 2h of nitrogen atmosphere, takes out after being cooled to room temperature, transfers in the three-necked flask;

II Add 80mL of pure PEG-400 solution to the flask, use an electric heating mantle to raise the temperature to 120°C, heat for 2 hours and then cool to room temperature;

III Use a Buchner funnel to filter at room temperature for 1h, take out the filter residue, vacuumize for 1h, then place it in a vacuum oven, dry it in vacuum at 120°C for 10h, and finally roast it in a nitrogen atmosphere at 500°C for 2h, and cool to Packaged after room temperature for use.

2. Loading auxiliary metals on activated carbon

① Dissolve a certain amount of ammonium molybdate precursor in deionized water to prepare an ammonium molybdate aqueous solution, and impregnate the treated AC carrier with a loading rate of 10wt%Mo;

② After impregnation, vacuumize for 1 h; then, dry in air atmosphere at 120 °C for 10 h; after drying, bake in nitrogen atmosphere at 500 °C for 2 h, that is, the additive metal Mo is successfully loaded onto the PEG-400 pretreated AC on the carrier.

3. Loading active metals on activated carbon

1) A certain amount of nickel nitrate hexahydrate precursor was dissolved in deionized water to prepare a nickel nitrate aqueous solution, which was impregnated on the above-mentioned AC carrier loaded with W at a loading rate of 10wt%Ni;

2) Same as 2②, get Ni-Mo/AC(PEG-400) catalyst (10wt%Ni-10wt%Mo).

4. Activate the catalyst

As in Example 1, an activated catalyst (10wt%Ni-10wt%Mo) was obtained.

Comparative example 2

With embodiment 2, change is:

Without any preprocessing steps.

Finally, the activated catalyst (10wt%Ni-10wt%Mo) was obtained.

Example 3

A method for preparing a catalyst that can be used for hydrogenolysis of glucose to prepare low-carbon dihydric alcohols, comprising the following steps:

1. Pretreatment of carbon fiber CNFs

I Weigh 5g of carbon fiber carrier and place it in a three-necked flask, add 80mL of nitric acid solution into the flask, use an electric heating mantle to raise the temperature to 80°C, heat for 2h and condense and reflux, then cool to room temperature; then, at 120°C in an air atmosphere Dry for 10 hours;

II Add 80mL of PEG-600 pure solution to the flask, use an electric heating mantle to raise the temperature to 120°C, heat for 2 hours and then cool to room temperature;

III is the same as embodiment 1.

2. Support additive metal on carbon fiber

① Dissolve a certain amount of zirconium oxynitrate precursor in deionized water to prepare a zirconium nitrate aqueous solution, and impregnate the treated CNFs carrier with an equal amount of 15wt% Zr loading rate;

②After impregnation, vacuumize for 1h; then, dry in air atmosphere at 120°C for 10h; after drying, bake in nitrogen atmosphere at 500°C for 2h, that is, the additive zirconia is successfully loaded onto the CNFs pretreated with PEG-600 on the carrier.

3. Load active metals on carbon fibers

1) A certain amount of RuCl ₃ ·nH ₂ O precursor was dissolved in deionized water to prepare a RuCl ₃ aqueous solution, which was impregnated in equal amounts on the above-mentioned Zr-loaded SiO ₂ carrier with a loading rate of 2wt% Ru;

2) Same as 2②, get Ru-Zr/CNFs (PEG-600) catalyst.

4. Activation catalyst

As in Example 1, an activated catalyst (2wt%Ru-15wt%Zr) was obtained.

Example 4

A method for preparing a catalyst that can be used for hydrogenolysis of glucose to prepare low-carbon dihydric alcohols, comprising the following steps:

With embodiment 1, change is:

1. Add 80mL TX-100 pure solution for pretreatment.

2. Take a certain amount of aluminum nitrate nonahydrate precursor and dissolve it in deionized water to prepare an aqueous solution of aluminum nitrate, and impregnate the treated _SiO2 carrier with an equivalent amount of 20wt% Al loading rate; obtain a _SiO2 carrier that has been loaded with Al .

