CN111389395B

CN111389395B - Ruthenium iridium catalyst, preparation method thereof and application of ruthenium iridium catalyst in hydrogenolysis reaction of 5-hydroxymethylfurfural

Info

Publication number: CN111389395B
Application number: CN202010373283.XA
Authority: CN
Inventors: 方文浩; 王英浩; 曹秋娥
Original assignee: Yunnan University YNU
Current assignee: Yunnan University YNU
Priority date: 2020-05-06
Filing date: 2020-05-06
Publication date: 2022-09-30
Anticipated expiration: 2040-05-06
Also published as: CN111389395A

Abstract

The invention discloses a ruthenium-iridium catalyst, a preparation method thereof and application of the ruthenium-iridium catalyst in 5-hydroxymethylfurfural hydrogenolysis reaction, wherein a ruthenium-iridium catalyst carrier is activated carbon, and supported metals are ruthenium and iridium. The catalyst does not use any corrosive acid solution in the catalytic reaction, can efficiently, cheaply, environmentally, safely and stably convert 5-hydroxymethylfurfural into 2, 5-dimethylfuran, the conversion rate of a reactant 5-hydroxymethylfurfural reaches 100%, the yield of a target product 2, 5-dimethylfuran reaches 97%, and a byproduct only contains trace corrosive substances.

Description

Ruthenium-iridium catalyst, preparation method thereof and application of ruthenium-iridium catalyst in hydrogenolysis reaction of 5-hydroxymethylfurfural

Technical Field

The invention relates to a catalyst, in particular to a ruthenium iridium catalyst, a preparation method thereof and application thereof in 5-hydroxymethylfurfural hydrogenolysis reaction.

Background

The stable supply of energy is crucial to the development of economic society, and at present, the main energy of human beings still comes from non-renewable fossil raw materials such as crude oil, coal, natural gas and the like. However, the large amount of fossil raw materials produced and burned worldwide has caused problems of environmental pollution, energy shortage, global warming, and the like. In recent years, the real pressure of environmental pollution and energy shortage has prompted worldwide researchers to look for new green renewable energy sources. Lignin biomass is a sustainable, renewable source of chemical energy, with the ability to be converted into a variety of important liquid fuels and high value-added chemicals and the potential to replace traditional fossil feedstock, with huge reserves in nature sufficient to meet the growing energy needs. 5-hydroxymethylfurfural obtained from lignin biomass is one of the most important platform compounds in the field of lignin biomass conversion. It can be used for preparing various high-quality liquid fuels, such as 2, 5-dimethylfuran, 5-ethoxymethylfurfural, levulinic acid, 2, 5-furandimethanol, 2, 5-furandicarbaldehyde, ethyl levulinate and the like. Wherein, the 5-hydroxymethyl furfural can produce the fuel additive 2, 5-dimethyl furan with wide application prospect, and has received wide attention.

2, 5-dimethylfuran is considered to be a very promising new liquid biofuel. It has many advantages over current biofuel ethanol: 1. has higher energy density (31.5MJ/L) and is basically close to gasoline; 2. the product has a higher boiling point (92-94 ℃), and is not easy to volatilize; 3. the octane number (119) is higher, and the explosion-proof performance is better; 4. is insoluble in water and easy to transport and store; 5. the energy consumption in the separation process is low, and the production cost is low. The advantages enable the 2, 5-dimethyl furan to become an excellent liquid biofuel source, and the liquid fuel is a renewable liquid fuel which is more suitable and has better development prospect than the mainstream ethanol liquid fuel.

The research work of preparing 2, 5-dimethylfuran by hydrogenolysis reaction of 5-hydroxymethylfurfural is still in the initial stage, is one of the hot problems of research of numerous scientists in the field of biomass energy at home and abroad, but has a plurality of problems to be overcome:

1. 5-hydroxymethylfurfural is used for synthesizing 2, 5-dimethylfuran, and corrosive acid solutions such as sulfuric acid, hydrochloric acid, formic acid and the like and low-toxicity organic solvents such as methanol, dioxane and the like are required to be added into a part of a catalytic system. These acid solutions and organic solvents cause environmental pollution and harm to the personal safety of reaction operators, so that acid-resistant, corrosion-resistant and highly-closed reaction equipment is required, and the cost is increased.

