Catalyst for catalytic conversion of furfuryl alcohol into 1,5-pentanediol, preparation method, and use

Abstract

Disclosed in the present invention are a catalyst for catalytic conversion of furfuryl alcohol into 1,5-pentanediol, a preparation method, and a use. In the present invention, the method comprises: using water as a medium to mix a soluble nickel salt with a soluble non-nickel metal salt, so as to obtain a mixed metal salt solution; then adjusting the pH value of the mixed metal salt solution to 13±0.3, carrying out full mixing and then aging the mixture, carrying out solid-liquid separation, washing the resulting solid until the solid is neutral, drying, grinding, and carrying out calcination at 300-600°C, and carrying out reduction using H2, so as to obtain the catalyst for catalytic conversion of furfuryl alcohol into 1,5-pentanediol. The catalyst comprises a Schottky junction, which facilitates improvement of the conversion efficiency of furfuryl alcohol and the yield of 1,5-pentanediol. The catalyst is free of precious metals, and involves a simple preparation method and requires low costs. By using the catalyst, using furfuryl alcohol as a reactant and a protic solvent as a reaction solvent, and catalytically synthesizing furfuryl alcohol into 1,5-pentanediol under the H2 atmosphere, the conversion rate of furfuryl alcohol can reach 100% and the yield of 1,5-pentanediol can reach 78.07%.

Description

Catalyst for catalytic conversion of furfuryl alcohol into 1,5-pentanediol, preparation method and application TECHNICAL FIELD

[0001] The present application belongs to the technical field of biomass resource utilization, and particularly relates to a catalyst for catalytic conversion of furfuryl alcohol into 1,5-pentanediol, a preparation method and application. BACKGROUND

[0002] Biomass resources are widely sourced, rich in reserves and low in price, and are the only renewable carbon resources in nature that can be directly converted into liquid fuels and chemicals. Among them, furfuryl alcohol prepared from biomass is an important platform compound, which can be used to produce a variety of high-value basic chemical raw materials and pharmaceutical intermediates, of which about 65% of furfural is used for industrial production of furfuryl alcohol every year. As an important compound, the hydrogenation or hydrogenolysis of biomass-based furfuryl alcohol into high-value polyols has important significance.

[0003] 1,5-pentanediol has broad application prospects, and is an important monomer for synthesis of polyester, polyurethane and pharmaceutical intermediates, and is also applied in the fields of plasticizer, high-grade ink, cosmetics, light-cured (UV) coating and synthetic perfume. However, its price is high, the demand is large, the production capacity in China is insufficient, and it is necessary to rely on import to some extent. At present, the production methods of 1,5-pentanediol in the prior art include: Chinese invention patent application CN101225022A and Chinese invention patent CN101270032B respectively report that 1,5-pentanediol is prepared by hydrogenation of glutaraldehyde with supported Ni and Ru catalysts. At present, glutaraldehyde is obtained by catalytic condensation of ethylene ether and propylene aldehyde, and then hydrolysis. Ethylene ether is very unstable and highly explosive, and has high safety risk. In addition, the raw material glutaraldehyde is not abundant in resources and has high price. Chinese invention patent application CN1565728A reports that 1,5-pentanediol is prepared by hydrogenation of 1,5-pentandioic acid dimethyl ester, and the main active component of the catalyst is copper oxide, and the reaction temperature and the reaction pressure are 150-350℃ and 3-5MPa respectively. The deficiencies in the method are that the process flow is time-consuming, and the raw material glutaric acid for preparing 1,5-pentandioic acid dimethyl ester is limited in reserve, which will increase the production cost. Chinese invention patent CN102872897B prepares a catalyst by introducing active metal component Pt with hydrogen type ultra-stable Y molecular sieve (H-USY) as the carrier, and hydrochloric acid as the additive, the reaction temperature is 100-140℃, the reaction pressure is 0.5-2.5Mpa, and the highest yield can reach 82.6%. However, the activity of the catalyst is still not high, the conversion rate of the reactant can only reach 86.1%, and the use of hydrochloric acid as the additive will also cause equipment corrosion. In addition, more and more researchers pay attention to the preparation of 1,5-pentanediol by catalytic conversion of tetrahydrofurfuryl alcohol with a supported bimetallic catalyst. Koso S et al. use 5% tetrahydrofurfuryl alcohol aqueous solution as the reaction raw material, and Rh-ReOx / SiO2 (Re / Rh=0.5) as the catalyst, and the yield of 1,5-pentanediol can reach 77% at 393K for 24 hours (Koso, S., Furikado, I., Shimao, A., Miyazawa, T., et al. Chemoselective Hydrogenolysis of Tetrahydrofurfuryl Alcohol to 1,5-Pentanediol. Chem Commun. 2009 (15): 2035-2037). However, iridium and rhenium metals are very expensive, and are easily lost in the reaction, so that the stability is very poor.Guan J et al successfully replaced Re with Mo to prepare Rh-MoOx / C catalyst and applied it to the reaction, and the yield of 1,5-pentanediol can reach about 80%, but it still failed to change the defect that the catalyst is easy to flow (Guan, J., Peng, G., Cao, Q., et al. Role of MoO3 on a Rhodium Catalyst in the Selective Hydrogenolysis of Biomass-Derived Tetrahydrofurfuryl Alcohol into 1,5-Pentanediol. J. Phys. Chem. C. 2014, 118 (44): 25555-25566.). Therefore, the stability problem of the catalyst in the reaction needs to be solved urgently.