3. A certain amount of nickel nitrate hexahydrate precursor is dissolved in deionized water to prepare an aqueous solution of nickel nitrate, which is impregnated in equal amounts with a loading rate of 15wt%Ni on the SiO carrier loaded with Al _{; Ni-Al/SiO 2 (} TX-100) catalyst.

Finally, the activated catalyst (15wt%Ni-20wt%Al) was obtained.

Example 5

A method for preparing a catalyst that can be used for hydrogenolysis of glucose to prepare low-carbon dihydric alcohols, comprising the following steps:

With embodiment 2, change is:

1. Add 80mL of EDTA ammonia solution (10wt% EDTA) to the flask, use an electric heating mantle to raise the temperature to 90°C, and heat for 2 hours.

2. Take a certain amount of cobalt nitrate precursor and dissolve it in deionized water to prepare a cobalt nitrate aqueous solution, and impregnate the treated AC carrier with a loading rate of 20wt% Co to obtain an AC carrier loaded with Co.

3. Dissolve the RuCl ₃ ·nH ₂ O precursor in deionized water to prepare a RuCl ₃ aqueous solution, and impregnate the above-mentioned Co-loaded AC carrier with a loading rate of 1wt% Ru; to obtain Ru-Co/AC (10wt% EDTA) catalyst.

Finally, the activated catalyst (1wt%Ru-20wt%Co) was obtained.

Example 6

A method for preparing a catalyst that can be used for hydrogenolysis of glucose to prepare low-carbon dihydric alcohols, comprising the following steps:

With embodiment 3, change is:

1. Add 80mL of citric acid aqueous solution (10wt% citric acid) to the flask, use an electric heating mantle to raise the temperature to 90°C, and heat for 2h.

2. Dissolve a certain amount of ammonium metatungstate precursor in deionized water to prepare an ammonium metatungstate aqueous solution, and impregnate the treated CNFs carrier with a loading rate of 15wt%W; obtain a CNFs carrier loaded with W .

3. Dissolving a certain amount of nickel nitrate hexahydrate precursor in deionized water to prepare an aqueous solution of nickel nitrate, and impregnating the above-mentioned W-loaded CNFs carrier with a loading rate of 15wt% Ni;

Ni-W/CNFs (10wt% citric acid) catalyst.

Finally, the activated catalyst (15wt%Ni-15wt%W) was obtained.

Example 7

A method for preparing a catalyst that can be used for hydrogenolysis of glucose to prepare low-carbon dihydric alcohols, comprising the following steps:

With embodiment 1, change is:

1. Add 80mL of 80V% PEG-200 aqueous solution into the flask.

2. Take a certain amount of ammonium molybdate precursor and dissolve it in deionized water to prepare an ammonium molybdate aqueous solution, and impregnate the treated _SiO2 support in equal amounts with a loading rate of 15wt% Mo.

Finally, the activated catalyst (1wt%Ru-15wt%Mo) was obtained.

Example 8

A method for preparing a catalyst that can be used for hydrogenolysis of glucose to prepare low-carbon dihydric alcohols, comprising the following steps:

With embodiment 2, change is:

1. Add 80mL of 60V% PEG-200 aqueous solution into the flask.

2. Take a certain amount of zirconyl nitrate precursor and dissolve it in deionized water to prepare a zirconium nitrate aqueous solution, and impregnate the treated AC carrier with a loading rate of 20wt% Zr.

Finally, the activated catalyst (10wt%Ni-20wt%Zr) was obtained.

Example 9

A method for preparing a catalyst that can be used for hydrogenolysis of glucose to prepare low-carbon dihydric alcohols, comprising the following steps:

With embodiment 3, change is:

1. Add 80mL of 40V% PEG-200 aqueous solution into the flask.

2. Take a certain amount of aluminum nitrate nonahydrate precursor and dissolve it in deionized water to prepare an aluminum nitrate aqueous solution, and impregnate the treated CNFs carrier with an equal amount of 10wt% Al loading rate.

