Modified MOFs carrier, supported catalyst as well as preparation method and application of modified MOFs carrier and supported catalyst

Abstract

The invention discloses a modified MOFs carrier, a supported catalyst and a preparation method and application of the modified MOFs carrier and the supported catalyst. The preparation method of the modified MOFs carrier comprises the following steps: carrying out dynamic crystallization reaction on a mixed reaction system containing carboxylate ligand, zircon salt, a stabilizer, a modifier and a first organic solvent to prepare a modified MOFs precursor, and then carrying out vacuum activation treatment to prepare the modified MOFs carrier. The invention also discloses a preparation method of the supported catalyst, which comprises the following steps: loading a metal element on the modified MOFs carrier, and then carrying out roasting treatment and reduction treatment in sequence to prepare the supported catalyst. The process for preparing the supported catalyst with the modified MOFs as the carrier is simple, safe and reliable, and when the metal supported catalyst is used for preparing 2, 5-furandimethanol, the controllability is high, the reaction activity is high, the selectivity is high, the reusability is good, the renewability is good, and safety and no pollution are achieved.

Description

Technical Field

[0001] The invention belongs to the field of chemical technology and relates to a modified MOFs carrier and a preparation method thereof, in particular to a supported catalyst with modified MOFs as a carrier and a preparation method thereof, and use thereof in preparing 2,5-furan dimethanol. Background Art

[0002] With the rapid development of the global economy, the contradiction between the decreasing traditional oil resources and the increasing demand for petrochemical fuels has become increasingly prominent. Due to the energy structure characteristics of my country, which is characterized by more coal, less oil and less gas, the current feasible development strategy is to efficiently convert excess production capacity or waste biomass into fine chemicals with high added value and functional gain, gradually promote the scale-up process of decentralized raw material processing to centralized processing, and finally realize the performance compensation of bio-based chemicals for mass petroleum-based chemicals, thereby effectively improving my country's energy structure and alleviating and reversing the situation of energy shortage.

[0003] With the help of the basic molding equipment of the petrochemical industry, through innovative and efficient catalytic processes, biomass resources can be directly converted into platform compounds that are difficult to prepare by petrochemical routes. This can not only give full play to the molecular structural characteristics of biomass, but also improve the gas barrier, heat resistance and biodegradability of petroleum-based products. At present, there are more than ten widely recognized bio-based platform compounds, among which 5-hydroxymethylfurfural has both disubstituted (polymerizable) and aromatic (structural rigidity) structural characteristics, and is considered to be a bridge compound connecting bio-based sugar chemistry and petroleum-based chemistry. The European Union listed 5-hydroxymethylfurfural (HMF) and 2,5-furandicarboxylic acid (FDCA) as the most important six-carbon platform compounds in the "Medium- and Long-Term Challenges of Using Biotechnology to Produce Bulk Chemical Products from Renewable Raw Materials 2006-2050", and the US Department of Energy listed HMF as one of the top ten bio-based platform compounds. HMF molecules contain furan rings, hydroxyl groups and aldehyde groups. Through chemical reactions such as hydrogenation, oxidation, esterification, halogenation and polymerization, they can be used to produce popular chemicals such as polymer monomers, liquid fuels, and green solvents, and can also be converted into fine chemicals such as drugs and dye intermediates.

[0004] MOFs (Metal-Organic Frameworks), also known as porous coordination polymers, are porous crystalline materials with two-dimensional or three-dimensional infinite structures formed by metal ions or clusters coordinated to multidentate organic ligands. MOFs materials are mainly divided into four categories: mesh structure, Lavoisier structure, UIO material, and zeolite imidazolate framework structure materials. Compared with traditional inorganic materials, MOFs have novel structures and highly ordered structures. They can be designed and grafted. MOFs materials have a large specific surface area and porosity due to their pore structure, making this type of material very suitable for stabilizing metal nanoparticles for heterogeneous catalytic reactions. In addition, MOFs materials are used as templates or precursors to construct nanoporous carbon materials or oxides, so that MOFs-derived materials have the advantages of high specific surface area and porous characteristics as well as uniform doping of heteroatoms.

[0005] MOF-based catalysts have also been widely used in the field of biomass conversion. MOFs materials have unique structures and physicochemical properties, and their performance in biomass conversion is significantly better than that of traditional porous materials. For example, the metal nodes and organic ligands of MOFs can be used directly or introduced as acid or base centers (-SO 3 H, -NH 2 ) or redox centers (Cr, Cu, Ti, Fe, Co, etc.), which can promote the improvement of reaction conversion and selectivity. The porosity of MOF can be fine-tuned by rationally selecting organic linkers or adjusting synthesis parameters, thereby promoting the diffusion of biomass-derived molecules and facilitating access to active centers deposited in the catalyst matrix. In addition, MOFs can also be used as carriers to uniformly fix or encapsulate a large number of active species (metal and metal oxide nanoparticles, polyoxometalates, quantum dots, organometallic molecules, etc.) to prevent them from being leached, agglomerated or deactivated during the reaction. Finally, MOFs can be used as sacrificial templates or precursors to synthesize metal-carbon composites for some special catalytic applications that require high thermal stability, high graphitization or metal-carbon synergy. The above characteristics endow MOF-based materials with suitable and adjustable physicochemical properties, which can be used in various biomass catalytic reactions, including dehydration, hydrolysis, isomerization, condensation, rearrangement, hydrogenation, oxidation, esterification, polymerization, hydrodeoxygenation, etc. Fan et al. prepared a porous carbon catalyst CuCo / Zn by multi-metal uniform doping and self-template method, and used it as an efficient non-precious metal catalyst for the hydrogenation of furfural to furfuryl alcohol. The selectivity of furfuryl alcohol can reach 99.1%, and the conversion rate of furfural can reach 95.8%. Through analysis, the high efficiency of the CuCo / Zn catalyst is mainly attributed to the high dispersion of metal nanoparticles, the pore structure formed by zinc overflow, and the synergistic effect between copper and cobalt.

[0006] At present, the most reported method is to use precious metals (Pt, Au, Pd) as catalysts to catalyze the transfer hydrogenation of 5-hydroxymethylfurfural to prepare 2,5-furan dimethanol. Although it has considerable yield and selectivity, its industrial development is restricted by the complex preparation process and high cost. Non-precious metals (Cu, Ni, Co) are used as catalysts to directly hydrogenate hydrogen to prepare 2,5-furan dimethanol. Although it has low cost and simple preparation process, it has low selectivity and low reaction substrate concentration. At the same time, the metal loaded on the catalyst is easy to fall off, the catalyst is easy to deactivate, difficult to regenerate, and has poor reuse rate, which has become a restriction on the research of its downstream derivative synthesis and limits its further industrial application. Summary of the invention

[0007] The main purpose of the present invention is to provide a modified MOFs carrier, a supported catalyst using the modified MOFs as a carrier and a preparation method thereof, so as to overcome the deficiencies in the prior art.

[0008] Another object of the present invention is to provide application of the supported catalyst.

[0009] In order to achieve the above-mentioned invention object, the technical solution adopted by the present invention includes:

[0010] An embodiment of the present invention provides a method for preparing a modified MOFs carrier, which includes: subjecting a mixed reaction system comprising a carboxylate ligand, a zirconium salt, a stabilizer, a modifier and a first organic solvent to a dynamic crystallization reaction to obtain a modified MOFs precursor, followed by vacuum activation treatment to obtain a modified MOFs carrier.

[0011] The embodiment of the present invention also provides a modified MOFs carrier prepared by the above-mentioned preparation method.

[0012] The present invention also provides a method for preparing a supported catalyst, which comprises:

[0013] The modified MOFs support was prepared according to the aforementioned method;

[0014] The metal element is loaded on the modified MOFs carrier, and then calcined and reduced in sequence to obtain a loaded catalyst.

[0015] The embodiment of the present invention also provides a supported catalyst prepared by the above preparation method.

[0016] Furthermore, the supported catalyst includes: a modified MOFs carrier, and metal nanoparticles uniformly supported on the modified MOFs carrier.

[0017] The embodiment of the present invention also provides the use of the supported catalyst in the preparation of 2,5-furan dimethanol.

[0018] Accordingly, an embodiment of the present invention further provides a method for preparing 2,5-furan dimethanol, which comprises:

[0019] Under hydrogen atmosphere and selected pressure conditions, 5-hydroxymethylfurfural is catalyzed by the supported catalyst to undergo catalytic hydrogenation reaction to obtain 2,5-furan dimethanol.

[0020] Compared with the prior art, the beneficial effects of the present invention include at least:

[0021] 1) The special spatial geometric configuration formed by Zr-O and modified atoms in the modified MOFs carrier prepared by the present invention has a large number of catalytic sites and porous structures distributed in its skeleton, which is conducive to increasing the contact area between the reactants and the catalytic active sites, thereby promoting the reaction; secondly, it has a multi-level pore structure and a large window, has an extremely high specific surface area and a hierarchical porous structure, can better stabilize metal nanoparticles, and can effectively help transport the reaction substrates in the catalytic reaction, and is used for heterogeneous catalytic reactions, having the advantages of both homogeneous catalysts and traditional heterogeneous catalysts.

[0022] 2) The surface of the modified MOFs carrier prepared by the present invention is modified, and the modified atoms accurately fill the O vacancies in the special geometric space configuration formed by Zr-O to achieve the regulation of the L acid site in the carrier, strengthen the adsorption of the carrier to HMF molecules in the hydrogenation reaction, and make the HMF molecules contact the hydrogenation sites more, better and faster to achieve efficient conversion and hydrogenation; and the L acid sites enhanced by the modified atoms are in close contact with the metal nanoparticles, shortening the physical distance between the two, and the efficient synergistic effect of the metal and the acid accelerates the diffusion rate between the active sites of the reactants, thereby improving the reaction rate and selectivity. And due to the intimacy between the metal and the acid, the metal nanoparticles of the supported catalyst with the modified MOFs as the carrier are less likely to fall off in multiple reactions under long-term high temperature conditions, and the performance remains the same after high-temperature regeneration, which can effectively reduce costs.

[0023] 3) The process for preparing the supported catalyst of the present invention is simple, easy to operate, low in price, simple to synthesize, safe and reliable. The supported metal nanoparticles are evenly dispersed due to the porosity and orderliness of the carrier, which can promote the transfer of substrates within the catalyst, and the selectivity and yield of the catalytic hydrogenation reduction to prepare 2,5-furan dimethanol are greatly improved.

[0024] 4) Compared with traditional supported catalysts, the catalyst prepared by the present invention has good reusability, is not easy to deactivate, has very high selectivity, strong specificity, and good regeneration. The catalyst can be washed and reused after the reaction, and the performance effect remains the same, which reduces the cost of use and has good application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0026] Figure 1a and Figure 1b This is a scanning electron microscope (SEM) image of the modified MOFs carrier prepared in Example 1 of the present invention;

[0027] Figure 2 The scanning electron microscope (SEM) images of the modified MOFs carrier prepared under different conditions in Comparative Example 2;

[0028] Figure 3 The XPS loaded metal (Cu) valence characterization diagram of the loaded catalysts with different loading amounts of modified MOFs as carriers in Examples 14 and 22-24 of the present invention;

[0029] Figure 4 This is a transmission electron microscope scanning (TEM) image of the supported catalyst using modified MOFs as a carrier in Example 14 of the present invention;

[0030] Figure 5a-5d They are TEM particle size distribution analysis diagrams of supported catalysts with different loading amounts of modified MOFs as carriers in Example 22, Example 14, and Examples 23-24 of the present invention, respectively;

[0031] Figure 6 This is the XRD diagram of the supported catalyst using modified MOFs as carrier in Example 22 of the present invention. DETAILED DESCRIPTION

[0032] In view of the above-mentioned defects of the prior art, the inventors of this case have proposed the technical solution of the present invention after long-term research and a large number of experiments, which mainly provides a supported catalyst with modified MOFs as a carrier. The technical solution, its implementation process and principle will be further explained as follows.

[0033] In the present invention, "HMF" is an abbreviation for 5-hydroxymethylfurfural, "BHMF" is an abbreviation for 2,5-furan dimethanol, "DMF" is an abbreviation for N,N-dimethylformamide, and "PTA" is an abbreviation for terephthalic acid.

[0034] As one aspect of the technical solution of the present invention, a method for preparing a modified MOFs carrier involves: subjecting a mixed reaction system comprising a carboxylate ligand, a zirconium salt, a stabilizer, a modifier and a first organic solvent to a dynamic crystallization reaction to obtain a modified MOFs precursor, followed by vacuum activation treatment to obtain a modified MOFs carrier.

[0035] In some embodiments, the carboxylate ligand may specifically include any one of terephthalic acid, trimesic acid, naphthalene dicarboxylic acid, biphenyl-4,4-dicarboxylic acid, etc., but is not limited thereto.

[0036] In some embodiments, the zirconium salt includes an organic solvent-soluble zirconium salt. Specifically, the zirconium salt includes any one or a combination of two or more of zirconium chloride (zirconium chloride), zirconium nitrate, zirconium sulfate, etc., but is not limited thereto.

[0037] In some embodiments, the molar ratio of zirconium ions contained in the zirconium salt to terephthalic acid (ie, the concentration ratio in the mixed reaction system) is 1:0.1 to 1:5.

[0038] In some embodiments, the concentration of zirconium ions contained in the zirconium salt in the mixed reaction system is 0.1 to 100 mmol / L.

[0039] In some embodiments, the stabilizer may include any one or a combination of two or more of acetic acid, citric acid, oxalic acid, ethylenediaminetetraacetic acid (EDTA), phosphoric acid, etc., but is not limited thereto.

[0040] In some more preferred embodiments, the volume of the stabilizer accounts for 0.01% to 15% of the total volume of the mixed reaction system. Specifically, the upper limit of the volume of the stabilizer added to the total volume ratio can be independently selected from 15%, 14%, 13%, 12%, 11%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%, 0.4%, 0.3%, 0.2%, 0.1%; the lower limit can be independently selected from 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%.

[0041] In some embodiments, the modifier may include any one or a combination of two or more of aluminum salt, tin salt, chromium salt, zinc salt, silicon dioxide, etc., but is not limited thereto.

[0042] In some more specific embodiments, the aluminum salt may include any one or a combination of two or more of aluminum chloride, aluminum nitrate, aluminum sulfate, etc., but not limited thereto; the tin salt may include any one or a combination of two or more of tin chloride, tin nitrate, tin sulfate, etc., but not limited thereto; the chromium salt may include any one or a combination of two or more of chromium chloride, chromium nitrate, chromium sulfate, etc., but not limited thereto; the zinc salt may include any one or a combination of two or more of zinc chloride, zinc nitrate, zinc sulfate, etc., but not limited thereto.

[0043] In some embodiments, the molar ratio of the modifier to terephthalic acid (ie, the concentration ratio in the mixed reaction system) is 1:0.1 to 1:20.

[0044] In some more preferred embodiments, the molar ratio of the modifier to terephthalic acid (ie, the concentration ratio in the mixed reaction system) is 1:5 to 1:20.

