CN104772141B

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

Info

Publication number: CN104772141B
Application number: CN201410018520.5A
Authority: CN
Inventors: 张燚; 刘昱浏; 陈建峰
Original assignee: SUZHOU HAIJI SHITONG ENERGY Co Ltd; Beijing University of Chemical Technology
Current assignee: SUZHOU HAIJI SHITONG ENERGY Co Ltd; Beijing University of Chemical Technology
Priority date: 2014-01-15
Filing date: 2014-01-15
Publication date: 2017-08-25
Anticipated expiration: 2034-01-15
Also published as: CN104772141A

Abstract

The invention discloses a kind of preparation method for the catalyst that low-carbon dihydric alcohol is prepared available for glucose hydrogenolysis；By being pre-processed first to catalyst carrier, pretreated catalyst carrier used additives metallic solution is impregnated afterwards；The catalyst carrier for loading promoter metal is impregnated with active metal solution again；Finally lead to hydrogen reducing, obtain the catalyst that can be used for glucose hydrogenolysis to prepare low-carbon dihydric alcohol；The preparation method is simple to operate, and cost is low, efficiency high, and the catalyst position that controllable glucose carbochain disconnects in catalytic hydrogenolysis glucose and degree and activity height, the selectivity to low-carbon dihydric alcohol are high.The invention also discloses the application of the catalyst, it can be used to catalytic hydrogenolysis glucose response, be particularly useful for the continuous fixed bed of high pressure, batch tank reactor and high-gravity rotating bed middle catalytic hydrogenolysis glucose response.

Description

Preparation method and application of catalyst for preparing low-carbon dihydric alcohol by hydrogenolysis of glucose

Technical Field

The invention belongs to the field of catalyst preparation, and particularly relates to a preparation method and application of a catalyst for preparing low-carbon dihydric alcohol by glucose hydrogenolysis.

Background

With the increasing exhaustion of petrochemical resources and the increasing severity of environmental pollution, the development and use of biomass energy have a profound influence on energy consumption, environmental protection and economic benefit. The catalyst used for biomass conversion at present is usually prepared by a common impregnation method, and although the preparation method is simple and convenient to operate, the prepared particles have different sizes, uneven dispersion and low utilization rate of metal surfaces, so that the conversion rate and selectivity are not high, and 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 causes corrosion to equipment and increases production cost. These drawbacks of the catalysts limit their use to a large extent. Especially in the field of preparing low-carbon dihydric alcohol by glucose hydrogenolysis, the defects of the catalyst can not realize large-scale preparation of the low-carbon dihydric alcohol by the glucose hydrogenolysis.

The patents for catalysts for biomass conversion that have been disclosed so far are mainly:

1. a ruthenium catalyst with a regular structure and a preparation method thereof, CN 101850249A; the method comprises the steps of soaking a regular-structure carbon nanofiber carrier with a ruthenium-containing compound solution in an equivalent manner or in an excessive manner, aging at room temperature, drying, and finally reducing to obtain a ruthenium catalyst loaded on the regular-structure carbon nanofiber; the catalyst can be used for preparing ethylene glycol and propylene glycol by hydrogenolysis of sorbitol; the conversion rate of sorbitol is about 50%, and the conversion rate is not high.

2. A plate-type carbon fiber supported ruthenium catalyst, a preparation method and application thereof, CN 101347731; purifying a plate-type carbon nanofiber carrier, equivalently dipping the plate-type carbon nanofiber by using a ruthenium compound-containing solution, aging at room temperature overnight, drying at 80-120 ℃ for 6-12 hours, and finally reducing to obtain a metal material-loaded catalyst; the catalyst can also be used for preparing ethylene glycol and propylene glycol by sorbitol hydrogenolysis reaction; the conversion rate of sorbitol is about 50%, and the conversion rate is not high.

3. A nickel/copper catalyst and a preparation method thereof and a method for directly preparing 1, 2-hexanediol from celloglycan by using the catalyst, CN 103055870A; firstly, respectively preparing carrier active carbon, ethylenediamine nickel and ethylenediamine copper, then fully and uniformly mixing ethylenediamine copper solution, ethylenediamine nickel solution and active carbon, then adding NaBH₄Carrying out ice-bath reaction on the solution to obtain a catalyst; or soaking nickel ethylenediamine and copper ethylenediamine on the activated carbon in equal volume, roasting, and reducing to obtain the catalyst; the catalyst can be used for catalyzing the direct preparation of 1, 2-hexanediol from the celloglycan; the yield is 30-50%, and the conversion rate is not high.

4. A ruthenium catalyst, a preparation method and application thereof in synthesizing tetrahydrofurfuryl alcohol, CN 102489315A; firstly, adding carrier TiO into aqueous solution of ruthenium-containing salt or aqueous solution of ruthenium-containing salt and metal auxiliary salt₂Then adding a potassium borohydride or hydrazine hydrate solution into the mixed solution to obtain a catalyst; the catalyst is applied to synthesizing tetrahydrofurfuryl alcohol by one-step hydrogenation of furfural; the yield can be more than 99 percent; however, sodium sulfate is required to be added as a solvent for hydrothermal treatment in the preparation process, and the introduction of sodium ions can affect the performance of the catalyst.