Finally, the activated catalyst (2wt%Ru-10wt%Al) was obtained.

Example 10

A method for preparing a catalyst that can be used for hydrogenolysis of glucose to prepare low-carbon dihydric alcohols, comprising the following steps:

With embodiment 5, change is:

1. Add 80mL of EDTA in ammonia solution (20wt% EDTA) solution to the flask.

2. Equal amount of impregnation on the treated AC support with a loading rate of 10wt% Co.

3. A certain amount of nickel nitrate hexahydrate precursor was dissolved in deionized water to prepare a nickel nitrate aqueous solution, which was impregnated on the above-mentioned AC carrier loaded with Co at a loading rate of 15wt% Ni.

Finally, the activated catalyst (15wt%Ni-10wt%Co) was obtained.

Example 11

A method for preparing a catalyst that can be used for hydrogenolysis of glucose to prepare low-carbon dihydric alcohols, comprising the following steps:

With embodiment 6, change is:

1. Add 80mL of citric acid aqueous solution (20wt% citric acid) to the flask.

3. The RuCl ₃ ·nH ₂ O precursor was dissolved in deionized water to prepare a RuCl ₃ aqueous solution, which was impregnated on the W-loaded CNFs carrier at a loading rate of 2wt% Ru.

Finally, the activated catalyst (2wt%Ru-15wt%W) was obtained.

Example 12

A method for preparing a catalyst that can be used for hydrogenolysis of glucose to prepare low-carbon dihydric alcohols, comprising the following steps:

Same as Example 2, the changes are as follows: First, a certain amount of ammonium metatungstate precursor is dissolved in deionized water to prepare an ammonium metatungstate aqueous solution, and the treated AC carrier is equally impregnated with a loading rate of 10wt%W ; Then impregnate 10wt%Mo and 10wt%Ni according to the operation process of Example 2; Finally, an activated catalyst (10wt%Ni-10wt%Mo-10wt%W) was obtained.

Example 13

A method for preparing a catalyst that can be used for hydrogenolysis of glucose to prepare low-carbon dihydric alcohols, comprising the following steps:

Same as Example 7, the change is: first, take a certain amount of ammonium metatungstate precursor and dissolve it in deionized water to prepare an ammonium metatungstate aqueous solution, and put an equal amount of it on the treated _SiO2 carrier with a loading rate of 10wt%W Dipping. Then impregnate 15wt% Mo and 1wt% Ru according to the operation process of Example 7; finally an activated catalyst (1wt%Ru-15wt%Mo-10wt%W) was obtained.

Example 14

A method for preparing a catalyst that can be used for hydrogenolysis of glucose to prepare low-carbon dihydric alcohols, comprising the following steps:

The same as in Example 11, the changes are: first, impregnate 15wt%W according to the operation process of Example 11; then take a certain amount of nickel nitrate hexahydrate precursor and dissolve it in deionized water to prepare a nickel nitrate aqueous solution, and the treated CNFs carrier impregnated with 10wt%Ni loading rate; finally impregnated 2wt%Ru according to the operation process of Example 11; finally obtained the activated catalyst (2wt%Ru-10wt%Ni-15wt%W).

Example 15

Applications of catalysts that can be used for the hydrogenolysis of glucose to prepare low-carbon diols:

The raw material glucose is dissolved in water, the catalyst of the present invention is added, and the catalytic reaction is carried out according to the experimental conditions in Tables 1, 3, and 5. The catalytic results are shown in Tables 2, 4, and 6.