[0045] In some embodiments, the first organic solvent may include any one or a combination of two or more of N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone, acetone, etc., but is not limited thereto.

[0046] In some embodiments, the preparation method further comprises: filtering the modified MOFs precursor obtained by the dynamic crystallization reaction after high-speed centrifugation, washing and drying to obtain a dried modified MOFs precursor.

[0047] In some specific embodiments, the preparation method of the modified MOFs carrier may specifically include the following steps: terephthalic acid and zirconium salt are uniformly dissolved in a first organic solvent containing a stabilizer, and under the action of the modifier, a modified MOFs precursor is obtained by dynamic crystallization reaction. The modified MOFs precursor obtained by the dynamic crystallization reaction is filtered after centrifugation at 700-1200rpm for 5-30min, washed and dried, and then vacuum activated at a specified temperature to obtain a modified MOFs carrier. Wherein, the washing includes washing with DMF 3-5 times, and then washing with acetone 3-5 times; the drying temperature is 60-80℃, and the time is 6-12h.

[0048] In some specific embodiments, the crystallization reaction of the present invention adopts a dynamic crystallization process to ensure that the morphology of the prepared modified MOFs precursor is uniform and stable. The present invention adopts a dynamic crystallization reaction process in the process of preparing the modified MOFs carrier to ensure that the morphology of the carrier is uniform and stable during the formation process, and at the same time, precise pore size control can be achieved.

[0049] In some more preferred embodiments, the dynamic crystallization reaction includes: heating the mixed reaction system from room temperature to a specified crystallization reaction temperature at a heating rate of 0.5 to 10°C / min to carry out a dynamic crystallization reaction; wherein the specified crystallization reaction temperature is 80 to 160°C, the time for the dynamic crystallization reaction at the specified crystallization reaction temperature is 6 to 96 hours, and the mechanical flipping speed of the dynamic crystallization is 10 to 60 rpm.

[0050] Further, the upper limit of the specified crystallization reaction temperature can be independently selected from 160°C, 155°C, 150°C, 145°C, 140°C, 135°C, 130°C, 125°C, 120°C, 115°C, 110°C, 105°C, 100°C, 95°C, and 90°C, and the lower limit can be independently selected from 89°C, 88°C, 87°C, 86°C, 85°C, 84°C, 83°C, 82°C, 81°C, and 80°C.

[0051] Furthermore, the upper limit of the crystallization reaction time can be independently selected from 96h, 84h, 72h, 60h, 48h, 36h, 24h, 12h, and the lower limit can be independently selected from 11h, 10h, 9h, 8h, 7h, 6h.

[0052] In some specific embodiments, the dried modified MOFs precursor is subjected to vacuum activation treatment under vacuum conditions, wherein the temperature of the vacuum activation treatment is 80 to 200° C., the time of the vacuum activation treatment is 6 to 96 hours, and the activation vacuum degree is -0.01 to -0.1 MPa.

[0053] Furthermore, the upper limit of the vacuum activation treatment temperature can be independently selected from 200°C, 190°C, 180°C, 170°C, 160°C, 150°C, 140°C, 130°C, 120°C, 110°C, 100°C, 95°C, 90°C, and the lower limit is independently selected from 89°C, 88°C, 87°C, 86°C, 85°C, 84°C, 83°C, 82°C, 81°C, 80°C.

[0054] Furthermore, the upper limit of the vacuum activation treatment time is independently selected from 96h, 90h, 84h, 78h, 72h, 66h, 60h, 54h, 48h, 42h, 36h, 30h, 24h, and the lower limit is independently selected from 22h, 20h, 18h, 16h, 14h, 12h, 10h, 8h, 6h.

[0055] As another aspect of the technical solution of the present invention, it also relates to a modified MOFs carrier prepared by the aforementioned method.

[0056] In some preferred embodiments, the modified MOFs carrier has a particle size of 200 nm to 250 nm and a specific surface area of ​​1200 to 1300 m 2 / g, the crystal form is octahedral.

[0057] The modified MOFs carrier prepared by the present invention has excellent heat resistance and chemical stability, and can still maintain the stability of its morphology during repeated use, so as to achieve better catalyst recycling.

[0058] The surface of the modified MOFs carrier prepared by the present invention is modified, and the modified atoms accurately fill the O vacancies in the special geometric space configuration formed by Zr-O to achieve the regulation of the L acid site in the carrier, enhance the adsorption of the carrier to HMF molecules in the hydrogenation reaction, and enable the HMF molecules to contact the hydrogenation sites more, better and faster to achieve efficient conversion hydrogenation.

[0059] Furthermore, the modified atom-enhanced L-acid sites in the modified MOFs carrier prepared by the present invention are in close contact with the metal nanoparticles, shortening the physical distance between the two. The efficient synergistic effect of the metal and the acid accelerates the diffusion rate between the active sites of the reactants, thereby improving the reaction rate and selectivity. And due to the intimacy between the metal and the acid, the metal nanoparticles of the supported catalyst with the modified MOFs as the carrier are less likely to fall off in multiple reactions under long-term high temperature conditions, and the performance remains the same after high-temperature regeneration, which can effectively reduce costs.

[0060] As another aspect of the technical solution of the present invention, a method for preparing a supported catalyst involves:

[0061] A modified MOFs carrier is prepared according to the aforementioned preparation method;

[0062] The metal element is loaded on the modified MOFs carrier, and then calcined and reduced in sequence to obtain a loaded catalyst.

[0063] In some embodiments, the metal element includes a transition metal element, and the transition metal element may include any one or a combination of two or more of Cu, Ni, Co, Fe, etc., but is not limited thereto.

[0064] In some specific embodiments, the preparation method comprises: fully immersing the modified MOFs carrier in a metal salt solution, so that the metal element is loaded on the modified MOFs carrier.

[0065] Furthermore, the metal salt may include any one or a combination of two or more of transition metal sulfates, transition metal nitrates, transition metal acetates, transition metal phosphates, transition metal chlorides, etc., but is not limited thereto.

[0066] In some embodiments, the preparation method comprises: in an inert atmosphere, gradually increasing the temperature of the modified MOFs carrier loaded with metal elements to a calcination temperature, and performing the calcination treatment.

[0067] Further, the inert atmosphere may include a nitrogen atmosphere, but is not limited thereto.

[0068] In some more specific embodiments, the preparation method comprises: heating from room temperature to a specified calcination temperature of 200 to 500° C. at a heating rate of 0.5 to 10° C. / min, and performing calcination at the specified calcination temperature for 1 h to 20 h.

[0069] Furthermore, the upper limit of the calcination temperature may be independently selected from 500°C, 450°C, 400°C, 350°C, 300°C, 250°C, and the lower limit may be independently selected from 250°C, 240°C, 230°C, 220°C, 210°C, 200°C.

[0070] Furthermore, the upper limit of the calcination time can be independently selected from 20h, 18h, 16h, 14h, 12h, 10h, and the lower limit can be independently selected from 8h, 6h, 4h, 2h, 1h.

[0071] In some embodiments, the preparation method comprises: performing the reduction treatment on the calcined product in a reducing atmosphere.

[0072] Furthermore, the reducing atmosphere includes a hydrogen atmosphere, but is not limited thereto.

[0073] In some more specific embodiments, the preparation method includes: reducing in a hydrogen atmosphere, the reduction temperature is increased from room temperature to a specified reduction temperature of 100 to 600°C at a heating rate of 0.5 to 10°C / min, and the reduction treatment time at the specified reduction temperature is 1h to 30h.

[0074] Furthermore, the upper limit of the temperature of the reduction treatment under a hydrogen atmosphere can be independently selected from 600°C, 550°C, 500°C, 450°C, 400°C, 350°C, 300°C, 250°C, and 200°C, and the lower limit can be independently selected from 150°C, 140°C, 130°C, 120°C, 110°C, and 100°C.

[0075] Furthermore, the upper limit of the reduction treatment time under hydrogen atmosphere can be independently selected from 30h, 28h, 26h, 24h, 22h, 20h, 18h, 16h, 14h, 12h, 10h, and the lower limit can be independently selected from 10h, 8h, 6h, 4h, 2h, 1h.

[0076] Among them, as one of the more specific embodiments, the preparation method of the supported catalyst with the modified MOFs as the carrier specifically comprises the following steps:

[0077] Terephthalic acid and zirconium salt are uniformly dissolved in a first organic solvent containing a stabilizer, and under the action of a modifier, a modified precursor is obtained by a dynamic crystallization reaction. After centrifugation, it is washed and dried, and then vacuum activated at a specified temperature to obtain a modified MOFs carrier. The saturated adsorption capacity of the prepared modified MOFs carrier is measured, and then the metal salt is dissolved in the water of the saturated water absorption capacity, and loaded on the modified MOFs carrier by an equal volume impregnation method. After drying, it is subjected to a gradient temperature rise calcination treatment in a nitrogen atmosphere, and then a gradient temperature rise reduction treatment is performed in a hydrogen atmosphere to obtain a supported catalyst with the modified MOFs as the carrier.

[0078] Furthermore, the saturated water absorption capacity of the carrier in the catalyst is the amount of water that the carrier absorbs to just penetrate the surface in a dry state.

[0079] In summary, the method for preparing the catalyst of the present invention has a simple loading mode, is easy to operate, can be adaptively adjusted according to actual conditions, has strong operability, is low in price, is simple to synthesize, and is safe and reliable. The loaded metal nanoparticles are evenly dispersed due to the porosity and orderliness of the carrier, which can promote substrate transfer within the catalyst, and greatly improve the selectivity and yield of catalytic hydrogenation reduction to prepare 2,5-furan dimethanol.

[0080] As another aspect of the technical solution of the present invention, it also relates to a supported catalyst prepared by the aforementioned method, which includes a modified MOFs carrier, and metal nanoparticles uniformly supported on the modified MOFs carrier.

[0081] In some embodiments, the loading amount of the metal nanoparticles on the modified MOFs carrier is 0.1 wt % to 20 wt %.

[0082] Furthermore, the upper limit of the metal nanoparticle loading can be independently selected from 20%, 15%, 10%, 5%, 1%, and the lower limit can be independently selected from 1%, 0.5%, 0.4%, 0.3%, 0.2%, 0.1%.

[0083] Furthermore, the material of the loaded metal nanoparticles is selected from transition metal elements; the transition metal elements are selected from any one or a combination of two or more of Cu, Ni, Co, Fe, etc.

[0084] The catalyst prepared by the present invention is very stable in thermal reactions under various types of solvents. The special spatial geometric configuration formed by Zr-O and modified atoms has a large number of catalytic sites and porous structures distributed in its skeleton, which is conducive to increasing the contact area between the reactants and the catalytic active sites, thereby promoting the reaction. Secondly, it has a multi-level pore structure and a large window, has an extremely high specific surface area and a hierarchical porous structure, can better stabilize metal nanoparticles, and can effectively help transport the reaction substrate in the catalytic reaction, and is used for multiphase catalytic reactions, and has the advantages of both homogeneous catalysts and traditional multiphase catalysts. And according to the reaction requirements, organic ligands with different functional groups can be selected to modify the carrier, so that it has a catalyst with different functional group effects.

[0085] Furthermore, compared with traditional supported catalysts, the catalyst prepared by the present invention has good reusability, is not easy to deactivate, has very high selectivity, strong specificity, and good regeneration. The catalyst after the reaction is washed and reused, the performance effect remains the same, the cost of use is reduced, and it has good application prospects.

[0086] Another aspect of the embodiments of the present invention further provides the use of the above-mentioned supported catalyst with the modified MOFs as a carrier in the preparation of 2,5-furandicarboxylic acid.

[0087] Specifically, the application includes the use of the supported catalyst in the preparation of 2,5-furan dimethanol by hydrogenation of 5-hydroxymethylfurfural.

[0088] Accordingly, another aspect of an embodiment of the present invention provides a method for preparing 2,5-furan dimethanol, comprising:

[0089] 5-Hydroxymethylfurfural is used as a raw material, the reaction solvent is a second organic solvent, a supported catalyst with modified MOFs as a carrier is added, and the 2,5-furan dimethanol is prepared by catalytic hydrogenation reaction under hydrogen pressure atmosphere.

[0090] In some preferred embodiments, the preparation method specifically comprises: mixing the supported catalyst, 5-hydroxymethylfurfural and a second organic solvent to form a reaction solution.

[0091] In some specific embodiments, the concentration of 5-hydroxymethylfurfural in the reaction solution is 0.1 to 3000 mmol / L.

[0092] Furthermore, the upper limit of the concentration of 5-hydroxymethylfurfural in the reaction solution can be independently selected from 3000mM, 2500mM, 2000mM, 1500mM, 1000mM, 500mM, 400mM, 300mM, 200mM, and 100mM, and the lower limit can be independently selected from 0.1mM, 0.5mM, 1mM, 5mM, 10mM, 20mM, 30mM, 40mM, 50mM, 60mM, 70mM, 80mM, and 90mM.

[0093] In some specific embodiments, the second organic solvent may include any one or a combination of two or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, etc., but is not limited thereto.

[0094] In some specific embodiments, the pressure of the hydrogen is 0.1 MPa to 8 MPa.

[0095] Furthermore, the upper limit of the hydrogen pressure can be independently selected from 8MPa, 7MPa, 6MPa, 5MPa, 4MPa, 3MPa, and 2MPa, and the lower limit can be independently selected from 1MPa, 0.8MPa, 0.6MPa, 0.4MPa, 0.2MPa, and 0.1MPa.

[0096] In some specific embodiments, the temperature of the catalytic hydrogenation reaction is 80-200° C., and the time of the catalytic hydrogenation reaction is 0.5-10 h.

[0097] Furthermore, the upper limit of the temperature of the catalytic hydrogenation reaction can be independently selected from 200°C, 190°C, 180°C, 170°C, 160°C, 150°C, 140°C, 130°C, 120°C, 110°C, and the lower limit can be independently selected from 105°C, 100°C, 95°C, 90°C, 85°C, 80°C.

[0098] In some specific embodiments, the mass ratio of 5-hydroxymethylfurfural to supported catalyst is 1:1 to 30:1.

[0099] Further, the upper limit of the mass ratio of the 5-hydroxymethylfurfural to the supported catalyst is independently selected from any one of 30:1, 29:1, 28:1, 27:1, 26:1, 25:1, 24:1, 23:1, 22:1, 21:1, 20:1, 19:1, 18:1, 17:1, 16:1, 15:1, 14:1, 13:1, 12:1, 11:1, 10:1, 9:1, 8:1, 7:1, 6:1, and 5:1; the lower limit is independently selected from any one of 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, and 4:1.

[0100] Furthermore, the reaction process for preparing 2,5-furan dimethanol of the present invention has a very high conversion rate, the reaction process is controllable (changing different reaction condition parameters), the selectivity is very strong, the interference of various intermediate products is avoided, the reaction yield is effectively improved, the difficulty of separation is reduced, and the yield is improved.