2. The requirements for the catalyst support are high: part of the catalyst support requires the use of high cost graphene or carbon nanotubes. The expensive price of graphene and carbon nanotubes (several hundreds to thousands yuan per gram) causes huge cost burden and reduces economic benefit, which is not beneficial to industrial mass production.

3. Most catalytic systems require harsh conditions such as:

the high efficiency of the catalyst depends on supporting expensive noble metals: at present, the basic research and development of the catalytic reaction mainly focuses on loading expensive noble metals such as platinum, palladium and the like; the loading required for such catalysts is also relatively high, and basically the mass fraction of the noble metal loading needs to be around 3-10%. Thus resulting in a substantial increase in the cost of the catalyst.

If non-noble metals such as copper, zinc and nickel with low cost are used as the active components of the catalyst, the reaction needs to be kept at high temperature, high pressure and long time to ensure the reaction is complete. The metal waste liquid generated during the reaction can pollute the water body, and the catalyst has large dosage and low economic benefit. The reaction temperature is higher: generally 180 ℃ to 240 ℃, the energy consumption is higher, and the reduction of the reaction temperature is compensated by adding acid solution or organic solvent or increasing the pressure of hydrogen; the reaction time is longer: most of the catalytic reactions need to be carried out for about 18-24 hours, so that the deep reduction of 5-hydroxymethylfurfural is easily caused, and byproducts are generated; the reaction pressure is higher: most catalytic reactions need to be carried out under the hydrogen pressure of 3-6MPa, which is easy to cause waste of hydrogen and potential danger.

The defects of the prior catalyst are unfavorable for practical application, influence on economic benefit, and have potential safety hazards of high pressure, high temperature, corrosiveness and low toxicity reaction solutions in the production process.

In addition, the 5-hydroxymethylfurfural molecule is an active organic substance, the molecule contains an aldehyde group and a hydroxymethyl group, the degree of the hydrogenation reduction reaction of the two functional groups is difficult to control, the product distribution is complex, and a large number of byproducts are produced. The double bond of the furan ring of the target product 2, 5-dimethylfuran is often deeply reduced to generate 2, 5-dimethyltetrahydrofuran, or the furan ring is opened to produce a chain compound. Resulting in low yield of the target product 2, 5-dimethylfuran and extremely difficult separation and purification.

Therefore, the key to realizing breakthrough in this field lies in developing a catalyst capable of efficiently, cheaply, environmentally, safely and stably converting 5-hydroxymethylfurfural into 2, 5-dimethylfuran.

Disclosure of Invention

The invention aims to provide a ruthenium iridium catalyst, a preparation method thereof and application of the ruthenium iridium catalyst in 5-hydroxymethylfurfural hydrogenolysis reaction, and solves the problems that the cost of noble metal used by the existing catalyst is high, or the activity of catalysts loaded with copper, zinc, nickel and the like is not high, the target yield is low, and the pollution of waste liquid to the environment is serious.

In order to solve the technical problem, the invention adopts the following technical scheme:

a ruthenium-iridium catalyst has active carbon as carrier and ruthenium and iridium as supported metals.

Preferably, the theoretical loading of iridium is 0.1 to 2.0wt% and the theoretical loading of ruthenium is 0.1 to 8.0 wt%.

Preferably, a solution containing ruthenium ions and iridium ions is prepared, the pH value of the solution is adjusted to be 4-9, then polyvinylpyrrolidone or polyvinyl alcohol with the molecular weight of 5000-30000 and activated carbon are sequentially added for reaction in a dark place, and after the reaction is finished, a solid phase is separated and dried and reduced to obtain the ruthenium-iridium catalyst.

Preferably, the mass ratio of the polyvinylpyrrolidone or the polyvinyl alcohol to the activated carbon is 9: 300-400.

Preferably, the reaction time is 4 to 8 hours.

Preferably, after the reaction is finished, the reaction solution is filtered, then filtered and washed by water with the temperature of 80-100 ℃ until the filtrate becomes colorless transparent liquid, and the solid phase on the filter membrane is dried, wherein the filter membrane used for filtering is an organic phase filter membrane with the specification of 50mm multiplied by 0.08um-50mm multiplied by 0.2 um.

Preferably, the drying temperature is 80-100 ℃ and the drying time is 10-24 h.