1. High pressure continuous fixed bed reactor

The reaction condition of table 1 fixed-bed reactor

serial number temperature(°C) Pressure (MPa) Catalyst mass (g) Glucose concentration (wt%) Liquid space velocity (h ^-1 ) Example 1 205 4 0.5 50 4 Example 2 195 5 0.5 5 300 Comparative example 2 205 4 0.5 5 300 Example 3 215 3 1 2 40 Example 4 205 4 1 10 40 Example 5 215 5 1 2 5 Example 6 195 3 0.5 10 30 Example 7 205 5 0.5 2 40 Example 8 215 4 1 5 40 Example 9 205 3 1 5 50 Example 10 215 5 1 2 40 Example 11 195 4 0.5 5 30 Example 12 205 5 0.5 10 40 Example 13 205 5 0.5 5 40 Example 14 215 4 1 10 40

Table 2 Catalytic result evaluation table of fixed bed reactor

2. Batch reactor

The reaction condition of table 3 batch tank reactor

serial number temperature(°C) Pressure (MPa) Catalyst mass (g) Glucose concentration (wt%) Speed(r/min) Example 1 205 4 0.5 10 1400 Example 2 215 5 1 5 1600 Comparative example 2 195 5 1 5 1800 Example 3 215 3 0.5 2 1400 Example 4 195 4 1 50 1600 Example 5 205 5 1 5 1800 Example 6 195 3 0.5 5 1400 Example 7 205 5 0.5 2 1400 Example 8 215 4 1 10 1600 Example 9 205 3 0.5 5 1800 Example 10 195 5 1 2 1400 Example 11 195 4 0.5 5 1600 Example 12 205 5 1 2 1400 Example 13 205 3 0.5 5 1800 Example 14 215 4 1 10 1400

Catalytic result evaluation table of table 4 batch tank reactor

3. High gravity rotating bed reactor

Table 5 The reaction conditions of the high-gravity rotating bed reactor

Table 6 Evaluation Table of Catalytic Results of High Gravity Rotating Bed Reactor

"Low carbon glycol" includes ethylene glycol, propylene glycol and butylene glycol. Among them, among propylene glycol and butanediol, 1,2-propanediol and 1,2-butanediol have the absolute dominant selectivity respectively. As can be seen from Tables 2, 4, and 6, in addition to low-carbon dihydric alcohols, the product also includes sorbitol, xylitol, erythritol, and others (mannitol, 5-hydroxymethylfurfural, 1, 2,4-butanetriol) and glycerin and other polyols. Among them, the selectivity of xylitol and erythritol is far lower than that of low-carbon diols, and the yield of glycerol is between xylitol and erythritol, while 5-hydroxymethylfurfural, 1,2 , The content of 4-butanetriol is extremely low.

From the catalytic results in Tables 2, 4, and 6, it can be seen that the nickel-based and ruthenium-based catalysts have different conversion rates and selectivities in the three different reactors. Therefore, for different operating conditions and target products, fixed bed reactors, batch tank reactors and rotating bed reactors have their own advantages.

Example 16

A method for preparing a catalyst that can be used for hydrogenolysis of glucose to prepare low-carbon dihydric alcohols, comprising the following steps:

1) Pretreatment of the catalyst carrier:

I purify the catalyst carrier;

II place the purified catalyst carrier in the pretreatment solution and heat to obtain a mixed solution;

III Suction filter the mixed solution, vacuumize, dry and calcinate to obtain the pretreated catalyst carrier.

2) impregnating the pretreated catalyst carrier with an auxiliary metal solution;

3) impregnating the catalyst carrier loaded with the auxiliary metal with the active metal solution;

4) Reduction with hydrogen to obtain a catalyst that can be used for the hydrogenolysis of glucose to prepare low-carbon diols;

The catalyst carrier is silicon dioxide. The pretreatment solution is a mixture of PEG-200 pure solvent and PEG-400 pure solvent (volume ratio 1:1). The auxiliary metal solution is an aqueous solution of W and Mo; the active metal solution is an aqueous solution of Ru. The mass ratio of the catalyst support to the promoter metal is 1:0.05; the mass ratio of the catalyst support to the active metal is 1:0.005.