6. A preparation method of an active carbon supported noble metal catalyst, CN 102658133A; treating activated carbon in an ethylene diamine tetraacetic acid disodium salt aqueous solution, then stirring in a nitrate solution or a chloride aqueous solution containing noble metals, adding an alkaline aqueous solution to adjust the pH value, continuously stirring, and finally reducing by using hydrazine hydrate or hydrogen to obtain a catalyst; the catalyst can be used for synthesizing DSD acid by catalytic hydrogenation; however, in the preparation process, the activated carbon is treated in an ethylenediaminetetraacetic acid disodium salt aqueous solution, and the pH value of the reaction is adjusted by adopting alkaline solutions such as sodium hydroxide and potassium hydroxide, and the introduced metal ions can influence the performance of the catalyst.

7. Nickel/ruthenium catalysts and processes for aqueous phase reactions, CN 1246077; the catalyst is characterized in that particles formed by a porous carrier are deposited with a certain amount of reduced nickel metal catalytic phase which provides catalyst activity on the porous carrier as a first dispersed phase, and ruthenium metal added on the porous carrier is also deposited on the particles as a second dispersed phase, wherein the amount of the ruthenium metal can effectively prevent agglomeration or sintering of the nickel metal catalytic phase, so that the service life of the catalyst in hydrogenation reaction is prolonged; however, the adopted reaction conditions are 350 ℃ and 340atm, the reaction temperature is slightly higher and the pressure is higher, so that energy consumption and potential safety hazards are caused.

8、Tungsten carbide catalyst supported on mesoporous carbon,preparation and application thereof,EP2495042A1。

The patents for preparing diols from saccharides disclosed so far are mainly:

1. a preparation method of dihydric alcohol, CN 101781166; carrying out hydrogenolysis on glucose by using Raney nickel, ruthenium/carbon, nickel/ruthenium or copper oxide-zinc oxide as a hydrogenolysis catalyst under an alkaline condition; the equipment which is easy to corrode under the alkaline condition can generate potential safety hazard when the reaction is carried out under the pressure of 10MPa to 13 MPa.

2. A preparation method of dihydric alcohol, CN 101781171; carrying out hydrogenolysis on glucose by using nickel-molybdenum-copper doped with chromium or iron, tin and zinc as a hydrogenolysis catalyst under an alkaline condition; the equipment which is easy to corrode under the alkaline condition can generate potential safety hazard when the reaction is carried out under the pressure of 10MPa to 13 MPa.

3. A preparation method of low-carbon polyol, CN 102020531; is made of non-noble metal Ni-W₂C/CNFs as hydrogenolysis catalysts for the hydrogenolysis of saccharides; the total yield of the low-carbon dihydric alcohol is not more than 30 percent, and the selectivity is not high.

4. A method for preparing micromolecular polyol by straw hydrolysis sugar liquid, CN 102898278; firstly, hydrogenation is carried out on soluble sugar solution by taking Raney nickel as a catalyst to obtain sugar alcohol solution, and then heating and hydrocracking are carried out until micromolecular polyol is generated; the total yield of the low-carbon dihydric alcohol is not more than 32 percent, and the selectivity is not high.

5. A preparation method of dihydric alcohol, CN 101781170; using a mixture of sorbitol and mannitol as raw materials, and nickel-molybdenum-copper doped with chromium or iron, tin and zinc as a hydrogenolysis catalyst to hydrogenolyze the mixed sugar alcohol; the amount of the catalyst is 3-10% of the total weight of the water phase, and the excessive use amount easily causes resource waste and water body pollution.

6. Synthetic methods for diols and polyols, CN 101781168; using sucrose as a raw material, and using nickel-molybdenum-copper doped with chromium or iron, tin and zinc as a hydrogenolysis catalyst to perform hydrogenolysis on the sucrose; the amount of the catalyst is 15-30% of the mass of the sucrose, and the excessive use amount easily causes resource waste and water body pollution.

7. A synthetic method of dihydric alcohol and polyhydric alcohol, CN 101781167; using sucrose as a raw material, and using Raney nickel, ruthenium/carbon, nickel/ruthenium or copper oxide-zinc oxide as a hydrogenolysis catalyst to carry out hydrogenolysis on the sucrose; the amount of the catalyst is 15-30% of the mass of the sucrose, and the excessive use amount easily causes resource waste.

Therefore, the method for preparing the novel catalyst for preparing the low-carbon dihydric alcohol by the hydrogenolysis of the glucose is of great significance.

Disclosure of Invention

The first technical problem to be solved by the invention is to provide a preparation method of a catalyst for preparing low-carbon dihydric alcohol by glucose hydrogenolysis; firstly, pretreating a catalyst carrier, and then, impregnating the pretreated catalyst carrier with an auxiliary agent metal solution; then dipping the catalyst carrier loaded with the auxiliary metal by using an active metal solution; finally, introducing hydrogen for reduction to obtain a catalyst for preparing low-carbon dihydric alcohol by glucose hydrogenolysis; the preparation method has the advantages of simple operation, low cost, high efficiency, high activity and high selectivity to low-carbon dihydric alcohol, and the catalyst can regulate and control the position and degree of glucose carbon chain disconnection when catalyzing glucose.

The second technical problem to be solved by the invention is to provide the application of the catalyst for preparing the low-carbon dihydric alcohol by glucose hydrogenolysis, and the catalyst containing a plurality of metal components can be used for catalyzing the glucose hydrogenolysis reaction, and especially can be used for catalyzing the glucose hydrogenolysis reaction in a high-pressure continuous fixed bed, a batch reactor and a hypergravity rotating bed.