[0004] Different from using other raw materials, using furfuryl alcohol as a raw material to prepare 1,5-pentanediol has great advantages. Furfuryl alcohol is prepared by hydrogenation of furfural, and furfural is obtained by common agricultural and sideline products such as grain husks, sugarcane residues and corn cobs in the traditional hydrolysis production mode, and about 65% of furfural is used for industrial production of furfuryl alcohol every year. The application of furfuryl alcohol to the catalytic synthesis of 1,5-pentanediol can improve the effective utilization of biomass resources, increase its added value, and reduce the dependence of China on the import of 1.5-pentanediol. Therefore, under the premise of using furfuryl alcohol as a raw material to prepare 1,5-pentanediol, it is necessary to further develop a catalyst with low production cost, stable effect and high activity. SUMMARY

[0005] In order to overcome the defects and deficiencies of the prior art, the primary purpose of the present application is to provide a preparation method of a catalyst for catalytic conversion of furfuryl alcohol into 1,5-pentanediol.

[0006] Another purpose of the present application is to provide a catalyst for catalytic conversion of furfuryl alcohol into 1,5-pentanediol obtained by the above preparation method.

[0007] Still another purpose of the present application is to provide the application of the above-mentioned catalyst for catalytic conversion of furfuryl alcohol into 1,5-pentanediol.

[0008] Still another purpose of the present application is to provide a method for preparing 1,5-pentanediol by using furfuryl alcohol.

[0009] The purpose of the present application is achieved by the following technical scheme: a preparation method of a catalyst for catalytic conversion of furfuryl alcohol into 1,5-pentanediol, comprising the following steps:

[0010] (1) mixing a soluble nickel salt and a soluble non-nickel metal salt in water to obtain a mixed metal salt solution; wherein the nickel ions and the non-nickel metal ions in the mixed metal salt solution are in a molar ratio of 0.5 to 3.0;

[0011] (2) adjusting the pH value of the mixed metal salt solution obtained in step (1) to 13±0.3, aging at 120-200°C for 24-48h after sufficient mixing, and then solid-liquid separation to obtain a solid;

[0012] (3) washing the solid obtained in step (2) to neutral, drying, and grinding; and then calcining at 300-600°C for 4-8h, and then reducing in H2 with a flow rate of 10-50mL / min at a reduction temperature of 250-450°C for 4-8h to obtain a catalyst for the catalytic conversion of furfuryl alcohol into 1,5-pentanediol; the catalyst has a Schottky junction formed by cubic phase nickel metal particles and a non-nickel metal compound.

[0013] The water in step (1) is preferably deionized water.

[0014] The soluble nickel salt in step (1) is preferably at least one of anhydrous nickel nitrate, nickel nitrate hydrate, anhydrous nickel chloride, nickel chloride hydrate, anhydrous nickel acetate, nickel acetate hydrate, anhydrous nickel sulfate, nickel sulfate hydrate, anhydrous nickel phosphate, nickel phosphate hydrate, anhydrous nickel carbonate, and nickel carbonate hydrate; and more preferably at least one of anhydrous nickel nitrate and nickel nitrate hydrate.

[0015] The non-nickel metal in step (1) is at least one of lanthanum, calcium, magnesium, yttrium, and aluminum; and is preferably lanthanum.

[0016] The soluble non-nickel metal salt in step (1) is preferably at least one of a soluble lanthanum salt, a soluble calcium salt, a soluble magnesium salt, a soluble yttrium salt, and a soluble aluminum salt; and more preferably a soluble lanthanum salt.

[0017] The soluble lanthanum salt is preferably at least one of anhydrous lanthanum nitrate, lanthanum nitrate hydrate, lanthanum chloride, lanthanum chloride hydrate, lanthanum sulfate, and lanthanum sulfate hydrate; and more preferably at least one of anhydrous lanthanum nitrate and lanthanum nitrate hydrate.

[0018] The soluble calcium salt is preferably at least one of anhydrous calcium nitrate, calcium nitrate hydrate, calcium chloride, calcium chloride hydrate, calcium sulfate, calcium sulfate hydrate, anhydrous calcium acetate, and calcium acetate hydrate; and more preferably at least one of anhydrous calcium nitrate and calcium nitrate hydrate.