Preferably, the reduction treatment is to reduce the catalyst for 30-120min under a hydrogen flow at 250-400 ℃.

An application of ruthenium iridium catalyst in 5-hydroxymethylfurfural hydrogenolysis reaction is characterized in that 5-hydroxymethylfurfural, the catalyst and a solvent are placed in a reaction kettle, air in the reaction kettle is discharged, hydrogen is filled in the reaction kettle, and the 5-hydroxymethylfurfural hydrogenolysis reaction is carried out.

Preferably, the mass ratio of the catalyst to the solvent to the 5-hydroxymethylfurfural is 45: 300-600: 100-150 ℃, the hydrogen pressure is 1.5-2.5MPa, the reaction time is 3-20h, and the reaction temperature is 140-200 ℃.

Compared with the prior art, the invention has the beneficial effects that:

the catalyst does not use any corrosive acid solution in the catalytic reaction, has small harm to reaction operators and can neglect environmental pollution.

The carrier used by the catalyst is low-cost, non-toxic and harmless activated carbon powder, so that the product is easy to separate and the catalyst is easy to recover.

The catalyst is an activated carbon-loaded ruthenium-iridium alloy nanoparticle reported for the first time. The ruthenium-iridium is used as a catalytic active metal, the price and the acquisition difficulty of a carrier and the metal are low, the total load mass fraction is only 1.5%, the cost is low compared with noble metals such as platinum, palladium and the like, and the catalytic efficiency is higher compared with non-noble metals such as copper, zinc, nickel and the like.

The preparation method optimizes the preparation conditions of the catalyst, and the influence of the ruthenium-iridium bimetallic ratio on the reaction is adjusted; microscopically high dispersion of the metal nanoparticles is achieved and the reaction achieves optimal conversion and yield.

The catalyst can improve the reaction speed, reduce the reaction temperature and pressure, and ensure relatively safe and efficient reaction.

The method optimizes the metal ratio of ruthenium to iridium and the preparation method of the catalyst, and improves the activity of the catalyst. The conversion rate of the reactant 5-hydroxymethylfurfural reaches 100 percent, the yield of the target product 2, 5-dimethylfuran reaches 97 percent, and the byproduct has only trace corrosive substances.

Drawings

FIG. 1 is a diagram of the reaction route and reaction intermediates for the preparation of 2, 5-dimethylfuran from 5-hydroxymethylfurfural;

FIG. 2 is a transmission electron micrograph of 0.5% Ir-1% Ru/C catalyst;

FIG. 3 is a graph of the particle size distribution of the corresponding iridium-ruthenium alloy nanoparticles in a 0.5% Ir-1% Ru/C catalyst;

FIG. 4 is a graph of energy dispersive X-ray-line scanning spectral signals for 0.5% Ir-1% Ru/C catalyst.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. The chemical reagents and solvents used in the examples of the present application are analytically pure; the stirring adopts a magnetic stirrer stirring mode. The electrochemical determination conditions are all within the potential range of 0.0-1.0V.

Example 1:

the preparation process of the target catalyst is 0.5% Ir-1% Ru/C:

firstly, 1mL of RuCl with the concentration of 5mg/mL ₃ ·3H ₂ O solution and 1mL of IrCl with the concentration of 2.5mg/mL ₃ ·xH ₂ The O solution is poured into a 250ml round-bottom flask, and then 100ml deionized water is poured into the flask to be stirred uniformly. While stirring, a 1mg/mL NaOH solution was added dropwise until the pH of the solution was around 5. Adding 18mg of polyvinylpyrrolidone with average molecular weight of 10000, and stirring for 15 min. 492.5mg of activated carbon are then added, so that the theoretical metal loading ratio is 0.5% iridium: 1% ruthenium. After stirring for 6 hours in the absence of light, the above solution was filtered with suction. The filtrate was washed with 1.5L of deionized water at 90 ℃ with suction until the filtrate became a colorless transparent liquid. The filtration membrane used in the suction filtration is an organic phase filtration membrane with the specification of 50mm multiplied by 0.08 um. The catalyst powder on the filter paper was then placed in an 80 ℃ oven to dry overnight. After drying, the catalyst was subjected to hydrogen reduction treatment, and the catalyst was reduced under a hydrogen stream at 350 ℃ for 30 min. And after the catalyst is prepared, drying and storing in dark for later use.