The invention provides a preparation method of a catalyst for preparing low-carbon dihydric alcohol by hydrogenolysis of glucose, which comprises 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 a pure solvent or aqueous solution of PEG-200, a pure solvent or aqueous solution of PEG-400, a pure solvent or aqueous solution of PEG-600, a pure solvent or aqueous solution of Triton X-100, an aqueous ammonia solution of EDTA and an aqueous solution of citric acid.

Preferably, 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 pretreated catalyst carrier is immersed in an auxiliary metal solution in an equal volume or in excess, and the catalyst carrier loaded with the auxiliary metal is immersed in an active metal solution in an equal volume or in excess.

Preferably, the mass ratio of the catalyst carrier to the promoter metal is 1: 0.05 to 0.5. The purpose of regulating and controlling the catalytic performance of the active component cannot be achieved due to too little metal of the auxiliary agent; when too much, the active site is easily masked, and the catalytic performance is lowered. The mass ratio of the catalyst carrier to the active metal is 1: 0.005-0.2. The active sites are insufficient due to too little active metal, and the catalytic performance is reduced; too much tends to agglomerate, also reducing the catalytic performance.

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

More preferably, the catalyst carrier is 20-40 mesh silicon dioxide, 20-40 mesh active carbon or 50 nm-15 μm carbon fiber. The silica and the activated carbon with 20-40 meshes are selected as carriers, so that the adverse effects of bed pressure drop and internal diffusion can be avoided; the carbon fiber with the diameter of 50 nm-15 mu m is used as a carrier, so that a larger specific surface area can be formed, and compared with the conventional carbon fiber which is used as a carrier, the carbon fiber has obvious structural advantages in the aspect of industrial application.

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

i, purifying the catalyst carrier;

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

and III, carrying out suction filtration, vacuumizing, drying and roasting on the mixed solution to obtain the pretreated catalyst carrier.

It is understood that the amount, concentration, etc. of the pretreatment solution need not be limited.

Preferably, the I catalyst support is purified as:

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 the reflux liquid.

Preferably, in the purification of the carbon fiber, the reflux liquid drying is to dry the reflux liquid in an air or nitrogen atmosphere at 100-150 ℃ for 6-12 h. The drying effect cannot be achieved when the temperature is too low and the time is too short; if the temperature is too high and the time is too long, the rate of removing the solvent is too high, and the structure and the stability of the catalyst are adversely affected.

Preferably, in II, the heating is: heating for 1-10 h at 80-120 ℃. The pretreatment effect cannot be achieved when the temperature is too low and the time is too short; if the temperature is too high and the time is too long, the pretreatment solution can generate carbon substances at catalyst pore channels and the like, and the impregnation and dispersion of metals are adversely affected.

Preferably, in said 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 suction filtration effect cannot be achieved when the suction filtration time is too short, and the pretreatment solvent entering the carrier pore passage is easily pumped out when the suction filtration time is too long, so that the pretreatment effect is influenced; the carrier hole is vacuumized for 1-2 hours, so that gas in the carrier hole can be expelled to the greatest extent, and the metal loading capacity is ensured;

the drying is as follows:

vacuum drying for 6-15 h at 100-150 ℃; the drying effect cannot be achieved when the temperature is too low and the time is too short; if the temperature is too high and the time is too long, the rate of removing the solvent is too high, and the structure and the stability of the catalyst are adversely affected;

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; the roasting effect cannot be achieved when the temperature is too low and the time is too short (namely, the finally obtained catalyst has stable catalytic performance, a certain crystal form, grain size, void structure and specific surface are obtained, and the mechanical strength of the catalyst is improved); if the temperature is too high and the time is too long, the sintering is easy to occur, so that the surface area of the carrier is not increased or decreased.

Preferably, in the step 2), the catalyst carrier is impregnated with the aid 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 drying effect cannot be achieved when the temperature is too low and the time is too short; if the temperature is too high and the time is too long, the rate of removing the solvent is too high, and the structure and the stability of the catalyst are adversely affected; drying is carried out in air.

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; the roasting effect can not be achieved when the temperature is too low and the time is too short (namely, the finally obtained catalyst has stable catalytic performance, a certain crystal form, grain size, void structure and specific surface are obtained, and the mechanical strength of the catalyst is improved); the catalyst is easy to sinter when the temperature is too high and the time is too long, so that the surface area of the catalyst is not increased or decreased.

Preferably, in the step 3), the catalyst carrier loaded with the assistant metal is impregnated with an active metal solution, and then the catalyst carrier is vacuumized, dried and roasted; wherein,

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; the roasting effect cannot be achieved when the temperature is too low and the time is too short (namely, the finally obtained catalyst has stable catalytic performance, a certain crystal form, grain size, void structure and specific surface are obtained, and the mechanical strength of the catalyst is improved); the catalyst is easy to sinter when the temperature is too high and the time is too long, so that the surface area of the catalyst is not increased or decreased.

Further, in the step 4), reducing for 6-12 hours at 300-500 ℃ in a hydrogen atmosphere. The activation effect cannot be achieved at too low temperature and too short time; if the temperature is too high and the time is too long, the structure and the stability of the catalyst are easily affected.