[0101] By means of the above technical scheme, the process for preparing a supported catalyst with modified MOFs as a carrier is simple, safe and reliable. At the same time, when the metal supported catalyst is used to prepare 2,5-furan dimethanol, it has strong controllability, strong reaction activity, high selectivity, good reusability, good renewability, safety and no pollution.

[0102] The technical solution of the present invention will be further described in detail below in conjunction with several embodiments and drawings. This embodiment is implemented on the premise of the technical solution of the invention, and a detailed implementation method and specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments.

[0103] Unless otherwise specified, the experimental materials used in the following examples can be purchased from conventional biochemical reagent companies.

[0104] The analysis method in the embodiment of the present invention is as follows:

[0105] In the examples, the products in the 5-hydroxymethylfurfural synthesis reaction were analyzed by using Agilent's LC1260 high performance liquid chromatograph, and the external standard method was used for quantification.

[0106] Time-of-flight mass spectrometry (TOF) was used to qualitatively analyze the products in the synthesis reaction of 5-hydroxymethylfurfural.

[0107] X-ray powder diffractometer (XRD) was used to qualitatively analyze the prepared supported catalyst with modified MOFs as carrier.

[0108] Transmission electron microscopy (TEM) was used to characterize the morphology of the prepared modified MOFs carrier and the metal particles supported by the supported catalyst based on the modified MOFs carrier.

[0109] Scanning electron microscopy (SEM) was used to characterize the morphology of the prepared modified MOFs carrier and the metal particles supported by the supported catalyst based on the modified MOFs.

[0110] X-ray photoelectron spectroscopy (XPS) was used to qualitatively and quantitatively analyze the chemical state of the metal particles supported by the prepared modified MOFs supported catalyst.

[0111] Inductively coupled plasma optical emission spectrometry (ICP-OES) was used to qualitatively and quantitatively analyze the metal loading of the supported catalyst with modified MOFs as the carrier.

[0112] The specific surface area of ​​the supported catalyst with modified MOFs as carrier was qualitatively and quantitatively analyzed using a specific surface area adsorption instrument.

[0113] The calculation method in the embodiments of the present application is as follows:

[0114] The calculation formulas for catalyst selectivity, 5-hydroxymethylfurfural conversion rate and 2,5-furan dimethanol yield are as follows:

[0115] 2,5-furan dimethanol yield = (mass of 2,5-furan dimethanol in the product / theoretical mass of 2,5-furan dimethanol produced) × 100%;

[0116] 5-Hydroxymethylfurfural conversion rate = (the mass of 5-Hydroxymethylfurfural actually involved in the reaction / the mass of 5-Hydroxymethylfurfural in the raw material) × 100%;

[0117] Catalyst selectivity = (2,5-furan dimethanol yield / 5-hydroxymethylfurfural conversion rate) × 100%.

[0118] Example 1

[0119] (1) Add 188 ml of DMF and 12 ml of stabilizer acetic acid to a 250 ml beaker, stir evenly, then add 0.473 g of PTA, 0.631 g of zirconium chloride and 0.038 g of modifier anhydrous AlCl 3 , stir thoroughly until completely dissolved. At this point, the volume of the stabilizer in the system accounts for 5.5% of the total system, PTA and Zr 4+ The concentration ratio of PTA and modifier Al is 1.05:1. 3+The concentration ratio is 10:1. The reaction solution is poured into a hydrothermal kettle and placed in an automatic homogeneous reactor for dynamic crystallization reaction. The temperature is raised from room temperature to the specified crystallization reaction temperature of 120°C at a heating rate of 1°C / min. The crystallization reaction time is 24h and the dynamic crystallization mechanical turning speed is 30rpm.

[0120] (2) After the crystallization reaction is completed, the product is cooled to room temperature, filtered after high speed rotation at 1000 rpm for 10 min, washed with DMF 3-5 times, and then with acetone 3-5 times, and dried at 80°C for 6 h to obtain a modified MOFs precursor.

[0121] (3) The modified MOFs precursor was placed in a vacuum drying oven for vacuum activation treatment at an activation temperature of 120°C and a vacuum degree of -0.1PMa for 24 hours to obtain a modified MOFs carrier, which was recorded as 1#. The morphology of sample 1# was scanned by transmission electron microscopy (TEM), and the results showed that Figure 1a and Figure 1b shown.

[0122] Example 2

[0123] (1) Add 188 ml of DMF and 12 ml of stabilizer acetic acid to a 250 ml beaker, stir evenly, then add 0.473 g of PTA, 0.631 g of zirconium chloride and 0.076 g of modifier anhydrous AlCl 3 , stir thoroughly until completely dissolved. At this point, the volume of the stabilizer in the system accounts for 5.5% of the total system, PTA and Zr 4+ The concentration ratio of PTA and modifier Al is 1.05:1. 3+ The concentration ratio is 5:1. The reaction solution is poured into a hydrothermal kettle and placed in an automatic homogeneous reactor for dynamic crystallization reaction. The temperature is raised from room temperature to the specified crystallization reaction temperature of 120°C at a heating rate of 1°C / min. The crystallization reaction time is 24h and the dynamic crystallization mechanical turning speed is 30rpm.

[0124] (2) After the crystallization reaction is completed, the product is cooled to room temperature, filtered after high speed rotation at 1000 rpm for 10 min, washed with DMF 3-5 times, and then with acetone 3-5 times, and dried at 80°C for 6 h to obtain a modified MOFs precursor.

[0125] (3) The modified MOFs precursor was placed in a vacuum drying oven for vacuum activation treatment at an activation temperature of 120°C and at a vacuum degree of -0.1PMa for 24 hours to obtain a modified MOFs carrier, which was recorded as 2#.

[0126] Compared with Example 1, the amount of modifier added in Example 2 during the preparation of the carrier is different, so that the amount of modifier is increased. The modified MOFs prepared under this condition are used as the load carrier to prepare a loaded catalyst.

[0127] Example 3

[0128] (1) Add 188 ml of DMF and 12 ml of stabilizer acetic acid to a 250 ml beaker, stir evenly, then add 0.473 g of PTA, 0.631 g of zirconium chloride and 0.019 g of modifier anhydrous AlCl 3 , stir thoroughly until completely dissolved. At this point, the volume of the stabilizer in the system accounts for 5.5% of the total system, PTA and Zr 4+ The concentration ratio of PTA and modifier Al is 1.05:1. 3+ The concentration ratio is 20:1. The reaction solution is poured into a hydrothermal kettle and placed in an automatic homogeneous reactor for dynamic crystallization reaction. The temperature is raised from room temperature to the specified crystallization reaction temperature of 120°C at a heating rate of 1°C / min. The crystallization reaction time is 24h and the dynamic crystallization mechanical turning speed is 30rpm.

[0129] (2) After the crystallization reaction is completed, the product is cooled to room temperature, filtered after high speed rotation at 1000 rpm for 10 min, washed with DMF 3-5 times, and then with acetone 3-5 times, and dried at 80°C for 6 h to obtain a modified MOFs precursor.

[0130] (3) The modified MOFs precursor was placed in a vacuum drying oven for vacuum activation treatment at an activation temperature of 120°C and at a vacuum degree of -0.1PMa for 24 hours to obtain a modified MOFs carrier, which was recorded as 3#.

[0131] Compared with Example 1, the amount of modifier added in the process of preparing the carrier in Example 3 is different, so that the amount of modifier is reduced. The modified MOFs prepared under this condition are used as the loading carrier to prepare the loaded catalyst.

[0132] Comparative Example 1

[0133] (1) Add 188 ml of DMF and 12 ml of stabilizer acetic acid to a 250 ml beaker, stir evenly, then add 0.473 g of PTA and 0.631 g of zirconium chloride, stir thoroughly until completely dissolved. At this point, the volume of the stabilizer in the system accounts for 5.5% of the total system. PTA and Zr 4+ The concentration ratio is 1.05: 1. The reaction solution is poured into a hydrothermal kettle and placed in an automatic homogeneous reactor for dynamic crystallization reaction. The temperature is raised from room temperature to the specified crystallization reaction temperature of 120°C at a heating rate of 1°C / min. The crystallization reaction time is 24h and the dynamic crystallization mechanical turning speed is 30rpm.

[0134] (2) After the crystallization reaction is completed, the product is cooled to room temperature, filtered after high speed at 1000 rpm for 10 min, washed with DMF 3-5 times, and acetone 3-5 times, and dried at 80°C for 6 h to obtain the MOFs precursor.

[0135] (3) The modified MOFs precursor is placed in a vacuum drying oven for vacuum activation treatment at an activation temperature of 120°C and at a vacuum degree of -0.1PMa for 24 hours to obtain a MOFs carrier, which is recorded as 4#.

[0136] Compared with Example 1, in this comparative example, no modifier was added to modify the carrier during the preparation of the carrier, and the MOFs prepared under this condition were used as the supported carrier to prepare a supported catalyst.

[0137] Example 4

[0138] (1) Add 188 ml of DMF and 12 ml of stabilizer acetic acid to a 250 ml beaker, stir evenly, then add 0.473 g of PTA, 0.631 g of zirconium chloride and 0.017 g of modifier SiO 2 , stir thoroughly until completely dissolved. At this point, the volume of the stabilizer in the system accounts for 5.5% of the total system, PTA and Zr 4+ The concentration ratio of PTA and modifier Si is 1.05:1. 4+ The concentration ratio is 10:1. The reaction solution is poured into a hydrothermal kettle and placed in an automatic homogeneous reactor for dynamic crystallization reaction. The temperature is raised from room temperature to the specified crystallization reaction temperature of 120°C at a heating rate of 1°C / min. The crystallization reaction time is 24h and the dynamic crystallization mechanical turning speed is 30rpm.

[0139] (2) After the crystallization reaction is completed, the product is cooled to room temperature, filtered after high speed rotation at 1000 rpm for 10 min, washed with DMF 3-5 times, and then with acetone 3-5 times, and dried at 80°C for 6 h to obtain a modified MOFs precursor.

[0140] (3) The modified MOFs precursor was placed in a vacuum drying oven for vacuum activation treatment at an activation temperature of 120°C and at a vacuum degree of -0.1PMa for 24 hours to obtain a modified MOFs carrier, which was recorded as 5#.

[0141] Example 4 Compared with Example 1, this example changes the type of modifier for the crystallization reaction during the preparation of the carrier, and the modified atom is Al 3+ Changed to Si 4+ The modified MOFs prepared under these conditions were used as loading carriers to prepare loaded catalysts.

[0142] Example 5

[0143] (1) Add 188 ml of DMF and 12 ml of stabilizer acetic acid to a 250 ml beaker, stir evenly, then add 0.473 g of PTA, 0.631 g of zirconium chloride and 0.074 g of modifier anhydrous SnCl 4, stir thoroughly until completely dissolved. At this point, the volume of the stabilizer in the system accounts for 5.5% of the total system, PTA and Zr 4+ The concentration ratio of PTA and modifier Sn is 1.05:1. 4+ The concentration ratio is 10:1. The reaction solution is poured into a hydrothermal kettle and placed in an automatic homogeneous reactor for dynamic crystallization reaction. The temperature is raised from room temperature to the specified crystallization reaction temperature of 120°C at a heating rate of 1°C / min. The crystallization reaction time is 24h and the dynamic crystallization mechanical turning speed is 30rpm.

[0144] (2) After the crystallization reaction is completed, the product is cooled to room temperature, filtered after high speed rotation at 1000 rpm for 10 min, washed with DMF 3-5 times, and then with acetone 3-5 times, and dried at 80°C for 6 h to obtain a modified MOFs precursor.

[0145] (3) The modified MOFs precursor was placed in a vacuum drying oven for vacuum activation treatment at an activation temperature of 120°C and at a vacuum degree of -0.1PMa for 24 hours to obtain a modified MOFs carrier, which was recorded as 6#.

[0146] Example 5 Compared with Example 1, the type of modifier for the crystallization reaction was changed during the preparation of the carrier in this example. The modified atom was Al 3+ Changed to Sn 4+ The modified MOFs prepared under these conditions were used as loading carriers to prepare loaded catalysts.

[0147] Comparative Example 2

[0148] (1) Add 188 ml of DMF and 12 ml of stabilizer acetic acid to a 250 ml beaker, stir evenly, then add 0.473 g of PTA, 0.631 g of zirconium chloride and 0.038 g of modifier anhydrous AlCl 3 , stir thoroughly until completely dissolved. At this point, the volume of the stabilizer in the system accounts for 5.5% of the total system, PTA and Zr 4+ The concentration ratio of PTA and modifier Al is 1.05:1. 3+ The concentration ratio is 10: 1. The reaction solution is poured into a hydrothermal reactor for crystallization reaction, and the temperature is raised from room temperature to the specified crystallization reaction temperature of 120°C at a heating rate of 1°C / min, and the crystallization reaction time is 24h.

[0149] (2) After the crystallization reaction is completed, the product is cooled to room temperature, filtered after high speed rotation at 1000 rpm for 10 min, washed with DMF 3-5 times, and then with acetone 3-5 times, and dried at 80°C for 6 h to obtain a modified MOFs precursor.

[0150] (3) The modified MOFs precursor was placed in a vacuum drying oven for vacuum activation treatment at an activation temperature of 120°C and at a vacuum degree of -0.1PMa for 24 hours to obtain a modified MOFs carrier, which was recorded as 7#.

[0151] Compared with Example 1, the crystallization reaction in this comparative example is a static crystallization process, and the modified MOFs prepared under this condition are used as a loading carrier to prepare a loaded catalyst. The morphology of sample 7# was scanned by scanning electron microscope (SEM), and the results showed that Figure 2 shown.

[0152] Example 6

[0153] (1) Add 188 ml of DMF and 12 ml of stabilizer acetic acid to a 250 ml beaker, stir evenly, then add 0.473 g of PTA, 0.631 g of zirconium chloride and 0.038 g of modifier anhydrous AlCl 3 , stir thoroughly until completely dissolved. At this point, the volume of the stabilizer in the system accounts for 5.5% of the total system, PTA and Zr 4+ The concentration ratio of PTA and modifier Al is 1.05:1. 3+ The concentration ratio is 10:1. The reaction solution is poured into a hydrothermal kettle and placed in an automatic homogeneous reactor for dynamic crystallization reaction. The temperature is raised from room temperature to the specified crystallization reaction temperature of 80°C at a heating rate of 1°C / min. The crystallization reaction time is 24h and the dynamic crystallization mechanical turning speed is 30rpm.

[0154] (2) After the crystallization reaction is completed, the product is cooled to room temperature, filtered after high speed rotation at 1000 rpm for 10 min, washed with DMF 3-5 times, and then with acetone 3-5 times, and dried at 80°C for 6 h to obtain a modified MOFs precursor.

[0155] (3) The modified MOFs precursor was placed in a vacuum drying oven for vacuum activation treatment at an activation temperature of 120°C and at a vacuum degree of -0.1PMa for 24 hours to obtain a modified MOFs carrier, which was recorded as 8#.

[0156] Example 6 Compared with Example 1, in the preparation process of this example, the temperature of the crystallization reaction is changed, and the crystallization reaction temperature is slightly lowered. The modified MOFs prepared under this condition are used as the loading carrier to prepare a loaded catalyst.