[0019] The soluble magnesium salt is preferably at least one of anhydrous magnesium nitrate, magnesium nitrate hydrate, magnesium chloride, magnesium chloride hydrate, magnesium sulfate, magnesium sulfate hydrate, anhydrous magnesium acetate, and magnesium acetate hydrate; more preferably at least one of anhydrous magnesium nitrate and magnesium nitrate hydrate.

[0020] The soluble yttrium salt is preferably at least one of anhydrous yttrium nitrate, yttrium nitrate hydrate, yttrium chloride, yttrium chloride hydrate, yttrium sulfate, and yttrium sulfate hydrate; more preferably at least one of anhydrous yttrium nitrate and yttrium nitrate hydrate.

[0021] The soluble aluminum salt is preferably at least one of anhydrous aluminum nitrate, aluminum nitrate hydrate, aluminum chloride, aluminum chloride hydrate, aluminum sulfate, aluminum sulfate hydrate, and sodium metaaluminate; more preferably at least one of anhydrous aluminum nitrate and aluminum nitrate hydrate.

[0022] The molar ratio of nickel ions to non-nickel metal ions in the mixed metal salt solution in step (1) is preferably 0.7-2.3; more preferably 0.7, 1.5, 1.8, or 2.3. By precisely controlling the feeding of the nickel solution and the salt solution containing metal elements of X in the preparation method, the metal nickel of the catalyst after calcination and reduction treatment is prevented from entering the structure of X in the form of doping, ensuring that the catalyst contains a Schottky junction formed by the cubic phase nickel metal particles and X.

[0023] The pH value in step (2) is preferably adjusted using an alkali solution.

[0024] The alkali solution is preferably at least one of a sodium hydroxide solution, a barium hydroxide solution, a potassium hydroxide solution, a calcium hydroxide solution, a sodium carbonate solution, a sodium bicarbonate solution, a potassium carbonate solution, and a potassium bicarbonate solution.

[0025] The sufficient mixing in step (2) is preferably stirring for 30-90 min; more preferably stirring for 60 min.

[0026] The aging conditions in step (2) are preferably aging at 150-180°C for 24-48 h; more preferably aging at 155-165°C for 30-40 h; most preferably aging at 160°C for 36 h. Through hydrothermal aging, a nano-sized metal precursor with uniform particle size distribution and a larger specific surface area can be obtained, which is beneficial to exposing more active sites in subsequent calcination and reduction treatment.

[0027] The calcination temperature in step (3) is preferably 400-500°C; more preferably 450°C.

[0028] The calcination time in step (3) is preferably 5-7 h; more preferably 6 h.

[0029] The reducing conditions in step (3) are preferably: a flow rate of H2 of 20-30 mL / min, a reducing temperature of 350-450 °C, and a reducing time of 5-7 hours; more preferably: a flow rate of H2 of 25 mL / min, a reducing temperature of 400 °C, and a reducing time of 6 hours.

[0030] A catalyst for catalytic conversion of furfuryl alcohol to 1,5-pentanediol, obtained by the above preparation method, has cubic phase nickel metal particles forming a Schottky junction with a non-nickel metal compound. When the non-nickel metal is lanthanum, the catalyst has cubic phase nickel metal particles forming a Schottky junction with hexagonal lanthanum hydroxide and lanthanum oxycarbonate. The metal nickel adsorbs the cyclic substrate to the surface and activates it under its action. The metal nickel also adsorbs and effectively activates the surface hydrogen and activates the molecular hydrogen into atomic hydrogen, further promoting the reaction of the hydrogen atoms with the furfuryl alcohol. The hexagonal lanthanum hydroxide and lanthanum oxycarbonate can form oxygen vacancies in situ on the surface during the catalytic reaction, adsorb and activate the furfuryl alcohol molecules and increase the reactivity of the material. The hexagonal lanthanum hydroxide and lanthanum oxycarbonate also form a Schottky junction with the metal nickel, and their synergistic effect is conducive to the decomposition of hydrogen molecules to form active hydrogen, which can participate in the subsequent catalytic hydrogenation reaction, improving the conversion efficiency of furfuryl alcohol and the yield of 1,5-pentanediol.

[0031] The above-mentioned catalyst for catalytic conversion of furfuryl alcohol to 1,5-pentanediol is used in the preparation of 1,5-pentanediol from furfuryl alcohol; preferably comprising the following steps: taking furfuryl alcohol as the reactant, using a protic solvent as the reaction solvent, adding the above-mentioned catalyst for catalytic conversion of furfuryl alcohol to 1,5-pentanediol, and reacting in a H2 atmosphere to obtain 1,5-pentanediol.

[0032] The furfuryl alcohol is furfuryl alcohol of any concentration; preferably furfuryl alcohol with a concentration of 10%-100wt%; more preferably 50wt% furfuryl alcohol.