The performance test operation process of the 0.5 percent Ir-1 percent Ru/C catalyst comprises the following steps:

90mg of catalyst, 10mL of tetrahydrofuran solvent, 2mmol of 5-hydroxymethylfurfural and stirring magnetons are poured into a polytetrafluoroethylene lining of a high-pressure reaction kettle in sequence. After the reaction kettle is installed, purging with 0.5MPa argon gas for three times. Then, the residual gas in the kettle is pumped by a high-pressure pump, and then the kettle is connected with a hydrogen steel cylinder, and hydrogen with 0.5MPa is introduced for purging three times. The hydrogen pressure was then increased to 2.0MPa, maintaining the aeration process for about 1 minute. And finally, placing the reaction kettle into a high-temperature magnetic stirring oil bath kettle with the preset temperature of 170 ℃, wherein the magnetic stirring speed is 800rpm, and reacting for 18 hours. And after the reaction is finished for 18 hours, putting the reaction kettle into ice water for cooling for 5-10min, releasing gas in the kettle, sucking reaction liquid in the kettle by using an injector, and filtering by using a 0.45nm filter head to obtain filtrate. The filtrate was quantitatively analyzed using a model 1310 gas chromatograph, model Sammerfel TRACE, equipped with a TR-5 capillary column and FID detector.

The catalyst in the application catalyzes a reactant 5-hydroxymethylfurfural to carry out hydrogenolysis reaction to obtain a target product 2, 5-dimethylfuran, and the reaction mechanism is shown as a path 2 in fig. 1. The structure and the particle size of the catalyst obtained in example 1 are characterized, and the results are shown in fig. 2 and fig. 3, and it is clear from fig. 2 and fig. 3 that the metal particles of the catalyst have diameters of 2-6nm, are uniformly supported on the surface of the activated carbon support, and are nano-sized catalysts. The EDS test of the catalyst obtained in example 1 shows that the concentration signals of ruthenium and iridium are superposed in the same position range, and the result is shown in figure 4, which indicates that the ruthenium-iridium bimetallic nanoparticles on the catalyst exist on the activated carbon carrier in the form of alloy.

In order to examine the influence of the catalyst obtained in this example on the progress of the reaction, the progress of the reaction was monitored to obtain the relationship between the progress of the reaction and the time, as shown in table 1.

Table 1: relationship between reaction progress and time

The reaction results in table 1 show that: after 9 hours of reaction, a conversion of 78% has been reached, exhibiting a very high efficiency of the present catalyst, after 18 hours a conversion of 100% has been reached. In the reaction process, intermediate products are generated: 5-methylfurfural and 5-methylfurfuryl alcohol. The intermediate product exists in the initial stage of the reaction, and the intermediate product is quickly converted into the target product 2, 5-dimethylfuran by the high-efficiency catalyst along with the reaction.

In order to investigate the effect of gas pressure on the catalytic performance of the catalyst obtained in this example, parameters such as the conversion of the raw material and the yield of the target product were measured under different hydrogen pressures, and the results are shown in table 2.

Table 2: effect of gas pressure on catalytic Performance

The reaction results in table 2 show that: when the hydrogen pressure in the reaction kettle is 2MPa, the catalyst shows the best catalytic effect, and the excessive pressure does not have great promotion effect on the conversion rate and the selectivity. When the hydrogen pressure is less than 2MPa, the selectivity and conversion rate of the reaction are greatly reduced. The reaction was not found to proceed if hydrogen was replaced with argon, indicating that the reaction required hydrogen as a source of hydrogen. Therefore, a hydrogen pressure of 2MPa is selected as the most suitable gas pressure for the reaction.

In order to examine the influence of the quality of the catalyst on the catalytic performance, parameters such as the conversion of the raw material and the yield of the objective product were measured for different amounts of the catalyst, and the results are shown in Table 3.

Table 3: effect of catalyst quality on catalytic Performance

Table 3 the reaction results show that: after 18 hours of reaction, the conversion of the reactants reached 100% only if the catalyst mass was greater than or equal to 90 mg. There was substantially no difference in the reaction results between the catalyst used at 120mg and 90 mg. Therefore, 90mg was selected as the most suitable catalyst mass for the reaction.