Example 17

With embodiment 16, difference is:

The catalyst carrier is 20 mesh silica. The pretreatment solution is a mixture of PEG-600 pure solvent and Triton X-100 pure solvent (volume ratio 1:3). The auxiliary metal solution is an aqueous solution of Zr and Co; the active metal solution is an aqueous solution of Ni. The mass ratio of the catalyst support to the promoter metal is 1:0.5; the mass ratio of the catalyst support to the active metal is 1:0.2.

Example 18

With embodiment 16, difference is:

The catalyst carrier is 40 mesh silica. The pretreatment solution is a mixture of PEG-600 aqueous solution and citric acid aqueous solution (volume ratio 2:3). The auxiliary metal solution is an aqueous solution of Co; the active metal solution is an aqueous solution of Ni. The mass ratio of the catalyst support to the promoter metal is 1:0.25; the mass ratio of the catalyst support to the active metal is 1:0.1.

The catalyst is used in the high-gravity rotating bed to catalyze the hydrogenolysis of glucose, and the process conditions are: temperature 215°C, pressure 3MPa, liquid space velocity 500h ^-1 , rotation speed 200r/min.

Example 19

With embodiment 16, difference is:

The catalyst carrier is 20 mesh activated carbon.

In I: Purification: Calcined activated carbon at 150°C for 2h in a nitrogen atmosphere.

In II: heating: heating at 80°C for 1h;

In III: filter the mixed solution at room temperature for 1 hour, take out the filter residue, and vacuumize for 1 hour; drying: vacuum drying at 100°C for 6 hours; roasting: nitrogen atmosphere, roasting at 300°C for 2 hours.

In 2), the catalyst carrier is impregnated with the metal solution of the auxiliary agent, then vacuumized, dried, and calcined; wherein, the drying method is: drying at 100° C. for 6 h; the calcining method is: calcining at 300° C. for 2 h in a nitrogen atmosphere.

In 3), impregnate the catalyst carrier loaded with the auxiliary metal with the active metal solution, vacuumize, dry, and calcinate; wherein, drying is: drying at 100°C for 6h; calcining is: calcining at 300°C for 2h in a nitrogen atmosphere.

4), in a hydrogen atmosphere, at 300 ° C for 6 h.

The catalyst is used in the high-gravity rotating bed to catalyze the hydrogenolysis of glucose, and the process conditions are: temperature 195°C, pressure 5MPa, liquid space velocity 1h ^-1 , rotation speed 1500r/min.

Example 20

With embodiment 16, difference is:

The catalyst carrier is 30 mesh activated carbon.

In I: Purification: Calcined activated carbon at 250°C for 3h in a nitrogen atmosphere.

In II: heating: heating at 120°C for 10h;

In III: filter the mixed solution at room temperature for 3 hours, take out the filter residue, and vacuumize for 2 hours; dry: vacuum dry at 150°C for 15 hours; roast: bake at 500°C for 6 hours in a nitrogen atmosphere.

In 2), the catalyst carrier is impregnated with the metal additive solution, vacuumed, dried, and calcined; wherein, the drying method is: drying at 150° C. for 15 h; the calcining method is: calcining at 500° C. for 6 h in a nitrogen atmosphere.

In 3), impregnate the catalyst carrier loaded with the auxiliary metal with the active metal solution, vacuumize, dry, and calcinate; wherein, the drying is: drying at 150°C for 15h; the calcining is: calcining at 500°C for 6h in a nitrogen atmosphere.

4), in a hydrogen atmosphere, 500 ℃ reduction for 12h.

The catalyst is used in a batch tank reactor to catalyze the hydrogenolysis of glucose, and the process conditions are: temperature 215°C, pressure 5MPa, liquid space velocity 300h ^-1 , rotation speed 1800r/min.

Example 21

With embodiment 16, difference is:

The catalyst carrier is 50nm carbon fiber.

In I: Purification: put the carbon fiber in 50mL nitric acid, heat at 60°C for 2h and condense to reflux, then dry the reflux at 100°C in air atmosphere for 6h.

In II: heating: heating at 80°C for 1h;

In III: filter the mixed solution at room temperature for 1 hour, take out the filter residue, and vacuumize for 1 hour; drying: vacuum drying at 100°C for 6 hours; roasting: nitrogen atmosphere, roasting at 300°C for 2 hours.