[0033] The protic solvent is preferably at least one of water, isopropyl alcohol, n-butyl alcohol and isobutyl alcohol. The protic solvent can provide protons to promote the reaction. In the hydrogenation reaction, the protic solvent can provide protons and combine with the negative charge species in the reaction, thereby accelerating the hydrogenation process. In the ring-opening reaction, the protic solvent can stabilize the intermediates and transition states, reduce the activation energy, and thus accelerate the reaction speed; the protons provided by the protic solvent can promote the bond breaking and accelerate the ring-opening of the cyclic structure.

[0034] The amount of the protic solvent is preferably calculated according to the ratio of catalyst:protic solvent = 0.2g:10-20mL; more preferably according to the ratio of catalyst:protic solvent = 0.2g:15mL.

[0035] The amount of the catalyst for catalytic conversion of furfuryl alcohol into 1,5-pentanediol is preferably calculated according to the mass ratio of catalyst to pure furfuryl alcohol of 1:100-1:10; more preferably calculated according to the mass ratio of catalyst to pure furfuryl alcohol of 1:10.

[0036] The reaction conditions are preferably: hydrogen pressure of 3-8 MPa, reaction time of 6-36 hours, and reaction temperature of 160-230℃; more preferably: hydrogen pressure of 3-8 MPa, reaction time of 20-28 hours, and reaction temperature of 170-220℃; most preferably: hydrogen pressure of 5 MPa, reaction time of 24 hours, and reaction temperature of 190℃.

[0037] The present application has the following advantages and effects relative to the prior art:

[0038] (1) The present application obtains a catalyst for catalytic conversion of furfuryl alcohol into 1,5-pentanediol through optimization of preparation process parameters, in particular selection of metal components and pH.

[0039] (2) When the catalyst for catalytic conversion of furfuryl alcohol into 1,5-pentanediol is composed of nickel element and non-nickel metal element (referred to as X), the catalyst contains a Schottky junction structure composed of cubic-structured metal nickel and non-nickel metal. The metal nickel adsorbs the cyclic substrate to the surface and activates it under its action; or forms a bond with some atom(s) in the cyclic substrate, thereby reducing the energy barrier of ring-opening reaction. In addition, the metal nickel can adsorb and effectively activate surface hydrogen, and activate molecular hydrogen into atomic hydrogen, further promoting the reaction of hydrogen atoms with the substrate. The formation of the Schottky junction can align the energy bands of the X semiconductor and the nickel metal, promote the migration of electrons from X to the metal nickel, optimize the surface electronic structure of the supported catalyst, and further increase the opportunity of contact between the electrons and the reactant furfuryl alcohol, thereby improving the rate and selectivity of the hydrogenation reaction.

[0040] (3) The conversion rate of the catalyst provided by the present application to furfuryl alcohol reaches 100%, and the yield of 1,5-pentanediol is up to 78.07%.

[0041] (4) The method for preparing 1,5-pentanediol by using furfuryl alcohol provided by the present application has high yield of 1,5-pentanediol and wide application prospect. BRIEF DESCRIPTION OF DRAWINGS

[0042] Fig. 1 is an X-ray diffraction pattern of the catalyst prepared in Example 1.

[0043] Fig. 2 is a scanning electron microscope image of the catalyst prepared in Example 1.

[0044] Fig. 3 is a Fourier transform infrared spectrum of the catalyst prepared in Example 1. DETAILED DESCRIPTION

[0045] In order to make the technical problems, technical solutions and beneficial effects to be solved in the present application clearer, the present application will be further described in detail below in conjunction with embodiments. It should be understood that the specific embodiments described herein are only intended to explain the present application and not to limit the present application.

[0046] The terms used in the embodiments of the present application are merely for the purpose of describing specific embodiments and are not intended to limit the present application. The singular forms "a", "an" and "the" used in the embodiments of the present application and the appended claims are also intended to include the plural forms, unless the context clearly indicates otherwise.

[0047] The weight of the related components mentioned in the embodiments of the present application can not only refer to the specific content of each component, but also represent the proportional relationship between the weights of each component. Therefore, as long as the content of the related components in the embodiments of the present application is proportionally enlarged or reduced, it is within the scope disclosed in the embodiments of the present application. Specifically, the mass mentioned in the embodiments of the present application can be μg, mg, g, kg and other mass units commonly known in the chemical field.

[0048] The conversion rate of furfuryl alcohol in the present application is calculated by the following formula:

[0049] In formula (1):

[0050] c: conversion rate of furfuryl alcohol (%);

[0051] m1: mass of furfuryl alcohol after reaction (g);

[0052] m0: mass of furfuryl alcohol before reaction (g).

[0053] The yield of 1,5-pentanediol in the present application is calculated by the following formula:

[0054] In formula (2):

[0055] y: yield of 1,5-pentanediol (%);

[0056] m1: mass of 1,5-pentanediol after reaction (g);

[0057] m0: mass of furfuryl alcohol before reaction (g).

[0058] The following will be described in conjunction with specific embodiments.