[0157] Example 7

[0158] (1) Add 188 ml of DMF and 12 ml of stabilizer acetic acid to a 250 ml beaker, stir evenly, then add 0.473 g of PTA, 0.631 g of zirconium chloride and 0.038 g of modifier anhydrous AlCl 3, stir thoroughly until completely dissolved. At this point, the volume of the stabilizer in the system accounts for 5.5% of the total system, PTA and Zr 4+ The concentration ratio of PTA and modifier Al is 1.05:1. 3+ The concentration ratio is 10:1. The reaction solution is poured into a hydrothermal kettle and placed in an automatic homogeneous reactor for dynamic crystallization reaction. The temperature is raised from room temperature to the specified crystallization reaction temperature of 160°C at a heating rate of 1°C / min. The crystallization reaction time is 24h and the dynamic crystallization mechanical turning speed is 30rpm.

[0159] (2) After the crystallization reaction is completed, the product is cooled to room temperature, filtered after high speed rotation at 1000 rpm for 10 min, washed with DMF 3-5 times, and then with acetone 3-5 times, and dried at 80°C for 6 h to obtain a modified MOFs precursor.

[0160] (3) The modified MOFs precursor was placed in a vacuum drying oven for vacuum activation treatment at an activation temperature of 120°C and at a vacuum degree of -0.1PMa for 24 hours to obtain a modified MOFs carrier, which was recorded as 9#.

[0161] Compared with Example 1, in the preparation process of Example 7, the temperature of the crystallization reaction is changed, and the crystallization reaction temperature is slightly increased. The modified MOFs prepared under this condition are used as the loading carrier to prepare a loaded catalyst.

[0162] Example 8

[0163] (1) Add 188 ml of DMF and 12 ml of stabilizer acetic acid to a 250 ml beaker, stir evenly, then add 0.473 g of PTA, 0.631 g of zirconium chloride and 0.038 g of modifier anhydrous AlCl 3 , stir thoroughly until completely dissolved. At this point, the volume of the stabilizer in the system accounts for 5.5% of the total system, PTA and Zr 4+ The concentration ratio of PTA and modifier Al is 1.05:1. 3+ The concentration ratio is 10:1. The reaction solution is poured into a hydrothermal kettle and placed in an automatic homogeneous reactor for dynamic crystallization reaction. The temperature is raised from room temperature to the specified crystallization reaction temperature of 120°C at a heating rate of 5°C / min. The crystallization reaction time is 24h and the dynamic crystallization mechanical turning speed is 30rpm.

[0164] (2) After the crystallization reaction is completed, the product is cooled to room temperature, filtered after high speed rotation at 1000 rpm for 10 min, washed with DMF 3-5 times, and then with acetone 3-5 times, and dried at 80°C for 6 h to obtain a modified MOFs precursor.

[0165] (3) The modified MOFs precursor was placed in a vacuum drying oven for vacuum activation treatment at an activation temperature of 120°C and at a vacuum degree of -0.1PMa for 24 hours to obtain a modified MOFs carrier, which was recorded as 10#.

[0166] Compared with Example 1, in the preparation process of Example 8, the heating rate of heating to the specified crystallization reaction temperature was changed, so that the rate of reaching the crystallization reaction temperature became faster, and the crystallization heating rate was increased from 1°C / min to 5°C / min. The other conditions were not changed, and the modified MOFs prepared under these conditions were used as the loading carrier to prepare the loaded catalyst.

[0167] Comparative Example 3

[0168] (1) In a 250 ml beaker, add 188 ml of DMF solvent, 0.473 g of PTA, 0.631 g of zirconium chloride and 0.038 g of anhydrous AlCl 3 , stir thoroughly until completely dissolved. At this time, PTA and Zr 4+ The concentration ratio of PTA and modifier Al is 1.05:1. 3+ The concentration ratio is 10:1. The reaction solution is poured into a hydrothermal kettle and placed in an automatic homogeneous reactor for dynamic crystallization reaction. The temperature is raised from room temperature to the specified crystallization reaction temperature of 120°C at a heating rate of 1°C / min. The crystallization reaction time is 24h and the dynamic crystallization mechanical turning speed is 30rpm.

[0169] (2) After the crystallization reaction is completed, the product is cooled to room temperature, filtered after high speed rotation at 1000 rpm for 10 min, washed with DMF 3-5 times, and then with acetone 3-5 times, and dried at 80°C for 6 h to obtain a modified MOFs precursor.

[0170] (3) The modified MOFs precursor was placed in a vacuum drying oven for vacuum activation treatment at an activation temperature of 120°C and at a vacuum degree of -0.1PMa for 24 hours to obtain a modified MOFs carrier, which was recorded as 11#.

[0171] Compared with Example 1, in this comparative example, no stabilizer was added to adjust the formation of crystals during the preparation of the carrier. The modified MOFs prepared under this condition were used as the support to prepare a supported catalyst.

[0172] Example 9

[0173] Compared with Example 1, the present embodiment is different in that: (1) the carboxylate ligand is tris-benzoic acid, the stabilizer is citric acid, and the volume of the stabilizer accounts for 5% of the total volume of the mixed reaction system. 4+ The concentration ratio of tribenzoic acid and modifier Al is 0.1:1. 3+The concentration ratio is 0.1:1. The reaction solution is poured into a hydrothermal kettle and placed in an automatic homogeneous reactor for dynamic crystallization reaction. The temperature is raised from room temperature to the specified crystallization reaction temperature of 160°C at a heating rate of 10°C / min. The crystallization reaction time is 6h and the dynamic crystallization mechanical turning speed is 60rpm.

[0174] (2) After the crystallization reaction is completed, the product is cooled to room temperature, filtered after high speed rotation at 1200 rpm for 5 min, washed with DMF 3-5 times, and then with acetone 3-5 times, and dried at 70 °C for 10 h to obtain the modified MOFs precursor.

[0175] (3) The modified MOFs precursor is placed in a vacuum drying oven for vacuum activation treatment at an activation temperature of 80°C and at a vacuum degree of -0.1PMa for 96 hours to obtain a modified MOFs carrier.

[0176] Example 10

[0177] Compared with Example 1, the present embodiment is different in that: (1) the carboxylate ligand is naphthalene dicarboxylic acid, the stabilizer is oxalic acid, and the volume of the stabilizer accounts for 10% of the total volume of the mixed reaction system. 4+ The concentration ratio of naphthalene dicarboxylic acid and modifier Al is 5:1. 3+ The concentration ratio is 5:1. The reaction solution is poured into a hydrothermal kettle and placed in an automatic homogeneous reactor for dynamic crystallization reaction. The temperature is raised from room temperature to the specified crystallization reaction temperature of 80°C at a heating rate of 0.5°C / min. The crystallization reaction time is 96h and the dynamic crystallization mechanical turning speed is 10rpm.

[0178] (2) After the crystallization reaction is completed, the product is cooled to room temperature, filtered after high speed rotation at 700 rpm for 30 min, washed with DMF 3-5 times, and then with acetone 3-5 times, and dried at 60 °C for 12 h to obtain the modified MOFs precursor.

[0179] (3) The modified MOFs precursor is placed in a vacuum drying oven for vacuum activation treatment at an activation temperature of 200°C and at a vacuum degree of -0.01PMa for 6 hours to obtain a modified MOFs carrier.

[0180] Embodiment 11

[0181] Compared with Example 1, the present embodiment differs in that the carboxylate ligand is biphenyl-4,4-dicarboxylic acid, the stabilizer is oxalic acid, and the volume of the stabilizer accounts for 10% of the total volume of the mixed reaction system.

[0182] Example 12

[0183] Compared with Example 1, this embodiment is different in that the stabilizer is ethylenediaminetetraacetic acid, and the volume of the stabilizer accounts for 15% of the total volume of the mixed reaction system.

[0184] Embodiment 13

[0185] The present embodiment is different from the embodiment 1 in that the stabilizer is phosphoric acid, and the volume of the stabilizer accounts for 0.1% of the total volume of the mixed reaction system.

[0186] Embodiment 14

[0187] Select the 1# modified MOFs carrier prepared in Example 1 as the loading

[0188] (1) Determination of saturated water absorption: Take 1g of the dried 1# modified MOFs carrier and place it in a beaker. Slowly and evenly add deionized water until 1g of the modified MOFs carrier is saturated with adsorption and the surface of the modified MOFs carrier is just soaked. At this time, the amount of water adsorbed by the modified MOFs carrier is the saturated water absorption of the carrier, and the saturated water absorption is 2ml.

[0189] (2) Add 2 ml of water and 0.202 g of copper nitrate trihydrate into a beaker and dissolve thoroughly to prepare Cu(NO 3 ) 2 Using the equal volume impregnation method, 1g of 1# modified MOFs carrier particles was slowly poured into the configured Cu(NO 3 ) 2 In the solution, mix the liquid and powder evenly, and leave it open in the air for 48 hours until the surface is completely dry.

[0190] (3) The sample is then placed in an oven and dried until completely dry. Finally, the sample is placed in a tubular furnace and calcined in a nitrogen atmosphere at a gradient temperature increase rate from room temperature to 300°C at a heating rate of 1°C / min. The sample is calcined at the specified temperature for 3 h, and taken out after cooling to obtain a supported catalyst with oxidized modified MOFs as the supported catalyst.

[0191] (4) Then, the sample was subjected to a gradient temperature reduction in a tubular furnace under a hydrogen atmosphere, and the temperature was increased from room temperature to 300°C at a rate of 1°C / min, and the sample was reduced at the specified temperature for 3 hours to obtain a modified Cu-MOFs supported catalyst with a Cu content of 5 wt%, denoted as 1-1#. XPS valence state characterization of sample 1-1# was performed, and the results showed that Figure 3 The results of TEM scanning of sample 1-1# show Figure 4 As shown in the particle size analysis diagram Figure 5b shown.

[0192] Embodiment 15

[0193] The 2# modified MOFs carrier prepared in Example 2 was selected as the support, and the same loading method as in Example 14 was adopted to obtain a modified Cu-MOFs supported catalyst, with a Cu content of 5 wt%, recorded as 1-2#.

[0194] Example 16

[0195] The 3# modified MOFs carrier prepared in Example 3 was selected as the support, and the same loading method as in Example 14 was adopted to obtain a modified Cu-MOFs supported catalyst, with a Cu content of 5 wt%, recorded as 1-3#.

[0196] Comparative Example 4

[0197] The 4# modified MOFs carrier prepared in Comparative Example 1 was selected as the support, and the same loading method as in Example 14 was adopted to prepare a modified Cu-MOFs supported catalyst, with a Cu content of 5 wt%, recorded as 1-4#.

[0198] Embodiment 17

[0199] The 5# modified MOFs carrier prepared in Example 4 was selected as the support, and the same loading method as in Example 14 was adopted to obtain a modified Cu-MOFs supported catalyst, with a Cu content of 5 wt%, recorded as 1-5#.

[0200] Embodiment 18

[0201] The 6# modified MOFs carrier prepared in Example 5 was selected as the support, and the same loading method as in Example 14 was adopted to obtain a modified Cu-MOFs supported catalyst, with a Cu content of 5 wt%, recorded as 1-6#.

[0202] Comparative Example 5

[0203] The 7# modified MOFs carrier prepared in Comparative Example 2 was selected as the support, and the same loading method as in Example 14 was adopted to obtain a modified Cu-MOFs supported catalyst, with a Cu content of 5 wt%, recorded as 1-7#.

[0204] Embodiment 19

[0205] The 8# modified MOFs carrier prepared in Example 6 was selected as the support, and the same loading method as in Example 14 was adopted to obtain a modified Cu-MOFs supported catalyst, with a Cu content of 5 wt%, recorded as 1-8#.

[0206] Embodiment 20

[0207] The 9# modified MOFs carrier prepared in Example 7 was selected as the support, and the same loading method as in Example 14 was adopted to obtain a modified Cu-MOFs supported catalyst, with a Cu content of 5 wt%, recorded as 1-9#.

[0208] Embodiment 21

[0209] The 10# modified MOFs carrier prepared in Example 8 was selected as the support, and the same loading method as in Example 14 was adopted to obtain a modified Cu-MOFs supported catalyst, with a Cu content of 5 wt%, recorded as 1-10#.

[0210] Comparative Example 6

[0211] The 11# modified MOFs carrier prepared in Comparative Example 3 was selected as the support, and the same loading method as in Example 14 was adopted to obtain a modified Cu-MOFs supported catalyst, with a Cu content of 5 wt%, recorded as 1-11#.

[0212] Embodiment 22

[0213] Select the 1# modified MOFs carrier prepared in Example 1 as the loading

[0214] (1) Add 2 ml of water and 0.099 g of copper nitrate trihydrate to a beaker and dissolve thoroughly to prepare Cu(NO 3 ) 2 The solution was loaded onto the 1# modified MOFs carrier by equal volume impregnation method, and then the same loading method as in Example 14 was adopted to obtain a modified Cu-MOFs supported catalyst, with a Cu content of 2.5 wt%, denoted as 2-1#. The oxidation state of sample 2-1# was characterized by XRD, and the results showed that Figure 6 shown.

[0215] Example 22 Compared with Example 14, the metal loading of the supported catalyst prepared in this example is changed to 2.5 wt %. XPS valence state characterization of the reduced state of sample 2-1# is performed, and the results show that Figure 3 The particle size analysis of sample 2-1# is shown in the figure below. Figure 5a shown.

[0216] Embodiment 23

[0217] Select the 1# modified MOFs carrier prepared in Example 1 as the loading

[0218] (1) Add 2 ml of water and 0.311 g of copper nitrate trihydrate to a beaker and dissolve thoroughly to prepare Cu(NO 3 ) 2 The solution was loaded onto the 1# modified MOFs carrier by an equal volume impregnation method, and then the same loading method as in Example 14 was adopted to obtain a modified Cu-MOFs supported catalyst, with a Cu content of 7.5 wt%, recorded as 3-1#.

[0219] Example 23 Compared with Example 14, the metal loading of the supported catalyst prepared in this example is changed to 7.5 wt%. XPS valence state characterization of the reduced state of sample 3-1# is performed, and the results show that Figure 3 The particle size analysis of sample 3-1# is shown in the figure below. Figure 5c shown.

[0220] Embodiment 24

[0221] Select the 1# modified MOFs carrier prepared in Example 1 as the loading

[0222] Add 2 ml of water and 0.427 g of copper nitrate trihydrate into a beaker and dissolve thoroughly to prepare Cu(NO 3 ) 2 The solution was loaded onto the 1# modified MOFs carrier by an equal volume impregnation method, and then the same loading method as in Example 14 was adopted to obtain a modified Cu-MOFs supported catalyst, the mass content of Cu was 10wt%, and was recorded as 4-1#.

[0223] Example 24 Compared with Example 14, the metal loading of the supported catalyst prepared in this example is changed to 10 wt%. XPS valence state characterization of the reduced state of sample 4-1# is performed, and the results show that Figure 3 The particle size analysis of sample 4-1# is shown in the figure below. Figure 5d shown.