The invention provides an application of a catalyst for preparing low-carbon dihydric alcohol by glucose hydrogenolysis, and the catalyst can be used for catalyzing the glucose hydrogenolysis reaction.

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

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

Preferably, when the catalyst is used in a 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 catalysis of a batch kettle type reactorIn the glucose hydrogenolysis reaction, 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 at 1400-1800 r/min;

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.

The traditional biomass hydrogenation is carried out in a batch still reactor, the reaction is in a slurry bed mode, hydrogen, glucose solution and catalyst are put into the reactor at one time, and most of the catalyst needs to be added with acid/alkali promoters to promote the hydrogenation reaction due to the influence of the performance of the catalyst.

In the fixed bed reaction, the reaction is in a trickle bed mode, raw material liquid slowly passes through a catalyst bed layer under the action of gravity, and a product is separated from the catalyst bed layer through gravity. The solid catalyst is fixed by quartz wool. Because the residence time is controllable, the aim of regulating and controlling the product distribution can be finally achieved by regulating and controlling the degree of the hydrogenolytic chain scission of the raw material. Compared with batch kettle reaction, the method has better continuity and operability.

In the reaction of the super-gravity rotating bed, the raw materials are rotated into finer liquid drops after entering the reactor, so that the contact effect with a catalyst bed layer is increased, and the raw materials are separated from the catalyst by centrifugal force, thereby greatly increasing the mass transfer efficiency. The hypergravity reactor reduces the reaction residence time by orders of magnitude in the operation process, but at the same time, the proportion of hydrogen dissolved into the liquid phase of the reaction is greatly increased, thereby promoting the hydrogenation chain scission reaction. Furthermore, by adjusting the rotational speed, there can be a choice between residence time and mass transfer rate that is optimal. The high-gravity reactor can be selected from a vertical reactor and a horizontal reactor.

The invention has the following beneficial effects:

1. by controlling specific operating conditions, the surface of the carrier is pretreated by adopting pretreatment solutions such as polyethylene glycol, Triton X-100, EDTA, citric acid and the like to change the types and the number of functional groups on the surface of the carrier (mainly generating oxygen-containing groups such as carboxyl, anhydride, carbonyl and the like), so that the dispersion degree of metal particles is improved, the utilization rate of the metal particles is improved, and the purpose of regulating and controlling the distribution (namely the hydrogen chain scission degree) of reaction products is finally achieved;

2. the addition of the auxiliary metal in the preparation process of the catalyst can adjust the acid property of the catalyst, adjust and control the number of acid centers and finally achieve the aim of adjusting and controlling the hydrogenation chain scission degree of glucose when the catalyst is used for catalyzing glucose;

3. the method is simple to operate, low in cost, high in efficiency and suitable for large-scale production, and the environment pollution is avoided by adopting the environment-friendly pretreatment solution;

4. when the catalyst is used for catalyzing glucose, only the raw material glucose is needed to be dissolved in water, and compared with the method for dissolving glucose in solvents such as dimethyl sulfoxide, valerolactone and the like, the catalyst can save cost and has high solubility; the mass concentration is selected within 50 percent, so that the problems of coking of the glucose raw material in the reactor and the like can be avoided; the activity is high, and the selectivity to low-carbon dihydric alcohol is high;

5. when the hydrogenolysis reaction of glucose is catalyzed in three reactors, namely a fixed bed reactor, a batch still reactor and a rotating bed reactor, no alkaline accelerant is needed to be added, and the damage to equipment is reduced to the minimum;

6. when the catalyst is used for catalyzing glucose, industrial glucose can be used as a raw material, and fermentation industry such as wine making industry and the like can also be used, and byproducts and even waste materials of rich polyol, aldehyde and acid can be used as the raw material.

Detailed Description

For a better understanding of the present invention, the following examples are provided to further illustrate the present invention and the scope of the present invention shall include the full scope of the claims but not be limited thereto.

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

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

Propylene glycol selectivity (%) = (number of moles of carbon in propylene glycol/number of moles of carbon in glucose participating in reaction) x 100

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

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

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

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

Example 1

A preparation method of a catalyst for preparing low-carbon dihydric alcohol by hydrogenolysis of glucose comprises the following steps:

1. pretreatment of silica supports

I, weighing 5g of silicon dioxide, roasting the silicon dioxide in an air atmosphere at 200 ℃ for 2h, cooling the silicon dioxide to room temperature, taking out the silicon dioxide, and transferring the silicon dioxide to a three-neck flask;

II, adding 80mL of PEG-200 pure solution into the flask, heating to 120 ℃ by using an electric heating sleeve, heating for 2 hours, and cooling to room temperature;

and III, performing suction filtration for 1 hour at room temperature by using a Buchner funnel, taking out filter residues, vacuumizing for 1 hour, then placing the filter residues in a vacuum drying oven, performing vacuum drying for 10 hours at 120 ℃, finally roasting for 2 hours at 500 ℃ in an air atmosphere, cooling to room temperature, and packaging for later use.

2. Supporting promoter metal on silicon dioxide

① dissolving ammonium metatungstate precursor in deionized water to obtain ammonium metatungstate aqueous solution, treating with SiO at a loading rate of 10wt% W₂Equal amount of impregnation of the carrier;

②, vacuumizing for 1h, drying at 120 deg.C in air atmosphere for 10h, and calcining at 500 deg.C in air atmosphere for 2h, i.e. successfully loading assistant metal W to PEG-200 pretreated SiO₂On a carrier.