[0059] Example 1

[0060] A method for catalytically synthesizing 1,5-pentanediol from furfuryl alcohol, comprising the following steps:

[0061] (1) Preparation of supported catalyst: 4.5736 g (15.7 mmol) of nickel nitrate hexahydrate (molecular weight 290.785) and 2.9264 g (6.8 mmol) of lanthanum nitrate hexahydrate (molecular weight 430.01) were weighed and dissolved in 48 mL of deionized water to prepare a solution, obtaining a mixed metal salt solution; the mixed metal salt solution was titrated to pH 13 by dropwise addition of a sodium hydroxide solution, stirred for one hour, and then placed in an autoclave for aging at 160°C for 36 hours; solid-liquid separation was performed, and the obtained solid was washed with water until neutral, dried, ground, and finally calcined in a muffle furnace at 450°C for 6 hours, and then reduced at a reduction temperature of 400°C for 6 hours in H2at a flow rate of 25 mL / min, obtaining a Ni-X supported catalyst.

[0062] (2) Preparation of 1,5-pentanediol: 0.2 g of the supported catalyst prepared in step (1) was added to 15 mL of isopropyl alcohol as a reaction solvent, and 0.2 g of furfuryl alcohol was added as a reactant, wherein the mass ratio of the catalyst to pure furfuryl alcohol was 1:10; the reaction was carried out in a high-pressure reaction kettle filled with H2atmosphere, at a hydrogen pressure of 5 MPa, a reaction temperature of 190°C, and a reaction time of 24 hours, obtaining 1,5-pentanediol.

[0063] The structure of the catalyst prepared in step (1) was analyzed, as shown in Figures 1, 2, and 3. Figure 1 shows that the catalyst contains a cubic structure of metallic nickel and a Schottky junction structure composed of hexagonal lanthanum hydroxide and lanthanum carbonate. The formation of the Schottky junction can align the energy bands of the lanthanum hydroxide or lanthanum carbonate semiconductor and the nickel metal, promote the migration of electrons from the lanthanum hydroxide or lanthanum carbonate to the nickel metal, optimize the surface electronic structure of the supported catalyst, and thus increase the opportunity for electrons to contact the reactant furfuryl alcohol, improving the rate and selectivity of the hydrogenation reaction. As can be clearly observed from Figure 2, the metallic nickel particles after calcination and reduction are in close contact with the rod-shaped lanthanum hydroxide and lanthanum carbonate, which supports the formation of the Schottky junction structure. Figure 3 shows that the characteristic signals at 1470, 1400, and 1050 cm -1 The characteristic signal at a position of the carbonate group at about 3500 cm -1 The characteristic signal at a position of the hydroxyl group further supports the presence of hexagonal lanthanum carbonate and lanthanum hydroxide in the structure.

[0064] Example 2

[0065] This example provides a method for catalytically synthesizing 1,5-pentanediol from furfuryl alcohol, which is basically the same as Example 1, except that the metal salt raw material used in the catalyst preparation step is different, as follows: 1.3782 g (5.4 mmol) of magnesium nitrate hexahydrate (molecular weight 256.401) was weighed and used instead of the lanthanum nitrate hexahydrate in Example 1.

[0066] Example 3

[0067] This example provides a method for catalytic synthesis of 1,5-pentanediol from furfuryl alcohol. The method is basically the same as that of Example 1, except that the metal salt raw material used in the catalyst preparation step is different, as follows: 2.6632 g (7.0 mmol) of yttrium nitrate hexahydrate (molecular weight 383.01) is used instead of lanthanum nitrate hexahydrate in Example 1.

[0068] Example 4

[0069] This example provides a method for catalytic synthesis of 1,5-pentanediol from furfuryl alcohol. The method is basically the same as that of Example 1, except that the metal salt raw material used in the catalyst preparation step is different, as follows: 2.4625 g (6.6 mmol) of aluminum nitrate nonahydrate (molecular weight 375.13) is used instead of lanthanum nitrate hexahydrate in Example 1.

[0070] Example 5

[0071] This example provides a method for catalytic synthesis of 1,5-pentanediol from furfuryl alcohol. The method is basically the same as that of Example 1, except that the metal salt raw material used in the catalyst preparation step is different, as follows: 2.1421 g (9.1 mmol) of calcium nitrate tetrahydrate (molecular weight 236.15) is used instead of lanthanum nitrate hexahydrate in Example 1.

[0072] The effect of the composition elements of the catalysts prepared in Examples 1-5 on the yield of 1,5-pentanediol is shown in Table 1. The results show that, under the same conditions, the catalyst with a heterojunction structure formed by lanthanum hydroxide with a rod-like hexagonal phase, lanthanum carbonate, and cubic nickel metal particles has a conversion rate of furfuryl alcohol as high as 100%, and the yield of 1,5-pentanediol is as high as 78.07%.