[0224] Embodiment 25

[0225] Select the 1# modified MOFs carrier prepared in Example 1 as the loading

[0226] (1) Add 2 ml of water and 0.243 g of nickel nitrate hexahydrate into a beaker and dissolve them thoroughly to prepare Ni(NO 3 ) 2 Using the equal volume impregnation method, 1g of 1# modified MOFs carrier particles was slowly poured into the configured Ni(NO 3 ) 2 In the solution, mix the liquid and powder evenly, and leave it open in the air for 48 hours until the surface is completely dry.

[0227] (2) The sample is then placed in an oven and dried until completely dry. Finally, the sample is placed in a tubular furnace and calcined in a nitrogen atmosphere at a gradient temperature increase rate from room temperature to 300°C at a heating rate of 1°C / min. The sample is calcined at the specified temperature for 3 h, and taken out after cooling to obtain a supported catalyst with oxidized modified MOFs as the supported catalyst.

[0228] (3) Then, the catalyst was reduced by gradient temperature increase in a tubular furnace under a hydrogen atmosphere, with the temperature rising from room temperature to 300°C at a rate of 1°C / min, and reduced at the specified temperature for 3 h to obtain a modified Ni-MOFs supported catalyst with a Ni content of 5 wt%, denoted as 5-1#.

[0229] Compared with Example 14, the supported catalyst prepared in Example 25 has a different type of supported metal.

[0230] Embodiment 26

[0231] Select the 1# modified MOFs carrier prepared in Example 1 as the loading

[0232] (1) Add 2 ml of water and 0.202 g of copper nitrate trihydrate into a beaker and dissolve thoroughly to prepare Cu(NO 3 ) 2 Using the equal volume impregnation method, 1g of 1# modified MOFs carrier particles was slowly poured into the configured Cu(NO 3 ) 2 In the solution, mix the liquid and powder evenly, and leave it open in the air for 48 hours until the surface is completely dry.

[0233] (2) The sample is then placed in an oven and dried until completely dry. Finally, the sample is placed in a tubular furnace and calcined in a nitrogen atmosphere at a gradient temperature increase rate from room temperature at 5°C / min to 300°C. The sample is calcined at the specified temperature for 3 h, and taken out after cooling to obtain a supported catalyst with oxidized modified MOFs as the supported catalyst.

[0234] (3) Then, the catalyst was reduced by gradient temperature increase in a tubular furnace under a hydrogen atmosphere, with the temperature rising from room temperature to 300°C at a rate of 1°C / min, and reduced at the specified temperature for 3 h to obtain a modified Cu-MOFs supported catalyst with a Cu content of 5 wt%, recorded as 6-1#.

[0235] Compared with Example 14, the supported catalyst prepared in this example changes the heating rate to the specified calcination temperature during the preparation process.

[0236] Embodiment 27

[0237] Select the 1# modified MOFs carrier prepared in Example 1 as the loading

[0238] (1) Add 2 ml of water and 0.202 g of copper nitrate trihydrate into a beaker and dissolve thoroughly to prepare Cu(NO 3 ) 2 Using the equal volume impregnation method, 1g of 1# modified MOFs carrier particles was slowly poured into the configured Cu(NO 3 ) 2In the solution, mix the liquid and powder evenly, and leave it open in the air for 48 hours until the surface is completely dry.

[0239] (2) The sample is then placed in an oven and dried until completely dry. Finally, the sample is placed in a tubular furnace and calcined in a nitrogen atmosphere at a gradient temperature increase rate from room temperature to 500°C at a heating rate of 1°C / min. The sample is calcined at the specified temperature for 3 h, and taken out after cooling to obtain a supported catalyst with oxidized modified MOFs as the supported catalyst.

[0240] (3) Then, the catalyst was reduced by gradient temperature increase in a tubular furnace under a hydrogen atmosphere, with the temperature rising from room temperature to 300°C at a rate of 1°C / min, and reduced at the specified temperature for 3 h to obtain a modified Cu-MOFs supported catalyst with a Cu content of 5 wt%, recorded as 7-1#.

[0241] Compared with Example 14, the calcination temperature of the supported catalyst prepared in Example 27 was changed from 300°C to 500°C.

[0242] Embodiment 28

[0243] Select the 1# modified MOFs carrier prepared in Example 1 as the loading

[0244] (1) Add 2 ml of water and 0.202 g of copper nitrate trihydrate into a beaker and dissolve thoroughly to prepare Cu(NO 3 ) 2 Using the equal volume impregnation method, 1g of 1# modified MOFs carrier particles was slowly poured into the configured Cu(NO 3 ) 2 In the solution, mix the liquid and powder evenly, and leave it open in the air for 48 hours until the surface is completely dry.

[0245] (2) The sample is then placed in an oven and dried until completely dry. Finally, the sample is placed in a tubular furnace and calcined in a nitrogen atmosphere at a gradient temperature increase rate from room temperature to 200°C at a heating rate of 1°C / min. The sample is calcined at the specified temperature for 3 h, and taken out after cooling to obtain a supported catalyst with oxidized modified MOFs as the supported catalyst.

[0246] (3) Then, the catalyst was reduced by gradient temperature increase in a tubular furnace under a hydrogen atmosphere, with the temperature rising from room temperature to 200°C at a rate of 1°C / min, and reduced at the specified temperature for 3 h to obtain a modified Cu-MOFs supported catalyst with a Cu content of 5 wt%, denoted as 8-1#.

[0247] Compared with Example 14, the calcination temperature of the supported catalyst prepared in Example 28 was changed from 300°C to 200°C.

[0248] Embodiment 29

[0249] Select the 1# modified MOFs carrier prepared in Example 1 as the loading

[0250] (1) Add 2 ml of water and 0.202 g of copper nitrate trihydrate into a beaker and dissolve thoroughly to prepare Cu(NO 3 ) 2 Using the equal volume impregnation method, 1g of 1# modified MOFs carrier particles was slowly poured into the configured Cu(NO 3 ) 2 In the solution, mix the liquid and powder evenly, and leave it open in the air for 48 hours until the surface is completely dry.

[0251] (2) The sample is then placed in an oven and dried until completely dry. Finally, the sample is placed in a tubular furnace and calcined in a nitrogen atmosphere at a gradient temperature increase rate from room temperature to 300°C at a heating rate of 1°C / min. The sample is calcined at the specified temperature for 3 h, and taken out after cooling to obtain a supported catalyst with oxidized modified MOFs as the supported catalyst.

[0252] (3) Then, the catalyst was reduced by gradient temperature increase in a tubular furnace under a hydrogen atmosphere, with the temperature rising from room temperature to 300°C at a rate of 5°C / min, and reduced at the specified temperature for 3 hours to obtain a modified Cu-MOFs supported catalyst with a Cu content of 5 wt%. The catalyst was recorded as 9-1#.

[0253] Compared with Example 14, when the supported catalyst prepared in this example was reduced in a hydrogen atmosphere, the heating rate to the specified reduction temperature was changed.

[0254] Embodiment 30

[0255] Select the 1# modified MOFs carrier prepared in Example 1 as the loading

[0256] (1) Add 2 ml of water and 0.202 g of copper nitrate trihydrate into a beaker and dissolve thoroughly to prepare Cu(NO 3 ) 2 Using the equal volume impregnation method, 1g of 1# modified MOFs carrier particles was slowly poured into the configured Cu(NO 3 ) 2 In the solution, mix the liquid and powder evenly, and leave it open in the air for 48 hours until the surface is completely dry.

[0257] (2) The sample is then placed in an oven and dried until completely dry. Finally, the sample is placed in a tubular furnace and calcined in a nitrogen atmosphere at a gradient temperature increase rate from room temperature to 300°C at a heating rate of 1°C / min. The sample is calcined at the specified temperature for 3 h, and taken out after cooling to obtain a supported catalyst with oxidized modified MOFs as the supported catalyst.

[0258] (3) Then, the catalyst was reduced by gradient temperature increase in a tubular furnace under a hydrogen atmosphere, with the temperature rising from room temperature to 600°C at a rate of 1°C / min, and reduced at the specified temperature for 3 hours to obtain a modified Cu-MOFs supported catalyst with a Cu content of 5 wt%, denoted as 10-1#.

[0259] Compared with Example 14, when the supported catalyst prepared in Example 30 was reduced in a hydrogen atmosphere, the specified reduction temperature was changed from 300° C. to 600° C.

[0260] Embodiment 31

[0261] Select the 1# modified MOFs carrier prepared in Example 1 as the loading

[0262] (1) Add 2 ml of water and 0.202 g of copper nitrate trihydrate into a beaker and dissolve thoroughly to prepare Cu(NO 3 ) 2 Using the equal volume impregnation method, 1g of 1# modified MOFs carrier particles was slowly poured into the configured Cu(NO 3 ) 2 In the solution, mix the liquid and powder evenly, and leave it open in the air for 48 hours until the surface is completely dry.

[0263] (2) The sample is then placed in an oven and dried until completely dry. Finally, the sample is placed in a tubular furnace and calcined in a nitrogen atmosphere at a gradient temperature increase rate from room temperature to 300°C at a heating rate of 1°C / min. The sample is calcined at the specified temperature for 3 h, and taken out after cooling to obtain a supported catalyst with oxidized modified MOFs as the supported catalyst.

[0264] (3) Then, the catalyst was reduced by gradient temperature increase in a tubular furnace under a hydrogen atmosphere, with the temperature rising from room temperature to 100°C at a rate of 1°C / min, and reduced at the specified temperature for 3 h to obtain a modified Cu-MOFs supported catalyst with a Cu content of 5 wt%, recorded as 11-1#.

[0265] Compared with Example 14, when the supported catalyst prepared in this example was reduced in a hydrogen atmosphere, the specified reduction temperature was changed from 300°C to 100°C.

[0266] Embodiment 32

[0267] Compared with Example 14, this embodiment is different in that:

[0268] (2) The sample is then placed in an oven and dried until completely dry. Finally, the sample is placed in a tubular furnace and calcined in a nitrogen atmosphere at a gradient temperature increase rate from room temperature to 200°C at a heating rate of 0.5°C / min. The sample is calcined at the specified temperature for 20 h, and taken out after cooling to obtain a supported catalyst with oxidized modified MOFs as the supported catalyst.

[0269] (3) Then, the modified Cu-MOFs supported catalyst was obtained by gradient temperature reduction in a tubular furnace under a hydrogen atmosphere, with the temperature rising at a rate of 0.5°C / min from room temperature to 100°C, and the reduction was carried out at the specified temperature for 30 hours.

[0270] Embodiment 33

[0271] Compared with Example 14, this embodiment is different in that:

[0272] (2) The sample is then placed in an oven and dried until completely dry. Finally, the sample is placed in a tubular furnace and calcined in a nitrogen atmosphere at a gradient temperature increase rate from room temperature to 500°C at a heating rate of 10°C / min. The sample is calcined at the specified temperature for 1 h, and taken out after cooling to obtain a supported catalyst with oxidized modified MOFs as the supported catalyst.

[0273] (3) Then, the modified Cu-MOFs supported catalyst was obtained by gradient temperature reduction in a tubular furnace under a hydrogen atmosphere, with the temperature rising at a rate of 10°C / min from room temperature to 600°C, and reducing at the specified temperature for 1 hour.

[0274] Embodiment 34

[0275] (1) Add 30 ml of isopropanol and 0.5 g of HMF to the polytetrafluoroethylene liner and stir thoroughly to make the raw materials dispersed evenly and stably in the reaction system. At this time, the concentration of HMF in the solution system is 132 mM. Take a sample as the concentration of the initial reaction;

[0276] (2) Then, 0.1 g of the 1-1# catalyst prepared in Example 14 was added, and the mass ratio of the substrate HMF to the catalyst was 5:1, and the mixture was transferred to the hydrogenation reactor. After three times of nitrogen replacement of the air, hydrogen was introduced to 2 MPa, the speed was adjusted to 800 rpm, and the temperature was programmed to 150°C for a hydrogenation reaction time of 2 h.

[0277] (3) After the reaction was completed, the reaction solution was cooled to room temperature and the contents in the reaction solution were analyzed by LC. The results are shown in Table 1.

[0278] Table 1 Reaction results of Example 34

[0279]

[0280]

[0281] Embodiment 35

[0282] (1) Add 30 ml of isopropanol and 0.5 g of HMF to the polytetrafluoroethylene liner and stir thoroughly to make the raw materials dispersed evenly and stably in the reaction system. At this time, the concentration of HMF in the solution system is 132 mM. Take a sample as the concentration of the initial reaction;

[0283] (2) Then, 0.1 g of the 1-2# catalyst prepared in Example 15 was added, and the mass ratio of the substrate HMF to the catalyst was 5:1, and the mixture was transferred to the hydrogenation reactor. After three times of nitrogen replacement of the air, hydrogen was introduced to 2 MPa, the speed was adjusted to 800 rpm, and the temperature was programmed to 150°C for a hydrogenation reaction time of 2 h.

[0284] (3) After the reaction was completed, the reaction solution was cooled to room temperature and the contents in the reaction solution were analyzed by LC. The results are shown in Table 2.

[0285] Table 2 Reaction results of Example 35

[0286] Example BHMF yield HMF conversion Catalyst selectivity 35 70 99 71

[0287] Compared with Example 34, Example 35, the catalyst sample used in this example has changed, and the catalyst sample used has changed from 1-1# to 1-2#, that is, the preparation method of the carrier has changed, and the amount of modifier in the precursor for preparing the modified MOFs carrier has increased, and the other preparation conditions have not changed. The conversion rate of HMF increases with the increase of the amount of modifier, but the increase in the amount of modified atoms leads to an excessive amount of acid in the carrier, which causes the reaction to proceed excessively, so that the generated target product BHMF undergoes excessive etherification reaction in the acid catalyst and solvent isopropanol, which ultimately affects its selectivity for HMF and the yield of BHMF during the catalytic reaction.

[0288] Embodiment 36

[0289] (1) Add 30 ml of isopropanol and 0.5 g of HMF to the polytetrafluoroethylene liner and stir thoroughly to make the raw materials dispersed evenly and stably in the reaction system. At this time, the concentration of HMF in the solution system is 132 mM. Take a sample as the concentration of the initial reaction;

[0290] (2) Then, 0.1 g of the 1-3# catalyst prepared in Example 16 was added, and the mass ratio of the substrate HMF to the catalyst was 5:1, and the mixture was transferred to the hydrogenation reactor. After three times of nitrogen replacement of the air, hydrogen was introduced to 2 MPa, the speed was adjusted to 800 rpm, and the temperature was programmed to 150°C for a hydrogenation reaction time of 2 h.

[0291] (3) After the reaction was completed, the reaction solution was cooled to room temperature and the contents in the reaction solution were analyzed by LC. The results are shown in Table 3.