3. Supporting reactive metals on silica

1) Adding a certain amount of RuCl₃nH2O precursor dissolved in deionized water to formulate RuCl₃An aqueous solution of the above W-supported SiO₂The carrier is equivalently impregnated with the load ratio of 1wt% Ru;

2) the same procedure as 2 ② was repeated to obtain Ru-W/SiO₂(PEG-200) catalyst (1 wt% Ru-10wt% W).

4. Activating catalyst

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

The activated catalyst is characterized and analyzed, the average particle size is 2nm, and the catalyst is uniformly dispersed and free from agglomeration.

Comparative example 1

The same as example 1, the changes are:

without any pretreatment step.

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

The activated catalyst is characterized and analyzed, the average grain diameter is 10nm, and the agglomeration phenomenon exists.

Example 2

1. pretreatment of activated carbon AC

I, weighing 5g of activated carbon, roasting the activated carbon in a nitrogen atmosphere at 200 ℃ for 2h, cooling the activated carbon to room temperature, taking out the activated carbon, and transferring the activated carbon to a three-neck flask;

II, adding 80mL of PEG-400 pure solution into the flask, heating to 120 ℃ by using an electric heating sleeve, heating for 2 hours, and cooling to room temperature;

and III, performing suction filtration for 1 hour at room temperature by using a Buchner funnel, taking out filter residues, vacuumizing for 1 hour, then placing the filter residues in a vacuum drying oven, performing vacuum drying for 10 hours at 120 ℃, finally roasting for 2 hours at 500 ℃ in a nitrogen atmosphere, cooling to room temperature, and packaging for later use.

2. Loading assistant metal on active carbon

Dissolving a certain amount of ammonium molybdate precursor in deionized water to prepare an ammonium molybdate aqueous solution, and soaking the ammonium molybdate aqueous solution on the treated AC carrier in equal amount at a loading rate of 10wt% of Mo;

secondly, after dipping, vacuumizing for 1 h; then, drying for 10 hours at 120 ℃ in an air atmosphere; after drying, the mixture is roasted for 2h at 500 ℃ in a nitrogen atmosphere, namely the auxiliary agent metal Mo is successfully loaded on the AC carrier pretreated by PEG-400.

3. Loading active metal on active carbon

1) Dissolving a certain amount of nickel nitrate hexahydrate precursor in deionized water to prepare a nickel nitrate aqueous solution, and equivalently impregnating the nickel nitrate aqueous solution on the W-loaded AC carrier at a loading rate of 10wt% of Ni;

2) as 2 ②, a Ni-Mo/AC (PEG-400) catalyst (10wt% Ni-10wt% Mo) was obtained.

4. Activating catalyst

An activated catalyst (10wt% Ni-10wt% Mo) was obtained in the same manner as in example 1.

Comparative example 2

The same as example 2, the changes are:

without any pretreatment step.

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

Example 3

1. pretreatment of carbon fiber CNFs

I, weighing 5g of carbon fiber carrier, placing the carbon fiber carrier in a three-neck flask, adding 80mL of nitric acid solution into the flask, heating to 80 ℃ by using an electric heating jacket, heating for 2h, condensing, refluxing and cooling to room temperature; subsequently, drying was carried out at 120 ℃ for 10h in an air atmosphere;

II, adding 80mL of PEG-600 pure solution into the flask, heating to 120 ℃ by using an electric heating sleeve, heating for 2 hours, and cooling to room temperature;

III is as in example 1.

2. Loading assistant metal on carbon fiber

Dissolving a certain amount of zirconyl nitrate precursor in deionized water to prepare a zirconium nitrate aqueous solution, and soaking the zirconium nitrate aqueous solution on the treated CNFs carrier at equal amount by the load rate of 15wt% of Zr;

secondly, after dipping, vacuumizing for 1 h; then, drying for 10 hours at 120 ℃ in an air atmosphere; after drying, roasting for 2h at 500 ℃ in a nitrogen atmosphere, namely successfully loading the auxiliary agent zirconium oxide on the PEG-600 pretreated CNFs carrier.

3. Loading active metal on carbon fiber

1) Adding a certain amount of RuCl₃·nH₂Dissolving O precursor in deionized water to prepare RuCl₃An aqueous solution of the above SiO supported with Zr₂The carrier is equally impregnated with 2wt% Ru;

2) the same 2 is adopted to obtain the Ru-Zr/CNFs (PEG-600) catalyst.

4. Activating catalyst

An activated catalyst (2 wt% Ru-15wt% Zr) was obtained in the same manner as in example 1.

Example 4

the same as example 1, the changes are:

1. add 80mL TX-100 neat solution for pretreatment.

2. Dissolving a certain amount of aluminum nitrate nonahydrate precursor in deionized water to prepare an aluminum nitrate aqueous solution, and treating SiO with the loading rate of 20wt% of Al₂Equal amount of impregnation of the carrier; obtaining SiO loaded with Al₂And (3) a carrier.

3. Dissolving a certain amount of nickel nitrate hexahydrate precursor in deionized water to prepare nickel nitrate aqueous solution, and dissolving the nickel nitrate aqueous solution in SiO loaded with Al₂The carrier is equally impregnated with Ni with a loading rate of 15 wt%; obtaining Ni-Al/SiO₂(TX-100) catalyst.