[0073] Table 1. Effect of composition elements of catalysts on yield of 1,5-pentanediol

[0074] Example 6

[0075] This example provides a method for catalytic synthesis of 1,5-pentanediol from furfuryl alcohol. The method is basically the same as that of Example 1, except that the metal salt raw material used in the catalyst preparation step is different, as follows: 1.4632 g (5.0 mmol) of nickel nitrate hexahydrate and 2.9264 g (6.8 mmol) of lanthanum nitrate hexahydrate are used.

[0076] Example 7

[0077] The present example provides a method for catalytic synthesis of 1,5-pentanediol from furfuryl alcohol. The method is basically the same as that of Example 1, except that the proportion of the metal salt raw materials used in the catalyst preparation step is different. Specifically, 3.4875 g (12.0 mmol) of nickel nitrate hexahydrate and 2.9264 g (6.8 mmol) of lanthanum nitrate hexahydrate are weighed.

[0078] Example 8

[0079] The present example provides a method for catalytic synthesis of 1,5-pentanediol from furfuryl alcohol. The method is basically the same as that of Example 1, except that the proportion of the metal salt raw materials used in the catalyst preparation step is different. Specifically, 3.4875 g (12.0 mmol) of nickel nitrate hexahydrate and 2.9264 g (6.8 mmol) of lanthanum nitrate hexahydrate are weighed.

[0080] Example 9

[0081] The present example provides a method for catalytic synthesis of 1,5-pentanediol from furfuryl alcohol. The method is basically the same as that of Example 1, except that the proportion of the metal salt raw materials used in the catalyst preparation step is different. Specifically, 3.4875 g (12.0 mmol) of nickel nitrate hexahydrate and 2.9264 g (6.8 mmol) of lanthanum nitrate hexahydrate are weighed.

[0082] The effects of the catalysts with different nickel loadings prepared in Examples 1, 6-9 on the yield of 1,5-pentanediol are shown in Table 2. The results show that the different molar ratios of nickel salt and lanthanum salt in the feedstock have a great influence on the performance of the final catalyst. When the molar ratio of nickel to lanthanum is 0.7-2.3, the conversion rate of furfuryl alcohol is 100%, and the yield of 1,5-pentanediol is 27.14%-78.07%.

[0083] Table 2 Effects of the difference in nickel loading on the yield of 1,5-pentanediol

[0084] Example 10

[0085] The present example provides a method for catalytic synthesis of 1,5-pentanediol from furfuryl alcohol. The method is basically the same as that of Example 1, except that the pH of the mixed metal salt is different. Specifically, the mixed metal salt solution is titrated to a pH of 10.2 by adding sodium hydroxide solution.

[0086] Example 11

[0087] The present example provides a method for catalytic synthesis of 1,5-pentanediol from furfuryl alcohol. The method is basically the same as that of Example 1, except that the pH of the mixed metal salt is different. Specifically, the mixed metal salt solution is titrated to a pH of 12 by adding sodium hydroxide solution.

[0088] Example 12

[0089] This example provides a method for catalytic synthesis of 1,5-pentanediol from furfuryl alcohol, which is basically the same as that of Example 1, except that the pH of the mixed metal salt is different, and the details are as follows: the mixed metal salt solution is titrated to pH 14 by adding sodium hydroxide solution dropwise.

[0090] The effects of the catalysts prepared at different pH in Example 1 and Examples 10-12 on the yield of 1,5-pentanediol are shown in Table 3. The results show that changing the pH of the catalyst preparation conditions under the same working conditions, the conversion rate of furfuryl alcohol and the yield of 1,5-pentanediol are different, when the pH is lower than 12, the conversion rate of furfuryl alcohol is lower than 90%; too high pH will also affect the yield of 1,5-pentanediol.

[0091] Table 3 Effects of catalysts prepared at different pH on the yield of 1,5-pentanediol

[0092] Example 13

[0093] This example provides a method for catalytic synthesis of 1,5-pentanediol from furfuryl alcohol, which is basically the same as that of Example 1, except that the hydrogenation reaction temperature in step (2) is different, and the details are as follows: the reaction is carried out in a high-pressure reaction kettle filled with H2 atmosphere, the hydrogen pressure is 5 MPa, the reaction time is 24 hours, and the reaction temperature is 170°C.

[0094] Example 14

[0095] This example provides a method for catalytic synthesis of 1,5-pentanediol from furfuryl alcohol, which is basically the same as that of Example 1, except that the hydrogenation reaction temperature in step (2) is different, and the details are as follows: the reaction is carried out in a high-pressure reaction kettle filled with H2 atmosphere, the hydrogen pressure is 5 MPa, the reaction time is 24 hours, and the reaction temperature is 180°C.

[0096] Example 15

[0097] This example provides a method for catalytic synthesis of 1,5-pentanediol from furfuryl alcohol, which is basically the same as that of Example 1, except that the hydrogenation reaction temperature in step (2) is different, and the details are as follows: the reaction is carried out in a high-pressure reaction kettle filled with H2 atmosphere, the hydrogen pressure is 5 MPa, the reaction time is 24 hours, and the reaction temperature is 200°C.