[0292] Table 3 Reaction results of Example 36

[0293] Example BHMF yield HMF conversion Catalyst selectivity 36 86 91 95

[0294] Compared with Example 34, the catalyst sample used in Example 36 was changed from 1-1# to 1-3#, that is, the preparation method of the carrier was changed, the amount of the modifier in the precursor for preparing the modified MOFs carrier was reduced, and the other preparation conditions remained unchanged. However, due to the reduction of the modified atoms, the acid content of the carrier was reduced, which slightly reduced the adsorption capacity of the carrier for HMF molecules, thereby slowing down the reaction rate, and ultimately affected its selectivity for HMF and the yield of BHMF during the catalytic reaction.

[0295] Comparative Example 7

[0296] (1) Add 30 ml of isopropanol and 0.5 g of HMF to the polytetrafluoroethylene liner and stir thoroughly to make the raw materials dispersed evenly and stably in the reaction system. At this time, the concentration of HMF in the solution system is 132 mM. Take a sample as the concentration of the initial reaction;

[0297] (2) Then, 0.1 g of the 1-4# catalyst prepared in Comparative Example 4 was added, and the mass ratio of the substrate HMF to the catalyst was 5:1, and the mixture was transferred to the hydrogenation reactor. After three nitrogen replacements of the air, hydrogen was introduced to 2 MPa, the speed was adjusted to 800 rpm, and the temperature was programmed to 150°C for a hydrogenation reaction time of 2 h.

[0298] (3) After the reaction was completed, the reaction solution was cooled to room temperature and the contents in the reaction solution were analyzed by LC. The results are shown in Table 4.

[0299] Table 4 Reaction results of comparative example 7

[0300] Comparative Example BHMF yield HMF conversion Catalyst selectivity 7 80 86 93

[0301] Compared with Example 34, the catalyst sample used in Comparative Example 7 has changed from 1-1# to 1-4#, that is, the preparation method of the carrier has changed, and no modifier is added to the precursor for preparing the modified MOFs carrier, and the other preparation conditions have not changed. Since no modified atoms are added, the adsorption capacity of the carrier for HMF molecules is significantly reduced, thereby slowing down the reaction rate. The final prepared catalyst affects its selectivity for HMF and the yield of BHMF during the catalytic reaction.

[0302] Embodiment 37

[0303] (1) Add 30 ml of isopropanol and 0.5 g of HMF to the polytetrafluoroethylene liner and stir thoroughly to make the raw materials dispersed evenly and stably in the reaction system. At this time, the concentration of HMF in the solution system is 132 mM. Take a sample as the concentration of the initial reaction;

[0304] (2) Then, 0.1 g of the 1-5# catalyst prepared in Example 17 was added, and the mass ratio of the substrate HMF to the catalyst was 5:1, and the mixture was transferred to the hydrogenation reactor. After three times of nitrogen replacement of the air, hydrogen was introduced to 2 MPa, the speed was adjusted to 800 rpm, and the temperature was programmed to 150°C for a hydrogenation reaction time of 2 h.

[0305] (3) After the reaction was completed, the reaction solution was cooled to room temperature and the contents in the reaction solution were analyzed by LC. The results are shown in Table 5.

[0306] Table 5 Reaction results of Example 37

[0307] Example BHMF yield HMF conversion Catalyst selectivity 37 95 96 99

[0308] Compared with Example 34, the catalyst sample used in Example 37 was changed from 1-1# to 1-5#, that is, the preparation method of the carrier was changed, and the type of the modifier added in the precursor of the modified MOFs carrier was changed, and the modified atom was changed from Al 3+ Changed to Si 4+ , the other preparation conditions remained unchanged, the conversion rate of HMF decreased slightly, while the yield of BHMF increased. This is due to the Si 4+ The amount of acid added is comparable to that of Al 3+ There is a slight deficiency, which makes the carrier slightly affect the adsorption capacity of HMF molecules, but it can promote the reducibility of the metal component to enhance the hydrogenation activity of the catalyst. The final prepared catalyst improves the selectivity of the catalyst in the catalytic reaction process. It can be seen that choosing a suitable modifier to modify the MOFs carrier is the key to affecting the hydrogenation reduction of HMF to BHMF.

[0309] Embodiment 38

[0310] (1) Add 30 ml of isopropanol and 0.5 g of HMF to the polytetrafluoroethylene liner and stir thoroughly to make the raw materials dispersed evenly and stably in the reaction system. At this time, the concentration of HMF in the solution system is 132 mM. Take a sample as the concentration of the initial reaction;

[0311] (2) Then, 0.1 g of the 1-6# catalyst prepared in Example 18 was added, and the mass ratio of the substrate HMF to the catalyst was 5:1, and the mixture was transferred to the hydrogenation reactor. After three nitrogen replacements of the air, hydrogen was introduced to 2 MPa, the speed was adjusted to 800 rpm, and the temperature was programmed to 150°C for a hydrogenation reaction time of 2 h.

[0312] (3) After the reaction was completed, the reaction solution was cooled to room temperature and the contents in the reaction solution were analyzed by LC. The results are shown in Table 6.

[0313] Table 6 Reaction results of Example 38

[0314] Example BHMF yield HMF conversion Catalyst selectivity 38 95 96 99

[0315] Compared with Example 34, the catalyst sample used in Example 38 was changed from 1-1# to 1-6#, that is, the preparation method of the carrier was changed, and the type of the modifier added in the precursor of the modified MOFs carrier was changed, and the modified atom was changed from Al 3+ Changed to Sn 4+ , the other preparation conditions were unchanged, and the conversion rate of HMF and the yield of BHMF were both insufficient compared with those in Example 34. It can be seen that selecting a suitable modifier to modify the MOFs support is the key to affecting the hydrogenation reduction of HMF to BHMF.

[0316] Comparative Example 8

[0317] (1) Add 30 ml of isopropanol and 0.5 g of HMF to the polytetrafluoroethylene liner and stir thoroughly to make the raw materials dispersed evenly and stably in the reaction system. At this time, the concentration of HMF in the solution system is 132 mM. Take a sample as the concentration of the initial reaction;

[0318] (2) Then, 0.1 g of the 1-7# catalyst prepared in Comparative Example 5 was added, and the mass ratio of the substrate HMF to the catalyst was 5:1, and the mixture was transferred to the hydrogenation reactor. After three nitrogen replacements of the air, hydrogen was introduced to 2 MPa, the speed was adjusted to 800 rpm, and the temperature was programmed to 150°C for a hydrogenation reaction time of 2 h.

[0319] (3) After the reaction was completed, the reaction solution was cooled to room temperature and the contents in the reaction solution were analyzed by LC. The results are shown in Table 7.

[0320] Table 7 Reaction results of comparative example 8

[0321] Comparative Example BHMF yield HMF conversion Catalyst selectivity 8 82 94 87

[0322] Compared with Example 34, the catalyst sample used in Comparative Example 8 has changed. The catalyst sample used has changed from 1-1# to 1-7#, that is, the preparation method of the carrier has changed. The crystallization reaction method has been changed in the precursor for preparing the modified MOFs carrier, from dynamic crystallization to conventional static crystallization reaction. The other preparation conditions have not changed. The conversion rate of HMF and the yield of BHMF have both decreased. The crystal arrangement order of the carrier prepared by static crystallization is worse than that of Example 34. Because of the heterogeneity of the size of the static crystallization carrier, the uniform stability of the metal nanoparticles loaded is relatively insufficient. The catalyst finally prepared affects its selectivity for HMF and the yield of BHMF during the catalytic reaction. Moreover, the carriers prepared by static crystallization have high yields, low yields, and poor repeatability.

[0323] Embodiment 39

[0324] (1) Add 30 ml of isopropanol and 0.5 g of HMF to the polytetrafluoroethylene liner and stir thoroughly to make the raw materials dispersed evenly and stably in the reaction system. At this time, the concentration of HMF in the solution system is 132 mM. Take a sample as the concentration of the initial reaction;

[0325] (2) Then, 0.1 g of the 1-8# catalyst prepared in Example 19 was added, and the mass ratio of the substrate HMF to the catalyst was 5:1, and the mixture was transferred to the hydrogenation reactor. After three nitrogen replacements of the air, hydrogen was introduced to 2 MPa, the speed was adjusted to 800 rpm, and the temperature was programmed to 150°C for a hydrogenation reaction time of 2 h.

[0326] (3) After the reaction was completed, the reaction solution was cooled to room temperature and the contents in the reaction solution were analyzed by LC. The results are shown in Table 8.

[0327] Table 8 Reaction results of Example 39

[0328] Example BHMF yield HMF conversion Catalyst selectivity 39 69 84 82

[0329] Compared with Example 34, Example 39 shows that the catalyst sample used in this example has changed from 1-1# to 1-8#, that is, the preparation method of the carrier has changed, and the specified crystallization reaction temperature has been changed in the process of preparing the modified MOFs carrier, so that the crystallization reaction temperature is lower, and the other preparation conditions have not changed. The lower crystallization reaction temperature affects the precursor molding, resulting in a low dispersion of the metal load on the carrier during the loading process, and the final prepared catalyst affects its selectivity for HMF and the yield of BHMF during the catalytic reaction.

[0330] Embodiment 40

[0331] (1) Add 30 ml of isopropanol and 0.5 g of HMF to the polytetrafluoroethylene liner and stir thoroughly to make the raw materials dispersed evenly and stably in the reaction system. At this time, the concentration of HMF in the solution system is 132 mM. Take a sample as the concentration of the initial reaction;

[0332] (2) Then, 0.1 g of the 1-9# catalyst prepared in Example 20 was added, and the mass ratio of the substrate HMF to the catalyst was 5:1, and the mixture was transferred to the hydrogenation reactor. After three times of nitrogen replacement of the air, hydrogen was introduced to 2 MPa, the speed was adjusted to 800 rpm, and the temperature was programmed to 150°C for a hydrogenation reaction time of 2 h.

[0333] (3) After the reaction was completed, the reaction solution was cooled to room temperature and the contents in the reaction solution were analyzed by LC. The results are shown in Table 9.

[0334] Table 9 Reaction results of Example 40

[0335] Example BHMF yield HMF conversion Catalyst selectivity 40 78 89 88

[0336] Compared with Example 34, Example 40, the catalyst sample used in this example has changed, and the catalyst sample used has changed from 1-1# to 1-9#, that is, the preparation method of the carrier has changed, and the specified crystallization reaction temperature has been changed in the process of preparing the modified MOFs carrier, so that the crystallization reaction temperature has increased, and the other preparation conditions have not changed. The increase in the crystallization reaction temperature causes the precursor to segregate at the grain boundaries during the molding process, which in turn causes the loaded metal atoms to aggregate at the grain boundaries, and the final prepared catalyst affects its selectivity for HMF and the yield of BHMF during the catalytic reaction.

[0337] Embodiment 41

[0338] (1) Add 30 ml of isopropanol and 0.5 g of HMF to the polytetrafluoroethylene liner and stir thoroughly to make the raw materials dispersed evenly and stably in the reaction system. At this time, the concentration of HMF in the solution system is 132 mM. Take a sample as the concentration of the initial reaction;

[0339] (2) Then, 0.1 g of the 1-10# catalyst prepared in Example 21 was added, and the mass ratio of the substrate HMF to the catalyst was 5:1, and the mixture was transferred to the hydrogenation reactor. After three nitrogen replacements of the air, hydrogen was introduced to 2 MPa, the speed was adjusted to 800 rpm, and the temperature was programmed to 150°C for a hydrogenation reaction time of 2 h.

[0340] (3) After the reaction was completed, the reaction solution was cooled to room temperature and the contents in the reaction solution were analyzed by LC. The results are shown in Table 10.

[0341] Table 10 Reaction results of Example 41

[0342] Example BHMF yield HMF conversion Catalyst selectivity 41 82 89 92

[0343] Compared with Example 33, Example 41, the catalyst sample used in this example has changed, and the catalyst sample used has changed from 1-1# to 1-10#, that is, the preparation method of the carrier has changed, and the heating rate for reaching the specified crystallization reaction has been changed in the process of preparing the modified MOFs carrier, so that the heating rate for reaching the specified crystallization reaction has become faster, and the final prepared catalyst has affected its selectivity for HMF and the yield of BHMF during the catalytic reaction. This is because the rapid temperature change will lead to the formation of a large number of crystal buds in the forming process of the precursor, and the crystals are often small because they are not fully developed, which makes it easier to wrap the impurities generated during the crystallization reaction, which will make the impurities difficult to remove in the subsequent washing and activation process, thereby affecting the performance of the final prepared catalyst.

[0344] Comparative Example 9

[0345] (1) Add 30 ml of isopropanol and 0.5 g of HMF to the polytetrafluoroethylene liner and stir thoroughly to make the raw materials dispersed evenly and stably in the reaction system. At this time, the concentration of HMF in the solution system is 132 mM. Take a sample as the concentration of the initial reaction;

[0346] (2) Then, 0.1 g of the 1-11# catalyst prepared in Comparative Example 6 was added, and the mass ratio of the substrate HMF to the catalyst was 5:1, and the mixture was transferred to a hydrogenation reactor. After three nitrogen replacements of the air, hydrogen was introduced to 2 MPa, the speed was adjusted to 800 rpm, and the temperature was programmed to 150°C for 2 h;

[0347] (3) After the reaction was completed, the reaction solution was cooled to room temperature and the contents in the reaction solution were analyzed by LC. The results are shown in Table 11.

[0348] Table 11 Reaction results of comparative example 9

[0349] Comparative Example BHMF yield HMF conversion Catalyst selectivity 9 21 52 40

[0350] Compared with Example 34 and Comparative Example 9, the catalyst sample used in this comparative example has changed, and the catalyst sample used has changed from 1-1# to 1-11#, that is, the preparation method of the carrier has changed, and no stabilizer is added in the process of preparing the modified MOFs carrier, and the other preparation conditions are unchanged. Since no stabilizer is added in the crystallization reaction, the carrier forms an irregular or unstable crystal structure during the molding process, and the dispersion and stability of the crystals are reduced, thereby affecting the selectivity of the catalyst finally prepared for HMF and the yield of BHMF during the catalytic reaction.

[0351] Embodiment 42

[0352] The 2-1# modified MOFs carrier (2.5wt% Cu) prepared in Example 22 was selected for catalytic hydrogenation reaction, and the same reaction conditions as in Example 34 were adopted. After the reaction, the contents in the reaction solution were analyzed by LC. The results are shown in Table 12.

[0353] Embodiment 43

[0354] The 3-1# modified MOFs carrier (7.5wt% Cu) prepared in Example 23 was selected for catalytic hydrogenation reaction, and the same reaction conditions as in Example 34 were adopted. After the reaction, the contents in the reaction solution were analyzed by LC. The results are shown in Table 12.

[0355] Embodiment 44

[0356] The 4-1# modified MOFs carrier (10 wt% Cu) prepared in Example 24 was selected for catalytic hydrogenation reaction, and the same reaction conditions as in Example 34 were adopted. After the reaction, the contents in the reaction solution were analyzed by LC. The results are shown in Table 12.