In 2), the catalyst carrier is impregnated with the auxiliary metal solution, vacuumed, dried, and calcined; wherein, the drying method is: drying at 120° C. for 6 to 15 hours; the calcining method is: calcining at 400° C. for 4 hours in a nitrogen atmosphere.

In 3), after impregnating the catalyst carrier loaded with the auxiliary metal with the active metal solution, vacuumize, dry, and roast; wherein, the drying is: drying at 150°C for 15h; the roasting is: carbon fiber: nitrogen atmosphere, and roasting at 400°C for 4h.

4), in a hydrogen atmosphere, 400 ℃ reduction 8h.

The catalyst was used to catalyze the hydrogenolysis reaction of glucose; the concentration of aqueous glucose solution was 2 wt%. The catalyst is used in a batch tank reactor to catalyze the hydrogenolysis of glucose. The process conditions are: temperature 195°C, pressure 3MPa, liquid space velocity 1h ^-1 , rotation speed 1400r/min.

Example 22

With embodiment 16, difference is:

The catalyst carrier is 15 μm carbon fiber.

In I: Purification: put carbon fiber in 120mL nitric acid, heat at 90°C for 3h and condense to reflux, then dry the reflux liquid at 150°C in a nitrogen atmosphere for 12h.

In II: heating: heating at 120°C for 10h;

In III: filter the mixed solution at room temperature for 3 hours, take out the filter residue, and vacuumize for 2 hours; dry: vacuum dry at 150°C for 15 hours; roast: bake at 500°C for 6 hours in a nitrogen atmosphere.

In 2), the catalyst carrier is impregnated with the metal solution of the auxiliary agent, then vacuumized, dried, and calcined; wherein, the drying method is: drying at 100° C. for 6 h; the calcining method is: calcining at 500° C. for 2 h in a nitrogen atmosphere.

In 3), after impregnating the catalyst carrier loaded with the auxiliary metal with the active metal solution, vacuumize, dry, and roast; wherein, the drying is: drying at 100°C for 15h; the roasting is: roasting at 300°C for 2h in a nitrogen atmosphere.

4), in a hydrogen atmosphere, 300 ℃ reduction for 12h.

The catalyst is used to catalyze the hydrogenolysis reaction of glucose; the concentration of glucose aqueous solution is 50wt%. Catalytic hydrogenolysis of glucose in a high-pressure continuous fixed bed, the process conditions are: temperature 175°C, pressure 3MPa, liquid space velocity 1h ^-1 .

Example 23

With embodiment 16, difference is:

The catalyst carrier is 30 mesh silica.

In I: Purification: Calcined silica at 150°C for 2 hours in air atmosphere.

In II: heating: heating at 80°C for 1h;

In III: filter the mixed solution at room temperature for 1 hour, take out the filter residue, and vacuumize for 1 hour; drying: vacuum drying at 100°C for 6 hours; roasting: air atmosphere, roasting at 300°C for 2 hours.

In 2), the catalyst carrier is impregnated with the metal additive solution, vacuumed, dried, and calcined; wherein, drying is: drying at 100°C for 6 hours; calcining is: calcining at 300°C for 2 hours in an air atmosphere.

In 3), impregnate the catalyst carrier loaded with the auxiliary metal with the active metal solution, vacuumize, dry, and calcinate; wherein, the drying is: drying at 100°C for 6h; calcining at 300°C for 2h in an air atmosphere.

4), in a hydrogen atmosphere, at 300 ° C for 6 h.

The catalyst is used to catalyze the hydrogenolysis reaction of glucose; the concentration of glucose aqueous solution is 25wt%. Catalytic hydrogenolysis of glucose in a high-pressure continuous fixed bed, the technological conditions are: temperature 215°C, pressure 5MPa, liquid space velocity 300h ^-1 .

Example 24

With embodiment 16, difference is:

The catalyst carrier is 20 mesh silica.