[0098] Example 16

[0099] The present example provides a method for catalytic synthesis of 1,5-pentanediol from furfuryl alcohol, which is basically the same as that of Example 1, except that the hydrogenation reaction temperature in step (2) is different, and the details are as follows: the reaction is carried out in a high-pressure reaction kettle filled with H2atmosphere, the hydrogen pressure is 5 MPa, the reaction time is 24 hours, and the reaction temperature is 210°C.

[0100] Example 17

[0101] The present example provides a method for catalytic synthesis of 1,5-pentanediol from furfuryl alcohol, which is basically the same as that of Example 1, except that the hydrogenation reaction temperature in step (2) is different, and the details are as follows: the reaction is carried out in a high-pressure reaction kettle filled with H2atmosphere, the hydrogen pressure is 5 MPa, the reaction time is 24 hours, and the reaction temperature is 220°C.

[0102] The effects of different temperatures on the yield of 1,5-pentanediol in the hydrogenation reaction of Example 1, Example 13-17 are shown in Table 4. The results show that for the Ni-X supported catalyst containing cubic nickel and hexagonal phase lanthanum hydroxide, lanthanum carbonate oxide, the reaction is carried out in a high-pressure reaction kettle filled with H2atmosphere, the hydrogen pressure is 5 MPa, the reaction time is 24 hours, and the reaction temperature is from 170-220°C, which can achieve 100% conversion of furfuryl alcohol, but the yield of 1,5-pentanediol is highest at 78.07% at a reaction temperature of 190°C.

[0103] Table 4 Effects of different reaction temperatures on the yield of 1,5-pentanediol

[0104] Example 18

[0105] The present example provides a method for catalytic synthesis of 1,5-pentanediol from furfuryl alcohol, which is basically the same as that of Example 1, except that the hydrogenation reaction temperature in step (2) is different, and the details are as follows: the reaction is carried out in a high-pressure reaction kettle filled with H2atmosphere, the hydrogen pressure is 5 MPa, the reaction time is 24 hours, and the reaction temperature is 210°C.

[0106] Example 19

[0107] The present example provides a method for catalytic synthesis of 1,5-pentanediol from furfuryl alcohol, which is basically the same as that of Example 1, except that the hydrogenation reaction temperature in step (2) is different, and the details are as follows: the reaction is carried out in a high-pressure reaction kettle filled with H2atmosphere, the hydrogen pressure is 5 MPa, the reaction time is 24 hours, and the reaction temperature is 210°C.

[0108] Example 20

[0109] The present example provides a method for catalytically synthesizing 1,5-pentanediol from furfuryl alcohol, which is basically the same as that of Example 1, except that the hydrogen pressure in the hydrogenation reaction of step (2) is different, and the details are as follows: the reaction is carried out in a high-pressure reaction kettle filled with H2 atmosphere, the hydrogen pressure is 6 MPa, the reaction time is 24 hours, and the reaction temperature is 190°C.

[0110] Example 21

[0111] The present example provides a method for catalytically synthesizing 1,5-pentanediol from furfuryl alcohol, which is basically the same as that of Example 1, except that the hydrogen pressure in the hydrogenation reaction of step (2) is different, and the details are as follows: the reaction is carried out in a high-pressure reaction kettle filled with H2 atmosphere, the hydrogen pressure is 6 MPa, the reaction time is 24 hours, and the reaction temperature is 190°C.

[0112] Example 22

[0113] The present example provides a method for catalytically synthesizing 1,5-pentanediol from furfuryl alcohol, which is basically the same as that of Example 1, except that the hydrogen pressure in the hydrogenation reaction of step (2) is different, and the details are as follows: the reaction is carried out in a high-pressure reaction kettle filled with H2 atmosphere, the hydrogen pressure is 6 MPa, the reaction time is 24 hours, and the reaction temperature is 190°C.

[0114] The effects of different temperatures in the hydrogenation reaction on the yield of 1,5-pentanediol in Examples 1, 18-22 are shown in Table 5. The results show that for the Ni-X supported catalyst containing cubic nickel and hexagonal phase lanthanum hydroxide, lanthanum carbonate oxide, when the reaction is carried out in a high-pressure reaction kettle filled with H2 atmosphere, the reaction temperature is 190°C, the reaction time is 24 hours, and the hydrogen pressure in the reaction is 3-8 MPa, 100% conversion of furfuryl alcohol can be achieved, but the yield of 1,5-pentanediol is highest at a hydrogen pressure of 5 MPa, which is 78.07%.

[0115] Table 5 Effects of different reaction pressures on the yield of 1,5-pentanediol

[0116] The above examples are preferred embodiments of the present application, but the embodiments of the present application are not limited by the above examples, and any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present application are equivalent replacement methods and are included in the protection scope of the present application.