[0357] Embodiment 45

[0358] The 5-1# modified MOFs carrier (5wt% Ni) prepared in Example 25 was selected for catalytic hydrogenation reaction, and the same reaction conditions as in Example 34 were adopted. After the reaction, the contents in the reaction solution were analyzed by LC. The results are shown in Table 12.

[0359] Table 12 Reaction results

[0360] Example Load status BHMF yield HMF conversion Catalyst selectivity 34 Cu (5wt%) 96 98 98 42 Cu (2.5 wt%) 86 90 95 43 Cu (7.5 wt%) 98 100 98 44 Cu (10wt%) 93 100 93 45 Ni(5wt%) 86 91 94

[0361] Compared with Example 34, Examples 42, 43 and 44, the catalyst samples used in this example have changed, that is, the metal loading amount is changed during the carrier loading process, and the other preparation conditions are not changed. From the data in Table 12, it can be seen that the metal loading amount is reduced, and the final BHMF yield is significantly reduced. However, if the metal loading amount is too large, other by-products will occur during the reaction, thereby affecting the final BHMF yield. It can be seen that the metal loading amount on the carrier affects the yield and selectivity of BHMF.

[0362] Compared with Example 34, Example 45 shows that the catalyst sample used in this example has changed from 1-1# to 5-1#, that is, the type of metal loaded in the prepared supported catalyst has changed, and the supported metal has changed from Cu to Ni, and the other preparation conditions have not changed, and the final yield of BHMF has significantly decreased. It can be seen that the different types of supported metals in the supported catalyst affect the yield of BHMF in the final catalytic reaction.

[0363] Embodiment 46

[0364] (1) Add 30 ml of isopropanol and 0.5 g of HMF to the polytetrafluoroethylene liner and stir thoroughly to make the raw materials dispersed evenly and stably in the reaction system. At this time, the concentration of HMF in the solution system is 132 mM. Take a sample as the concentration of the initial reaction;

[0365] (2) Then, 0.1 g of the 6-1# catalyst prepared in Example 26 was added, and the mass ratio of the substrate HMF to the catalyst was 5:1, and the mixture was transferred to the hydrogenation reactor. After three times of nitrogen replacement of the air, hydrogen was introduced to 2 MPa, the speed was adjusted to 800 rpm, and the temperature was programmed to 150°C for the hydrogenation reaction time of 2 h.

[0366] (3) After the reaction was completed, the reaction solution was cooled to room temperature and the contents in the reaction solution were analyzed by LC. The results are shown in Table 13.

[0367] Table 13 Reaction results of Example 46

[0368] Example BHMF yield HMF conversion Catalyst selectivity 46 65 81 80

[0369] Compared with Example 34, Example 46, the catalyst sample used in this example has changed, and the catalyst sample used has changed from 1-1# to 6-1#, that is, the preparation method of the carrier has changed, that is, in the process of preparing the supported catalyst, the heating rate of heating to the specified calcination temperature has been changed, and the heating rate has been increased from 1°C / min to 5°C / min, and the other preparation conditions have not changed, and the final selectivity and yield of BHMF have decreased significantly. It can be seen that if the heating rate is too fast, the metal particles loaded on the carrier will agglomerate, thereby affecting the selectivity of the catalyst and the yield of BHMF in the final catalytic reaction.

[0370] Embodiment 47

[0371] (1) Add 30 ml of isopropanol and 0.5 g of HMF to the polytetrafluoroethylene liner and stir thoroughly to make the raw materials dispersed evenly and stably in the reaction system. At this time, the concentration of HMF in the solution system is 132 mM. Take a sample as the concentration of the initial reaction;

[0372] (2) Then, 0.1 g of the 7-1# catalyst prepared in Example 27 was added, and the mass ratio of the substrate HMF to the catalyst was 5:1, and the mixture was transferred to the hydrogenation reactor. After three times of nitrogen replacement of the air, hydrogen was introduced to 2 MPa, the speed was adjusted to 800 rpm, and the temperature was programmed to 150°C for the hydrogenation reaction time of 2 h.

[0373] (3) After the reaction was completed, the reaction solution was cooled to room temperature and the contents in the reaction solution were analyzed by LC. The results are shown in Table 14.

[0374] Table 14 Reaction results of Example 47

[0375]

[0376]

[0377] Compared with Example 34, Example 47, the catalyst sample used in this example is changed from 1-1# to 7-1#, that is, the preparation method of the carrier is changed, that is, in the process of preparing the supported catalyst, the specified calcination temperature is changed from 300°C to 500°C, and the other preparation conditions are unchanged. The final selectivity and yield of BHMF are significantly reduced. It can be seen that too high a calcination temperature may burn down the spatial structure of MOFs and affect the dispersion of the metal atom load, thereby affecting the selectivity of the catalyst and the yield of BHMF in the final catalytic reaction.

[0378] Embodiment 48

[0379] (1) Add 30 ml of isopropanol and 0.5 g of HMF to the polytetrafluoroethylene liner and stir thoroughly to make the raw materials dispersed evenly and stably in the reaction system. At this time, the concentration of HMF in the solution system is 132 mM. Take a sample as the concentration of the initial reaction;

[0380] (2) Then, 0.1 g of the 8-1# catalyst prepared in Example 28 was added, and the mass ratio of the substrate HMF to the catalyst was 5:1, and the mixture was transferred to the hydrogenation reactor. After three nitrogen replacements of the air, hydrogen was introduced to 2 MPa, the speed was adjusted to 800 rpm, and the temperature was programmed to 150°C for a hydrogenation reaction time of 2 h.

[0381] (3) After the reaction was completed, the reaction mixture was cooled to room temperature and the contents in the reaction solution were analyzed by LC. The results are shown in Table 15.

[0382] Table 15 Reaction results of Example 48

[0383] Example BHMF yield HMF conversion Catalyst selectivity 48 61 77 79

[0384] Compared with Example 34, Example 48, the catalyst sample used in this example is changed, and the catalyst sample used is changed from 1-1# to 8-1#, that is, the preparation method of the carrier is changed, that is, in the process of preparing the supported catalyst, the specified calcination temperature is changed from 300°C to 200°C, and the other preparation conditions are unchanged. The final selectivity and yield of BHMF are significantly reduced. It can be seen that insufficient calcination temperature will reduce the activity of the catalyst, resulting in a smaller specific surface area of ​​the catalyst, thereby limiting the contact area between the reactant and the catalyst, further reducing the catalytic efficiency, thereby affecting the selectivity of the catalyst and the yield of BHMF in the final catalytic reaction.

[0385] Embodiment 49

[0386] (1) Add 30 ml of isopropanol and 0.5 g of HMF to the polytetrafluoroethylene liner and stir thoroughly to make the raw materials dispersed evenly and stably in the reaction system. At this time, the concentration of HMF in the solution system is 132 mM. Take a sample as the concentration of the initial reaction;

[0387] (2) Then, 0.1 g of the 9-1# catalyst prepared in Example 29 was added, and the mass ratio of the substrate HMF to the catalyst was 5:1, and the mixture was transferred to the hydrogenation reactor. After three times of nitrogen replacement of the air, hydrogen was introduced to 2 MPa, the speed was adjusted to 800 rpm, and the temperature was programmed to 150°C for the hydrogenation reaction time of 2 h.

[0388] (3) After the reaction was completed, the reaction solution was cooled to room temperature and the contents in the reaction solution were analyzed by LC. The results are shown in Table 16.

[0389] Table 16 Reaction results of Example 49

[0390] Example BHMF yield HMF conversion Catalyst selectivity 49 82 91 90

[0391] Compared with Example 34, Example 49 shows that the catalyst sample used in this example has changed, and the catalyst sample used has changed from 1-1# to 9-1#, that is, the preparation method of the carrier has changed, that is, in the process of preparing the supported catalyst, when reducing in a hydrogen atmosphere, the heating rate of heating to the specified reduction temperature is changed, and the heating rate is increased from 1°C / min to 5°C / min, and the other preparation conditions are unchanged, and the final yield and selectivity of BHMF have decreased significantly. It can be seen that when reducing in a hydrogen atmosphere, the heating rate is too fast, which will cause the metal particles on the carrier to agglomerate, thereby affecting the selectivity of the catalyst and the yield of BHMF in the final catalytic reaction.

[0392] Embodiment 50

[0393] (1) Add 30 ml of isopropanol and 0.5 g of HMF to the polytetrafluoroethylene liner and stir thoroughly to make the raw materials dispersed evenly and stably in the reaction system. At this time, the concentration of HMF in the solution system is 132 mM. Take a sample as the concentration of the initial reaction;

[0394] (2) Then, 0.1 g of the 10-1# catalyst prepared in Example 30 was added, and the mass ratio of the substrate HMF to the catalyst was 5:1, and the mixture was transferred to the hydrogenation reactor. After three nitrogen replacements of the air, hydrogen was introduced to 2 MPa, the speed was adjusted to 800 rpm, and the temperature was programmed to 150°C for a hydrogenation reaction time of 2 h.

[0395] (3) After the reaction was completed, the reaction solution was cooled to room temperature and the contents in the reaction solution were analyzed by LC. The results are shown in Table 17.

[0396] Table 17 Reaction results of Example 50

[0397] Example BHMF yield HMF conversion Catalyst selectivity 50 57 79 72

[0398] Compared with Example 34, Example 50, the catalyst sample used in this example has changed, and the catalyst sample used has changed from 1-1# to 10-1#, that is, the preparation method of the carrier has changed, that is, in the process of preparing the supported catalyst, the specified reduction temperature is changed during the reduction in the hydrogen atmosphere, and the specified reduction temperature is increased from 300°C to 600°C, and the other preparation conditions are unchanged. The final yield and selectivity of BHMF have decreased significantly. It can be seen that too high a reduction temperature will burn down the spatial structure of MOFs and affect the dispersion of the metal atom load. At the same time, at too high a temperature, the skeleton of the MOFs carrier collapses, causing a large number of metal particles loaded on the carrier to agglomerate, thereby seriously affecting the selectivity of the catalyst in the final catalytic reaction and the yield of BHMF.

[0399] Embodiment 51

[0400] (1) Add 30 ml of isopropanol and 0.5 g of HMF to the polytetrafluoroethylene liner and stir thoroughly to make the raw materials dispersed evenly and stably in the reaction system. At this time, the concentration of HMF in the solution system is 132 mM. Take a sample as the concentration of the initial reaction;

[0401] (2) Then, 0.1 g of the 11-1# catalyst prepared in Example 31 was added, and the mass ratio of the substrate HMF to the catalyst was 5:1, and the mixture was transferred to the hydrogenation reactor. After three nitrogen replacements of the air, hydrogen was introduced to 2 MPa, the speed was adjusted to 800 rpm, and the temperature was programmed to 150°C for a hydrogenation reaction time of 2 h.

[0402] (3) After the reaction was completed, the reaction solution was cooled to room temperature and the contents in the reaction solution were analyzed by LC. The results are shown in Table 18.

[0403] Table 18 Reaction results of Example 51

[0404] Example BHMF yield HMF conversion Catalyst selectivity 51 64 86 74

[0405] Compared with Example 34, Example 51, the catalyst sample used in this example is changed, and the catalyst sample used is changed from 1-1# to 11-1#, that is, the preparation method of the carrier is changed, that is, in the process of preparing the supported catalyst, during the reduction in hydrogen atmosphere, the specified reduction temperature is changed from 300°C to 100°C, and the other preparation conditions are unchanged. The final yield and selectivity of BHMF are significantly reduced. It can be seen that insufficient reduction temperature will result in the failure to completely reduce the active components of the catalyst, thereby affecting the activity and efficiency of the catalyst.

[0406] Embodiment 52

[0407] (1) Add 30 ml of isopropanol and 1 g of HMF to the polytetrafluoroethylene liner and stir thoroughly to make the raw materials dispersed evenly and stably in the reaction system. At this time, the concentration of HMF in the solution system is 264 mM. Take a sample as the concentration of the initial reaction;

[0408] (2) Then, 0.1 g of the 1-1# catalyst prepared in Example 14 was added, and the mass ratio of the substrate HMF to the catalyst was 10:1, and the mixture was transferred to the hydrogenation reactor. After three times of nitrogen replacement of the air, hydrogen was introduced to 2 MPa, the speed was adjusted to 800 rpm, and the temperature was programmed to 150°C for the hydrogenation reaction time of 2 h.

[0409] (3) After the reaction was completed, the reaction mixture was cooled to room temperature and the contents in the reaction mixture were analyzed by LC. The results are shown in Table 19.

[0410] Table 19 Reaction results of Example 52

[0411] Example BHMF yield HMF conversion Catalyst selectivity 52 81 88 92

[0412] Example 52 Compared with Example 34, the mass of HMF in the raw material used in this example has changed, and the other conditions have not changed. As the mass of HMF in the raw material increases, the concentration of HMF in the reaction solution system increases, and the final yield of BHMF decreases. It can be seen that increasing the concentration of the raw material in the system does not necessarily increase the yield of BHMF. The excess raw material is densely distributed in the reaction system, which inhibits the activity of the catalyst, resulting in a decrease in the yield of BHMF and a decline in the selectivity of the catalyst.

[0413] Embodiment 53

[0414] (1) Add 30 ml of isopropanol and 0.25 g of HMF to the polytetrafluoroethylene liner and stir thoroughly to make the raw materials dispersed evenly and stably in the reaction system. At this time, the concentration of HMF in the solution system is 66 mM. Take a sample as the concentration of the initial reaction;

[0415] (2) Then, 0.1 g of the 1-1# catalyst prepared in Example 14 was added, and the mass ratio of the substrate HMF to the catalyst was 2.5:1, and the mixture was transferred to the hydrogenation reactor. After three nitrogen replacements of the air, hydrogen was introduced to 2 MPa, the speed was adjusted to 800 rpm, and the temperature was programmed to 150°C for a hydrogenation reaction time of 2 h.

[0416] (3) After the reaction was completed, the reaction mixture was cooled to room temperature and the contents in the reaction solution were analyzed by LC. The results are shown in Table 20.

[0417] Table 20 Reaction results of Example 53

[0418] Example BHMF yield HMF conversion Catalyst selectivity 53 99 100 99

[0419] Example 53 Compared with Example 34, the mass of HMF in the raw material used in this example has changed, and the other conditions have not changed. As the mass of HMF in the raw material decreases, the concentration in the reaction solution system of HMF decreases, and the final yield of BHMF increases. It can be seen that reducing the concentration of the raw material in the system, while the mass of the catalyst does not change, reduces the ratio of the raw material HMF and the catalyst in a disguised manner. A very small amount of raw material greatly disperses the reaction system, reduces the ratio of the raw material HMF and the catalyst in a disguised manner, makes it more convenient for the catalyst to act on the raw material, and leads to an increase in yield. Therefore, the appropriate raw material HMF concentration and the optimal catalyst ratio are in line with the efficiency of the experiment.