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

Example 5

the same as example 2, the changes are:

1. 80mL of an aqueous solution of EDTA (10wt% EDTA) in ammonia was added to the flask, and the temperature was raised to 90 ℃ using an electric heating mantle and heated for 2 hours.

2. Dissolving a certain amount of cobalt nitrate precursor in deionized water to prepare a cobalt nitrate aqueous solution, and soaking the cobalt nitrate aqueous solution on the treated AC carrier in equal amount at a loading rate of 20wt% of Co; the AC support loaded with Co was obtained.

3. Adding RuCl₃·nH₂Dissolving O precursor in deionized water to prepare RuCl₃An aqueous solution impregnated in an equal amount on the Co-supported AC support at a loading rate of 1wt% Ru; a Ru-Co/AC (10wt% EDTA) catalyst was obtained.

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

Example 6

the same as example 3, the changes are:

1. 80mL of an aqueous solution of citric acid (10wt% citric acid) was added to the flask, and the temperature was raised to 90 ℃ using an electric heating mantle and heated for 2 hours.

2. Dissolving a certain amount of ammonium metatungstate precursor in deionized water to prepare an ammonium metatungstate aqueous solution, and soaking the ammonium metatungstate aqueous solution on the treated CNFs carrier in equal amount at a load rate of 15wt% W; and obtaining the W-loaded CNFs carrier.

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

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

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

Example 7

the same as example 1, the changes are:

1. to the flask was added 80mL of 80V% aqueous PEG-200 solution.

2. Dissolving a certain amount of ammonium molybdate precursor in deionized water to prepare an ammonium molybdate aqueous solution, and treating SiO with a loading rate of 15wt% Mo₂The support is impregnated in equal amounts.

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

Example 8

the same as example 2, the changes are:

1. to the flask was added 80mL of a 60V% aqueous PEG-200 solution.

2. A certain amount of zirconyl nitrate precursor is dissolved in deionized water to prepare a zirconium nitrate aqueous solution, and the zirconium nitrate aqueous solution is impregnated on the treated AC carrier in equal amount at a loading rate of 20wt% of Zr.

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

Example 9

the same as example 3, the changes are:

1. to the flask was added 80mL of a 40V% aqueous PEG-200 solution.

2. A certain amount of aluminum nitrate nonahydrate precursor is dissolved in deionized water to prepare an aluminum nitrate aqueous solution, and the aluminum nitrate aqueous solution is uniformly impregnated on the treated CNFs carrier at a loading rate of 10wt% of Al.

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

Example 10

the same as example 5, the changes are:

1. to the flask was added 80mL of an aqueous solution of EDTA in ammonia (20 wt% EDTA).

2. The treated AC support was impregnated at a loading of 10wt% Co in equal amounts.

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

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

Example 11

the same as example 6, the changes are:

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

3. Adding RuCl₃·nH₂Dissolving O precursor in deionized water to prepare RuCl₃An aqueous solution was impregnated equally on W-loaded CNFs supports at a loading of 2wt% Ru.

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

Example 12

the same as example 2, the changes are: firstly, dissolving a certain amount of ammonium metatungstate precursor in deionized water to prepare an ammonium metatungstate aqueous solution, and soaking the ammonium metatungstate aqueous solution on the treated AC carrier in equal amount at a load rate of 10wt% W; then 10wt% Mo and 10wt% Ni were impregnated according to the procedure of example 2; finally, the activated catalyst (10wt% Ni-10wt% Mo-10wt% W) is obtained.

Example 13

the same as example 7, the changes are: firstly, a certain amount of ammonium metatungstate precursor is dissolved in deionized water to prepare an ammonium metatungstate aqueous solution, and SiO treated by a load rate of 10wt% W₂The support is impregnated in equal amounts. Then 15wt% Mo and 1wt% Ru were impregnated according to the procedure of example 7; finally, the activated catalyst (1 wt% Ru-15wt% Mo-10wt% W) is obtained.

Example 14

the same as example 11, the changes are: first, 15wt% W was impregnated following the procedure of example 11; then dissolving a certain amount of nickel nitrate hexahydrate precursor in deionized water to prepare a nickel nitrate aqueous solution, and equivalently impregnating the treated CNFs carrier at a loading rate of 10wt% Ni; finally 2wt% Ru was impregnated following the procedure of example 11; finally, the activated catalyst (2 wt% Ru-10wt% Ni-15wt% W) is obtained.

Example 15

The application of the catalyst for preparing the low-carbon dihydric alcohol by glucose hydrogenolysis comprises the following steps:

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

1. High-pressure continuous fixed bed reactor

TABLE 1 reaction conditions of fixed bed reactor

Numbering	Temperature (. degree.C.)	Pressure (MPa)	Mass of catalyst (g)	Glucose concentration (wt%)	Liquid phase 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 evaluation table of catalytic results of fixed bed reactor

2. Batch kettle type reactor

TABLE 3 reaction conditions of batch kettle reactors

Numbering	Temperature (. degree.C.)	Pressure (MPa)	Mass of catalyst (g)	Glucose concentration (wt%)	Rotating 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

TABLE 4 evaluation of catalytic results for batch tank reactor

3. High-gravity rotating bed reactor

TABLE 5 reaction conditions of the hypergravity rotating bed reactor

Table 6 table for evaluating catalytic results of supergravity rotary bed reactor