In I: Purification: Calcined silica at 250°C for 3 hours in air atmosphere.

In II: heating: heating at 120°C for 10h;

In III: filter the mixed solution at room temperature for 3 hours, take out the filter residue, and vacuumize for 2 hours; dry: vacuum dry at 150°C for 15 hours; roast: air atmosphere, roast at 500°C for 6 hours.

In 2), after impregnating the catalyst support with the metal solution of the auxiliary agent, vacuumize, dry, and roast; wherein, drying is: drying at 150°C for 15 hours; roasting is: air atmosphere, roasting at 500°C for 6 hours.

In 3), impregnate the catalyst carrier loaded with the auxiliary metal with the active metal solution, vacuumize, dry, and calcinate; wherein, the drying method is: drying at 150°C for 15 hours; the calcining method is: calcining at 500°C for 6 hours in an air atmosphere.

4), in a hydrogen atmosphere, 500 ℃ reduction for 12h.

The catalyst is used in a batch reactor to catalyze the hydrogenolysis of glucose. The process conditions are: temperature 195-215°C, pressure 3-5MPa, liquid space velocity 1-300h ^-1 , rotation speed 1400-1800r/min.

Apparently, the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. Those of ordinary skill in the art can also make It is impossible to exhaustively list all the implementation modes here, and any obvious changes or changes derived from the technical solutions of the present invention are still within the scope of protection of the present invention.

Claims (12)

1. A preparation method of a catalyst for preparing low-carbon dihydric alcohol by glucose hydrogenolysis is characterized by comprising the following steps:

1) pretreating a catalyst carrier;

2) dipping the pretreated catalyst carrier by using an auxiliary agent metal solution;

3) impregnating the catalyst carrier loaded with the auxiliary metal with an active metal solution;

4) introducing hydrogen for reduction to obtain a catalyst for preparing low-carbon dihydric alcohol by glucose hydrogenolysis;

wherein the pretreatment is to treat the catalyst carrier by one or a mixture of more than two of PEG-200 or an aqueous solution thereof, PEG-400 or an aqueous solution thereof, PEG-600 or an aqueous solution thereof, Triton X-100 or an aqueous solution thereof, an aqueous ammonia solution of EDTA and an aqueous solution of citric acid;

in the step 1), the pretreatment of the catalyst carrier comprises the following steps:

step I: purifying the catalyst support;

step II: placing the purified catalyst carrier in a pretreatment solution, and heating to obtain a mixed solution;

step III: carrying out suction filtration, vacuumizing, drying and roasting on the mixed solution to obtain a pretreated catalyst carrier;

the assistant metal solution is one or more than two aqueous solutions of W, Mo, Zr, Al and Co; the active metal solution is an aqueous solution of Ru and/or Ni;

the mass ratio of the catalyst carrier to the auxiliary metal is 1: 0.05 to 0.5; the mass ratio of the catalyst carrier to the active metal is 1: 0.005 to 0.2;

the catalyst carrier is silicon dioxide, activated carbon or carbon fiber.

2. The preparation method of the catalyst for preparing the lower dihydric alcohol by hydrogenolysis of glucose according to claim 1, wherein the catalyst carrier is 20-40 mesh silica, 20-40 mesh activated carbon or 50 nm-15 μm carbon fiber.

3. The method for preparing the catalyst for the hydrogenolysis of glucose to lower alcohol according to claim 1,

in the step I:

and (3) purifying the silica: calcining silicon dioxide for 2-3 hours at 150-250 ℃ in an air atmosphere; and (3) activated carbon purification: calcining the activated carbon for 2-3 hours at 150-250 ℃ in a nitrogen atmosphere; and (3) purifying the carbon fiber: placing the carbon fiber in 50-120 mL of nitric acid, heating at 60-90 ℃ for 2-3 h, condensing and refluxing, and then drying a reflux liquid;

in the step II:

the heating is as follows: heating for 1-10 h at 80-120 ℃;

in the step III:

and (4) performing suction filtration, wherein the vacuum pumping is as follows: carrying out suction filtration on the mixed solution at room temperature for 1-3 h, taking out filter residues, and vacuumizing for 1-2 h;

the drying is as follows: vacuum drying for 6-15 h at 100-150 ℃;

the roasting is as follows: silicon dioxide: roasting for 2-6 h at 300-500 ℃ in air atmosphere; activated carbon: roasting for 2-6 h at 300-500 ℃ in nitrogen atmosphere; carbon fiber: roasting for 2-6 h at 300-500 ℃ in nitrogen atmosphere.