Example 2:

the preparation process of the target catalyst 0.5% Ir-0.5% Ru/C:

firstly, 0.5mL of RuCl with the concentration of 5mg/mL ₃ ·3H ₂ O solution and 1mL of IrCl with the concentration of 2.5mg/mL ₃ ·xH ₂ The O solution is poured into a 250ml round-bottom flask, and then 100ml deionized water is poured into the flask to be stirred uniformly. While stirring, a 1mg/mL NaOH solution was added dropwise until the pH of the solution was about 4. 12mg of polyethylene having an average molecular weight of 20000 were further addedPyrrolidone, stirring for 15 min. 492.5mg of activated carbon are then added, so that the theoretical metal loading ratio is 0.5% iridium: 0.5% ruthenium. After stirring for 6 hours in the absence of light, the above solution was filtered with suction. The reaction mixture was washed with 1.5L of deionized water at 90 ℃ by suction filtration until the filtrate became a colorless transparent liquid. The filter membrane used in the suction filtration is an organic phase filter membrane with the specification of 50mm multiplied by 0.08 um. The catalyst powder on the filter paper was then placed in an oven at 90 ℃ for 15 h. After drying, the catalyst was subjected to hydrogen reduction treatment, and the catalyst was reduced under a hydrogen stream at 350 ℃ for 30 min. And after the catalyst is prepared, drying and storing in dark for later use.

Example 3:

the preparation process of the target catalyst is 0.5% Ir-4% Ru/C:

firstly, 4mL of RuCl with the concentration of 5mg/mL ₃ ·3H ₂ O solution and 1mL of IrCl with a concentration of 2.5mg/mL ₃ ·xH ₂ The O solution is poured into a 250ml round-bottom flask, and then 100ml deionized water is poured into the flask to be stirred uniformly. While stirring, a 1mg/mL NaOH solution was added dropwise until the pH of the solution was about 6. 54mg of polyvinylpyrrolidone having an average molecular weight of 30000 were further added and stirred for 15 min. Thereafter 477.5mg of activated carbon are added, giving a theoretical metal loading ratio of 0.5% iridium: 4% ruthenium. After stirring for 6 hours in the absence of light, the above solution was filtered with suction. The reaction mixture was washed with 1.5L of deionized water at 100 ℃ by suction filtration until the filtrate became a colorless transparent liquid. The filter membrane used for suction filtration is an organic phase filter membrane with the specification of 50mm multiplied by 0.1 um. The catalyst powder on the filter paper was then placed in an oven at 100 ℃ for 10 h. After drying, the catalyst was subjected to hydrogen reduction treatment, and the catalyst was reduced under a hydrogen flow at 400 ℃ for 30 min. And after the catalyst is prepared, drying and storing in dark for later use.

Example 4:

the preparation process of the target catalyst is 0.5% Ir-8% Ru/C:

firstly, 8mL of RuCl with the concentration of 5mg/mL ₃ ·3H ₂ O solution and 1mL of IrCl with the concentration of 2.5mg/mL ₃ ·xH ₂ The O solution is poured into a 250ml round-bottom flask, and then 100ml deionized water is poured into the flask to be stirred evenly. While stirring, a 1mg/mL NaOH solution was added dropwise until the pH of the solution was about 9. Continuously adding into100mg of polyvinylpyrrolidone having an average molecular weight of 5000 was stirred for 15 min. Then 457.5mg of activated carbon are added, so that the theoretical metal loading ratio is 0.5% iridium: 8% of ruthenium. After stirring for 8 hours in the absence of light, the above solution was filtered with suction. The filtrate was washed with 1.5L of deionized water at 80 ℃ with suction until the filtrate became a colorless transparent liquid. The filter membrane used in the suction filtration is an organic phase filter membrane with the specification of 50mm multiplied by 0.2 um. The catalyst powder on the filter paper was then placed in an 80 ℃ oven to dry overnight. After drying, the catalyst was subjected to hydrogen reduction treatment, and the catalyst was reduced under a hydrogen flow at 250 ℃ for 120 min. And after the catalyst is prepared, drying and storing in dark for later use.

To understand the effect of the ruthenium-iridium composition in the catalysts on the catalytic performance, the catalytic performance of the catalysts obtained in examples 1-4 was tested, as well as the 1.5% Ir/C catalyst and 1.5% Ru/C catalyst, and the results are shown in Table 4.