Claims

1. A method for preparing a catalyst for catalytic conversion of furfuryl alcohol into 1,5-pentanediol, characterized in that The steps include: (1) Using water as a medium, mixing a soluble nickel salt and a soluble non-nickel metal salt to obtain a mixed metal salt solution; wherein the nickel ions and the non-nickel metal ions in the mixed metal salt solution are in a molar ratio of 0.5 to 3.0; (2) adjusting the pH value of the mixed metal salt solution obtained in step (1) to 13±0.3, mixing thoroughly, aging at 120-200° C. for 24-48 hours, separating the solid and the liquid, and collecting the solid; (3) washing the solid obtained in step (2) until neutral, drying, and grinding; then calcining at 300-600° C. for 4-8 hours, and then reducing it in H2 at a flow rate of 10-50 mL / min at a reduction temperature of 250-450° C. for 4-8 hours to obtain a catalyst for catalytic conversion of furfuryl alcohol to 1,5-pentanediol; the catalyst having a Schottky junction formed by cubic nickel metal particles and a non-nickel metal compound; The non-nickel metal described in step (1) is at least one of lanthanum, calcium, magnesium, yttrium and aluminum.

2. The method for preparing a catalyst for catalytic conversion of furfuryl alcohol into 1,5-pentanediol according to claim 1, characterized in that: The nickel ions and the non-nickel metal ions in the mixed metal salt solution described in step (1) are mixed in a molar ratio of 0.7 to 2.

3.

3. The method for preparing a catalyst for catalytic conversion of furfuryl alcohol into 1,5-pentanediol according to claim 1 or 2, characterized in that: The pH value in step (2) is adjusted using an alkaline solution; The thorough mixing in step (2) is stirring for 30 to 90 minutes; The aging conditions in step (2) are aging at 150-180° C. for 24-48 hours; The calcination temperature in step (3) is 400-500° C. The reduction conditions described in step (3) are: H2 flow rate of 20-30 mL / min, reduction temperature of 350-450°C, and reduction time of 5-7 hours.

4. The method for preparing a catalyst for catalytic conversion of furfuryl alcohol into 1,5-pentanediol according to claim 1, characterized in that: The alkaline solution is at least one of sodium hydroxide solution, barium hydroxide solution, potassium hydroxide solution, calcium hydroxide solution, sodium carbonate solution, sodium bicarbonate solution, potassium carbonate solution and potassium bicarbonate solution.

5. The method for preparing a catalyst for catalytic conversion of furfuryl alcohol into 1,5-pentanediol according to claim 1, characterized in that: The soluble nickel salt described in step (1) is at least one of anhydrous nickel nitrate and nickel nitrate hydrate; The soluble non-nickel metal salt described in step (1) is at least one of anhydrous lanthanum nitrate and lanthanum nitrate hydrate; The pH value in step (2) is adjusted by adding sodium hydroxide solution dropwise; The thorough mixing described in step (2) is stirring for 60 minutes; The aging condition in step (2) is aging at 160° C. for 36 h; The calcination temperature in step (3) is 450°C; The calcination time in step (3) is 6 hours; The reduction conditions in step (3) are: H2 flow rate of 25 mL / min, reduction temperature of 400°C, and reduction time of 6 hours; The catalyst comprises cubic nickel metal particles and hexagonal rod-shaped lanthanum hydroxide and lanthanum oxycarbonate to form a Schottky junction.

6. A catalyst for catalytic conversion of furfuryl alcohol into 1,5-pentanediol, characterized by: The method is obtained by the preparation method according to any one of claims 1 to 5.

7. Use of the catalyst for catalytic conversion of furfuryl alcohol into 1,5-pentanediol according to claim 6 in the preparation of 1,5-pentanediol using furfuryl alcohol as a raw material.

8. The use according to claim 7, characterized in that The method comprises the following steps: using furfuryl alcohol as a reactant, adopting a protic solvent as a reaction solvent, adding the catalyst for catalytic conversion of furfuryl alcohol into 1,5-pentanediol as claimed in claim 6, and reacting in an H2 atmosphere to obtain 1,5-pentanediol.

9. The use according to claim 8, characterized in that: The furfuryl alcohol is 10%-100wt% furfuryl alcohol; The protic solvent is at least one of water, isopropanol, n-butanol and isobutanol; The amount of the catalyst used for catalytic conversion of furfuryl alcohol into 1,5-pentanediol is calculated based on a mass ratio of catalyst to neat furfuryl alcohol of 1:100 to 1:10; The reaction conditions are: hydrogen pressure of 3-8 MPa, reaction time of 6-36 hours, and reaction temperature of 160-230°C.

10. The use according to claim 9, characterized in that: The furfuryl alcohol is 50wt% furfuryl alcohol; The protic solvent is isopropanol; The amount of the catalyst used for catalytic conversion of furfuryl alcohol into 1,5-pentanediol is calculated based on a mass ratio of catalyst to neat furfuryl alcohol of 1:10; The reaction conditions are: hydrogen pressure of 5 MPa, reaction time of 24 hours, and reaction temperature of 190°C.

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