"lower glycols" include ethylene glycol, propylene glycol and butylene glycol. Wherein, 1, 2-propylene glycol and 1, 2-butylene glycol are respectively used as the propylene glycol and the butylene glycol which have absolute dominance in selectivity. As can be seen from tables 2,4 and 6, the product contains polyhydroxy compounds such as sorbitol, xylitol, erythritol, other (mannitol, 5-hydroxymethylfurfural, 1,2, 4-butanetriol) and glycerol besides the lower dihydric alcohol. Wherein, the selectivity of the xylitol and the erythritol is far lower than that of the lower dihydric alcohol, the yield of the glycerol is between that of the xylitol and the erythritol, and the contents of the 5-hydroxymethylfurfural and the 1,2, 4-butanetriol are extremely low.

As can be seen from the catalytic results of tables 2,4 and 6, the nickel-based and ruthenium-based catalysts show different conversions and selectivities in three different reactors. Thus, fixed bed reactors, batch tank reactors and rotating bed reactors are advantageous for different operating conditions and products of interest.

Example 16

1) pretreating a catalyst carrier:

i, purifying the catalyst carrier;

the catalyst carrier is silica. The pretreatment solution was a mixture of pure PEG-200 and pure PEG-400 solvents (volume ratio 1: 1). The assistant metal solution is W, Mo aqueous solution; the active metal solution is an aqueous solution of Ru. The mass ratio of the catalyst carrier to the auxiliary metal is 1: 0.05; the mass ratio of the catalyst carrier to the active metal is 1: 0.005.

example 17

The difference from example 16 is that:

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

example 18

The difference from example 16 is that:

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

the catalyst is used for the glucose catalytic hydrogenolysis reaction of a hypergravity rotating bed, and the process conditions are as follows: the temperature is 215 ℃, the pressure is 3MPa, and the liquid space velocity is 500h^-1And the rotating speed is 200 r/min.

Example 19

The difference from example 16 is that:

the catalyst carrier is 20-mesh active carbon.

In I: and (3) purification: calcining the activated carbon for 2 hours at 150 ℃ in a nitrogen atmosphere.

In II: the heating is as follows: heating at 80 deg.C for 1 h;

in III: filtering the mixed solution at room temperature for 1h, taking out the filter residue, and vacuumizing for 1 h; the drying is as follows: vacuum drying at 100 deg.C for 6 h; the roasting is as follows: roasting for 2 hours at 300 ℃ in a nitrogen atmosphere.

2) After dipping the catalyst carrier in an auxiliary agent metal solution, vacuumizing, drying and roasting; wherein, the drying is as follows: drying at 100 deg.C for 6 h; the roasting is as follows: roasting for 2 hours at 300 ℃ in a nitrogen atmosphere.

3) After dipping the catalyst carrier loaded with the auxiliary metal by using an active metal solution, vacuumizing, drying and roasting; wherein, the drying is as follows: drying at 100 deg.C for 6 h; the roasting is as follows: roasting for 2 hours at 300 ℃ in a nitrogen atmosphere.

4) In a hydrogen atmosphere, the mixture is reduced for 6h at 300 ℃.

The catalyst is used for the glucose catalytic hydrogenolysis reaction of a hypergravity rotating bed, and the process conditions are as follows: the temperature is 195 ℃, the pressure is 5MPa, and the liquid space velocity is 1h^-1And the rotating speed is 1500 r/min.

Example 20

The difference from example 16 is that:

the catalyst carrier is 30-mesh active carbon.

In I: and (3) purification: calcining the activated carbon for 3 hours at 250 ℃ in a nitrogen atmosphere.

In II: the heating is as follows: heating at 120 deg.C for 10 h;

in III: filtering the mixed solution at room temperature for 3h, taking out the filter residue, and vacuumizing for 2 h; the drying is as follows: vacuum drying at 150 deg.C for 15 h; the roasting is as follows: roasting for 6h at 500 ℃ in a nitrogen atmosphere.

2) After dipping the catalyst carrier in an auxiliary agent metal solution, vacuumizing, drying and roasting; wherein, the drying is as follows: drying at 150 deg.C for 15 h; the roasting is as follows: roasting for 6h at 500 ℃ in a nitrogen atmosphere.

3) After dipping the catalyst carrier loaded with the auxiliary metal by using an active metal solution, vacuumizing, drying and roasting; wherein, the drying is as follows: drying at 150 deg.C for 15 h; the roasting is as follows: roasting for 6h at 500 ℃ in a nitrogen atmosphere.

4) In a hydrogen atmosphere, the mixture is reduced for 12 hours at 500 ℃.

The catalyst is used for the glucose catalytic hydrogenolysis reaction of a batch kettle type reactor, and the process conditions are as follows: the temperature is 215 ℃, the pressure is 5MPa, and the liquid space velocity is 300h^-1And the rotating speed is 1800 r/min.

Example 21

The difference from example 16 is that:

the catalyst carrier is 50nm carbon fiber.

In I: and (3) purification: the carbon fiber was placed in 50mL of nitric acid, heated at 60 ℃ for 2h and condensed to reflux, and then the reflux was dried at 100 ℃ for 6h in an air atmosphere.