Table 4: effect of ruthenium-iridium composition in catalysts on catalytic Performance

The reaction results in table 4 show that: in the catalyst, the iridium-ruthenium bimetallic synergistic effect greatly improves the conversion rate of 5-hydroxymethylfurfural, and when the iridium-ruthenium metal mass composition ratio is 0.5: 1, the best catalytic effect is achieved. The excessive loading of ruthenium can cause the selectivity of the catalyst to the target product 2, 5-dimethylfuran to be reduced, and a large amount of corrosive substances can be generated after the reaction is finished.

In addition, the application researches that the mass ratio of the catalyst to the solvent to the 5-hydroxymethylfurfural is 45: 300-600: the results of the conversion rate of 5-hydroxymethylfurfural under different reaction conditions of 100-150, 1.5-2.5MPa of hydrogen pressure, 3-20h of reaction time, 140-200 ℃ of reaction temperature and the like show that the catalysts all have better catalytic effects, but the effects are better when the reaction conditions are 2.0mmol of 5-hydroxymethylfurfural, 10mL of tetrahydrofuran, 90mg of catalyst, 170 ℃ of reaction temperature, 2MPa of hydrogen pressure and 18h of reaction time.

Although the invention has been described herein with reference to a number of illustrative embodiments thereof, it should be understood that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure. More specifically, various variations and modifications are possible in the component parts and/or arrangements of the subject combination arrangement within the scope of the disclosure, the drawings and the appended claims. In addition to variations and modifications in the component parts and/or arrangements, other uses will also be apparent to those skilled in the art.

Claims

1. An application of a ruthenium iridium catalyst in 5-hydroxymethylfurfural hydrogenolysis reaction is characterized in that: placing 5-hydroxymethylfurfural, ruthenium iridium catalyst and solvent in a reaction kettle, discharging air in the reaction kettle, filling hydrogen, and carrying out 5-hydroxymethylfurfural hydrogenolysis reaction; the preparation method of the ruthenium iridium catalyst comprises the following steps:

preparing a solution containing ruthenium ions and iridium ions, adjusting the pH value of the solution to 4-9, then sequentially adding polyvinylpyrrolidone with the molecular weight of 5000-30000 and active carbon, carrying out light-resistant reaction, separating a solid phase after the reaction is finished, and drying and reducing the solid phase to obtain the ruthenium-iridium catalyst; the ruthenium-iridium catalyst carrier is active carbon, and the supported metal is ruthenium-iridium alloy nano particles.

2. Use of a ruthenium iridium catalyst according to claim 1 wherein: the theoretical load proportion of iridium is 0.1-2.0wt%, and the theoretical load proportion of ruthenium is 0.1-8.0 wt%.

3. Use of a ruthenium iridium catalyst according to claim 1 wherein: the mass ratio of the polyvinylpyrrolidone to the activated carbon is 9: 250-410.

4. Use of a ruthenium iridium catalyst according to claim 1 wherein: the reaction time of the light-shielding reaction is 4-8 h.

5. Use of a ruthenium iridium catalyst according to claim 1 wherein: after the reaction is finished, carrying out suction filtration on the reaction solution, then carrying out suction filtration and washing by using water with the temperature of 80-100 ℃ until the filtrate becomes colorless transparent liquid, and drying the solid phase on the filter membrane, wherein the specification of the filter membrane used in the suction filtration is an organic phase filter membrane with the thickness of 50mm multiplied by 0.08um-50mm multiplied by 0.2 um.

6. Use of a ruthenium iridium catalyst according to claim 1 wherein: the drying temperature is 80-100 ℃, and the drying time is 10-24 h.

7. Use of a ruthenium iridium catalyst according to claim 1 wherein: the reduction treatment is to reduce the catalyst for 30-120min under the hydrogen flow at the temperature of 250-400 ℃.

8. Use of a ruthenium iridium catalyst according to claim 1 wherein: the mass ratio of the ruthenium iridium catalyst to the solvent to the 5-hydroxymethylfurfural is 45: 300-600: 100-150 ℃, the hydrogen pressure is 1.5-2.5MPa, the reaction time is 3-20h, and the reaction temperature is 140-200 ℃.