4. The method for preparing the catalyst for preparing the lower alcohol by hydrogenolysis of glucose according to claim 3, wherein in the purification of the carbon fiber, the reflux liquid is dried for 6-12 hours at 100-150 ℃ in the air or nitrogen atmosphere.

5. The method for preparing the catalyst for preparing the lower dihydric alcohol by the hydrogenolysis of glucose according to claim 1, wherein in the step 2), the catalyst carrier is impregnated with the assistant metal solution, and then the catalyst carrier is vacuumized, dried and roasted; wherein,

the drying is as follows: drying for 6-15 h at 100-150 ℃;

the roasting is as follows: silicon dioxide: roasting for 2-6 h at 300-500 ℃ in air atmosphere; activated carbon: roasting for 2-6 h at 300-500 ℃ in nitrogen atmosphere; carbon fiber: roasting for 2-6 h at 300-500 ℃ in nitrogen atmosphere.

6. The method for preparing the catalyst for preparing the lower alcohol by hydrogenolysis of glucose according to claim 1, wherein in the step 3), the catalyst carrier loaded with the auxiliary metal is immersed in the active metal solution, and then is vacuumized, dried and roasted; wherein,

the drying is as follows: drying for 6-15 h at 100-150 ℃;

the roasting is as follows: silicon dioxide: roasting for 2-6 h at 300-500 ℃ in air atmosphere; activated carbon: roasting for 2-6 h at 300-500 ℃ in nitrogen atmosphere; carbon fiber: roasting for 2-6 h at 300-500 ℃ in nitrogen atmosphere.

7. The method for preparing the catalyst for preparing the lower alcohol by hydrogenolysis of glucose according to claim 1, wherein in the step 4), the reduction is performed for 6 to 12 hours at 300 to 500 ℃ in a hydrogen atmosphere.

8. The application of the catalyst prepared by the preparation method for preparing the lower dihydric alcohol by glucose hydrogenolysis as claimed in any one of claims 1 to 7, wherein the catalyst is used for catalyzing glucose hydrogenolysis reaction.

9. The use according to claim 8, wherein the concentration of the aqueous glucose solution is 2 to 50wt% when the catalyst catalyzes the hydrogenolysis of glucose.

10. The use according to claim 8, wherein the catalyst is used for catalytic hydrogenolysis of glucose in high pressure continuous fixed bed, batch tank reactor and high gravity rotating bed.

11. The use according to claim 8, wherein the catalyst is used for catalytic hydrogenolysis of glucose in a high pressure continuous fixed bed, high gravity rotating bed.

12. The use according to claim 10, wherein when the catalyst is used in the high pressure continuous fixed bed catalytic hydrogenolysis of glucose, the process conditions are: the temperature is 175-215 ℃, the pressure is 3-5 MPa, and the liquid airspeed is 1-300 h^-1；

When the catalyst is used for the glucose catalytic hydrogenolysis reaction of a batch kettle type reactor, the process conditions are as follows: the temperature is 195-215 ℃, the pressure is 3-5 MPa, and the liquid airspeed is 1-300 h^-1Rotating speed of 1400-1800 rmin；

When the catalyst is used for the catalytic hydrogenolysis of glucose by the super-gravity rotating bed, the process conditions are as follows: the temperature is 195-215 ℃, the pressure is 3-5 MPa, and the liquid airspeed is 1-500 h^-1The rotation speed is 200 to 1500 r/min.