In II: the heating is as follows: heating at 80 deg.C for 1 h;

2) After dipping the catalyst carrier in an auxiliary agent metal solution, vacuumizing, drying and roasting; wherein, the drying is as follows: drying for 6-15 h at 120 ℃; the roasting is as follows: roasting for 4 hours at 400 ℃ in a nitrogen atmosphere.

3) After dipping the catalyst carrier loaded with the auxiliary metal by using an active metal solution, vacuumizing, drying and roasting; wherein, the drying is as follows: drying at 150 deg.C for 15 h; the roasting is as follows: carbon fiber: roasting for 4 hours at 400 ℃ in a nitrogen atmosphere.

4) In a hydrogen atmosphere, the mixture is reduced for 8 hours at 400 ℃.

The catalyst is used for catalyzing glucose hydrogenolysis reaction; the concentration of the aqueous glucose solution was 2 wt%. The catalyst is used for the glucose catalytic hydrogenolysis reaction of a batch kettle type reactor, and the process conditions are as follows: the temperature is 195 ℃, the pressure is 3MPa, and the liquid space velocity is 1h^-1And the rotating speed is 1400 r/min.

Example 22

The difference from example 16 is that:

the catalyst carrier is 15 μm carbon fiber.

In I: and (3) purification: the carbon fiber was placed in 120mL of nitric acid, heated at 90 ℃ for 3 hours and condensed to reflux, and then the reflux was dried at 150 ℃ for 12 hours in a nitrogen atmosphere.

In II: the heating is as follows: heating at 120 deg.C for 10 h;

2) After dipping the catalyst carrier in an auxiliary agent metal solution, vacuumizing, drying and roasting; wherein, the drying is as follows: drying at 100 deg.C for 6 h; the roasting is as follows: roasting for 2 hours at 500 ℃ in a nitrogen atmosphere.

3) After dipping the catalyst carrier loaded with the auxiliary metal by using an active metal solution, vacuumizing, drying and roasting; wherein, the drying is as follows: drying at 100 deg.C for 15 h; the roasting is as follows: roasting for 2 hours at 300 ℃ in a nitrogen atmosphere.

4) In a hydrogen atmosphere, the mixture is reduced for 12 hours at 300 ℃.

The catalyst is used for catalyzing glucose hydrogenolysis reaction; the concentration of the aqueous glucose solution was 50 wt%. The glucose catalytic hydrogenolysis reaction is carried out in a high-pressure continuous fixed bed under the following process conditions: the temperature is 175 ℃, the pressure is 3MPa, and the liquid space velocity is 1h^-1。

Example 23

The difference from example 16 is that:

the catalyst carrier is 30-mesh silica.

In I: and (3) purification: calcining the silicon dioxide for 2h at 150 ℃ in an air atmosphere.

In II: the heating is as follows: heating at 80 deg.C for 1 h;

in III: filtering the mixed solution at room temperature for 1h, taking out the filter residue, and vacuumizing for 1 h; the drying is as follows: vacuum drying at 100 deg.C for 6 h; the roasting is as follows: roasting for 2 hours at 300 ℃ in an air atmosphere.

2) After dipping the catalyst carrier in an auxiliary agent metal solution, vacuumizing, drying and roasting; wherein, the drying is as follows: drying at 100 deg.C for 6 h; the roasting is as follows: roasting for 2 hours at 300 ℃ in an air atmosphere.

3) After dipping the catalyst carrier loaded with the auxiliary metal by using an active metal solution, vacuumizing, drying and roasting; wherein, the drying is as follows: drying at 100 deg.C for 6 h; roasting in air atmosphere at 300 deg.c for 2 hr.

4) In a hydrogen atmosphere, the mixture is reduced for 6h at 300 ℃.

The catalyst is used to catalyze the glucose hydrogenolysis reaction; the concentration of the aqueous glucose solution was 25 wt%. The glucose catalytic hydrogenolysis reaction is carried out in a high-pressure continuous fixed bed under the following process conditions: the temperature is 215 ℃, the pressure is 5MPa, and the liquid space velocity is 300h^-1。

Example 24

The difference from example 16 is that:

the catalyst carrier is 20-mesh silica.

In I: and (3) purification: calcining the silicon dioxide for 3 hours at 250 ℃ in an air atmosphere.

In II: the heating is as follows: heating at 120 deg.C for 10 h;

in III: filtering the mixed solution at room temperature for 3h, taking out the filter residue, and vacuumizing for 2 h; the drying is as follows: vacuum drying at 150 deg.C for 15 h; the roasting is as follows: roasting for 6h at 500 ℃ in an air atmosphere.

2) After dipping the catalyst carrier in an auxiliary agent metal solution, vacuumizing, drying and roasting; wherein, the drying is as follows: drying at 150 deg.C for 15 h; the roasting is as follows: roasting for 6h at 500 ℃ in an air atmosphere.

3) After dipping the catalyst carrier loaded with the auxiliary metal by using an active metal solution, vacuumizing, drying and roasting; wherein, the drying is as follows: drying at 150 deg.C for 15 h; the roasting is as follows: roasting for 6h at 500 ℃ in an air atmosphere.

4) In a hydrogen atmosphere, the mixture is reduced for 12 hours at 500 ℃.

The catalyst is used for the glucose catalytic hydrogenolysis reaction of a batch kettle type reactor, and 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^-1The rotation speed is 1400 to 1800 r/min.

It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.

Claims

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;

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 ℃;

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 ℃;

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；