[0420] Embodiment 54

[0421] (1) Add 30 ml of isopropanol and 0.5 g of HMF to the polytetrafluoroethylene liner and stir thoroughly to make the raw materials dispersed evenly and stably in the reaction system. At this time, the concentration of HMF in the solution system is 132 mM. Take a sample as the concentration of the initial reaction;

[0422] (2) Then, 0.1 g of the 1-1# catalyst prepared in Example 14 was added, and the mass ratio of the substrate HMF to the catalyst was 5:1, and the mixture was transferred to the hydrogenation reactor. After three times of nitrogen replacement of the air, hydrogen was introduced to 2 MPa, the speed was adjusted to 800 rpm, and the temperature was programmed to 80°C for a hydrogenation reaction time of 2 h.

[0423] (3) After the reaction was completed, the reaction solution was cooled to room temperature and the contents in the reaction solution were analyzed by LC. The results are shown in Table 21.

[0424] Table 21 Reaction results of Example 54

[0425] Example BHMF yield HMF conversion Catalyst selectivity 54 65 87 75

[0426] Example 54 Compared with Example 34, the final constant reaction temperature of this example has changed, and the other conditions have not changed. With the decrease of the final constant reaction temperature, the conversion of HMF is not complete, the selectivity of the catalyst is also not strong, and the final yield of BHMF is reduced. It can be seen that the decrease in temperature leads to a decrease in the activity of the catalyst, affects the conversion rate of HMF and the selectivity of the catalyst, and finally reduces the yield of BHMF. It can be proved that the appropriate temperature can better accelerate the conversion of HMF and improve the yield of BHMF.

[0427] Embodiment 55

[0428] (1) Add 30 ml of isopropanol and 0.5 g of HMF to the polytetrafluoroethylene liner and stir thoroughly to make the raw materials dispersed evenly and stably in the reaction system. At this time, the concentration of HMF in the solution system is 132 mM. Take a sample as the concentration of the initial reaction;

[0429] (2) Then, 0.1 g of the 1-1# catalyst prepared in Example 14 was added, and the mass ratio of the substrate HMF to the catalyst was 5:1, and the mixture was transferred to the hydrogenation reactor. After three nitrogen replacements of the air, hydrogen was introduced to 2 MPa, the speed was adjusted to 800 rpm, and the temperature was programmed to 200°C for the hydrogenation reaction time of 2 h.

[0430] (3) After the reaction was completed, the reaction solution was cooled to room temperature and the contents in the reaction solution were analyzed by LC. The results are shown in Table 22.

[0431] Table 22 Reaction results of Example 55

[0432] Example BHMF yield HMF conversion Catalyst selectivity 55 87 100 87

[0433] Example 55 Compared with Example 34, the final constant reaction temperature of this example has changed, and the other conditions have not changed. As the final constant reaction temperature increases, HMF has been substantially completely converted, but the final yield of BHMF is reduced. As a result, due to the high heat conditions, part of the raw material HMF is not directional while proceeding in the direction of the product BHMF and polymerization. BHMF also proceeds in the direction of side reactions such as polymerization due to excessively high temperatures, resulting in a decrease in the selectivity of the catalyst and a decrease in the yield of BHMF. It can be proved that the appropriate temperature maintains the stability of the raw material HMF and the product BHMF, ensuring the selectivity of the catalyst and the yield of BHMF in the final catalytic reaction.

[0434] Embodiment 56

[0435] (1) Add 30 ml of isopropanol and 0.1 g of HMF to the polytetrafluoroethylene liner and stir thoroughly to make the raw materials dispersed evenly and stably in the reaction system. At this time, the concentration of HMF in the solution system is 26.4 mM. Take a sample as the concentration of the initial reaction;

[0436] (2) Then, 0.1 g of the 1-1# catalyst prepared in Example 14 was added, and the mass ratio of the substrate HMF to the catalyst was 1:1, and the mixture was transferred to the hydrogenation reactor. After three times of nitrogen replacement of the air, hydrogen was introduced to 2 MPa, the speed was adjusted to 800 rpm, and the temperature was programmed to 150°C for a hydrogenation reaction time of 2 h.

[0437] (3) After the reaction was completed, the reaction solution was cooled to room temperature and the contents in the reaction solution were analyzed by LC. The results are shown in Table 23.

[0438] Table 23 Reaction results of Example 56

[0439] Example BHMF yield HMF conversion Catalyst selectivity 56 97 99 98

[0440] Example 56 Compared with Example 34, the ratio of the substrate and the catalyst used in this example is changed, and the other conditions are unchanged. As the ratio of the substrate and the catalyst used is reduced, the contact between the catalyst and the raw material is more complete, resulting in an increase in the yield and an increase in the catalyst selectivity, and the final yield of BHMF is increased.

[0441] Embodiment 57

[0442] (1) Add 30 ml of isopropanol and 2.5 g of HMF to the polytetrafluoroethylene liner and stir thoroughly to make the raw materials dispersed evenly and stably in the reaction system. At this time, the concentration of HMF in the solution system is 660 mM. Take a sample as the concentration of the initial reaction;

[0443] (2) Then, 0.1 g of the 1-1# catalyst prepared in Example 14 was added, and the mass ratio of the substrate HMF to the catalyst was 25:1, and the mixture was transferred to the hydrogenation reactor. After three nitrogen replacements of the air, hydrogen was introduced to 2 MPa, the speed was adjusted to 800 rpm, and the temperature was programmed to 150°C for a hydrogenation reaction time of 2 h.

[0444] (3) After the reaction was completed, the reaction solution was cooled to room temperature and the contents in the reaction solution were analyzed by LC. The results are shown in Table 24.

[0445] Table 24 Reaction results of Example 57

[0446] Example BHMF yield HMF conversion Catalyst selectivity 57 80 87 92

[0447] Example 57 Compared with Example 34, the ratio of substrate to catalyst used in this example has changed, and the other conditions have not changed. As the ratio of substrate to catalyst used increases, the content of catalyst in the same system is significantly reduced, resulting in incomplete conversion of HMF and intermediates in the reaction process, and ultimately leading to a serious shortage of BHMF yield. It can be seen that an appropriate catalyst content to support the reaction is a necessary condition for the generation of BHMF.

[0448] Embodiment 58

[0449] (1) Add 30 ml of isopropanol and 0.5 g of HMF to the polytetrafluoroethylene liner and stir thoroughly to make the raw materials dispersed evenly and stably in the reaction system. At this time, the concentration of HMF in the solution system is 132 mM. Take a sample as the concentration of the initial reaction;

[0450] (2) Then, 0.1 g of the 1-1# catalyst prepared in Example 14 was added, and the mass ratio of the substrate HMF to the catalyst was 5:1, and the mixture was transferred to the hydrogenation reactor. After three times of nitrogen replacement of the air, hydrogen was introduced to 2 MPa, the speed was adjusted to 800 rpm, and the temperature was programmed to 150°C for a hydrogenation reaction time of 4 h.

[0451] (3) After the reaction was completed, the reaction solution was cooled to room temperature and the contents in the reaction solution were analyzed by LC. The results are shown in Table 25.

[0452] Table 25 Reaction results of Example 58

[0453] Example BHMF yield HMF conversion Catalyst selectivity 58 98 100 98

[0454] Example 58 Compared with Example 34, the reaction time of this example has changed, and the other conditions have not changed. As the reaction time is prolonged, the yield of BHMF still shows an upward trend. It can be seen that the catalyst prepared by the present invention has strong tolerance in reaction time, is selective for HMF, and does not undergo other side reactions such as ring opening due to the extension of time. Reaction time is a necessary condition to ensure efficient conversion of HMF and BHMF yield, but it can be seen that the extension of time does not improve the yield much, so it can be appropriately selected in pursuit of experimental efficiency and industrial economy.

[0455] Embodiment 59

[0456] (1) Add 30 ml of isopropanol and 0.5 g of HMF to the polytetrafluoroethylene liner and stir thoroughly to make the raw materials dispersed evenly and stably in the reaction system. At this time, the concentration of HMF in the solution system is 132 mM. Take a sample as the concentration of the initial reaction;

[0457] (2) Then, 0.1 g of the 1-1# catalyst prepared in Example 14 was added, and the mass ratio of the substrate HMF to the catalyst was 5:1, and the mixture was transferred to the hydrogenation reactor. After three times of nitrogen replacement of the air, hydrogen was introduced to 2 MPa, the speed was adjusted to 800 rpm, and the temperature was programmed to 150°C for a hydrogenation reaction time of 0.5 h.

[0458] (3) After the reaction was completed, the reaction solution was cooled to room temperature and the contents in the reaction solution were analyzed by LC. The results are shown in Table 26.

[0459] Table 26 Reaction results of Example 59

[0460] Example BHMF yield HMF conversion Catalyst selectivity 59 53 57 93

[0461] Compared with Example 34, the reaction time of Example 59 was changed, and the other conditions were unchanged. As the reaction time was shortened, the conversion rate of HMF and the yield of BHMF were obviously insufficient. It can be seen that the reaction time is a necessary condition to ensure the efficient conversion of HMF and the yield of BHMF.

[0462] Embodiment 60

[0463] (1) Add 30 ml of isopropanol and 0.5 g of HMF to the polytetrafluoroethylene liner and stir thoroughly to make the raw materials dispersed evenly and stably in the reaction system. At this time, the concentration of HMF in the solution system is 132 mM. Take a sample as the concentration of the initial reaction;

[0464] (2) Then, 0.1 g of the 1-1# catalyst prepared in Example 14 was added, and the mass ratio of the substrate HMF to the catalyst was 5:1, and the mixture was transferred to the hydrogenation reactor. After three times of nitrogen replacement of the air, hydrogen was introduced to 4 MPa, the speed was adjusted to 800 rpm, and the temperature was programmed to 150°C for a hydrogenation reaction time of 2 h.

[0465] (3) After the reaction was completed, the reaction solution was cooled to room temperature and the contents in the reaction solution were analyzed by LC. The results are shown in Table 27.

[0466] Table 27 Reaction results of Example 60

[0467] Example BHMF yield HMF conversion Catalyst selectivity 60 97 99 98

[0468] Example 60 Compared with Example 34, the reaction pressure of this example has changed, and the other conditions have not changed. As the pressure in the system increases, the conversion rate of HMF and the yield of BMHF are slightly improved. It can be seen that the pressure has an effect on the reaction, which not only serves as a hydrogen supply condition, but also has a certain effect on the catalytic hydrogenation reaction of the carrier.

[0469] Embodiment 61

[0470] (1) Add 30 ml of isopropanol and 0.5 g of HMF to the polytetrafluoroethylene liner and stir thoroughly to make the raw materials dispersed evenly and stably in the reaction system. At this time, the concentration of HMF in the solution system is 132 mM. Take a sample as the concentration of the initial reaction;

[0471] (2) Then, 0.1 g of the 1-1# catalyst prepared in Example 14 was added, and the mass ratio of the substrate HMF to the catalyst was 5:1, and the mixture was transferred to the hydrogenation reactor. After three times of nitrogen replacement of the air, hydrogen was introduced to 0.1 MPa, the speed was adjusted to 800 rpm, and the temperature was programmed to 150°C for a hydrogenation reaction time of 2 h.

[0472] (3) After the reaction was completed, the reaction solution was cooled to room temperature and the contents in the reaction solution were analyzed by LC. The results are shown in Table 28.

[0473] Table 28 Reaction results of Example 61

[0474] Example BHMF yield HMF conversion Catalyst selectivity 61 64 72 89

[0475] Example 61 Compared with Example 34, the reaction pressure of this example was changed, and the other conditions were not changed. As the pressure in the system decreased, the conversion rate of HMF and the yield of BMHF were obviously insufficient. It can be seen that the pressure has an effect on the reaction.

[0476] Embodiment 62

[0477] The difference between this embodiment and embodiment 34 is that the hydrogen gas is 8 MPa, the temperature of the catalytic hydrogenation reaction is 100° C., and the time is 10 h.

[0478] Embodiment 63

[0479] The difference between this embodiment and embodiment 34 is that the mass ratio of 5-hydroxymethylfurfural to supported catalyst is 30:1.

[0480] Embodiment 64

[0481] Catalyst recycling experiment

[0482] (1) Add 30 ml of isopropanol and 0.5 g of HMF to the polytetrafluoroethylene liner and stir thoroughly to make the raw materials dispersed evenly and stably in the reaction system. At this time, the concentration of HMF in the solution system is 132 mM. Take a sample as the concentration of the initial reaction;

[0483] (2) Then, 0.1 g of the 1-1# catalyst prepared in Example 14 was added, and the mass ratio of the substrate HMF to the catalyst was 5:1, and the mixture was transferred to the hydrogenation reactor. After three nitrogen replacements of the air, hydrogen was introduced to 4 MPa, the speed was adjusted to 800 rpm, and the temperature was programmed to 150°C for 2 h.

[0484] (3) After the reaction is completed, the mixture is cooled to room temperature and the contents of the reaction mixture in the first reaction are analyzed by LC.

[0485] (4) Filter out the catalyst, wash it three times with water, then wash it three times with isopropanol, put it into a polytetrafluoroethylene liner and seal it with 15 ml of isopropanol (minimize the contact time with air), then add 0.5 g of HMF and 15 ml of isopropanol solvent to the liner (maintain the amount of solvent in the system unchanged). At this time, the mass ratio of substrate HMF and catalyst is still 5:1, and it is transferred to the hydrogenation reactor. After three times of nitrogen replacement of air, hydrogen is introduced to 2Mpa, the speed is adjusted to 800rpm, and the temperature is programmed to start, the reaction temperature is 150°C, and the reaction time is 2h;

[0486] (5) After the reaction is completed, the mixture is cooled to room temperature and the contents of the reaction mixture of the second reaction are analyzed by LC.

[0487] (6) Repeat the steps (4)-(5) and recycle the catalyst for 5 times. The LC analysis results are shown in Table 29.

[0488] Table 29 Reaction results of Example 64 - LC analysis

[0489] Number of reactions BHMF yield HMF conversion Catalyst selectivity first 96 98 98 Second time 96 98 98 The third time 96 98 98 Fourth 95 98 97 Fifth 92 98 94

[0490] The present embodiment evaluates the catalyst by a replication experiment. From the data in Table 29, it can be found that the selectivity does not change much after three consecutive reactions. The catalyst selectivity slightly decreases after the fourth reaction. From this experiment, it can be seen that the carrier prepared by the present invention has good heat resistance and chemical stability, and can still maintain the stability of its morphology during repeated use. Multiple cycles will not cause the load metal particles to fall off, and it has a strong specificity for catalytic hydrogenation of HMF to prepare BHMF.

[0491] Embodiment 65

[0492] Catalyst regeneration

[0493] (1) The catalyst temporarily stored after five application reactions in Example 64 was washed three times with isopropanol, washed three times with water, and then placed in an oven at 100°C for 2 h until completely dry. Finally, the sample was placed in a muffle furnace and calcined at a gradient temperature from room temperature to 300°C at a heating rate of 1°C / min. It was calcined at the specified temperature for 3 h, and taken out after cooling to obtain an oxidized catalyst after removing deposited impurities.

[0494] (2) Then, the catalyst was reduced by gradient heating in a tubular furnace under a hydrogen atmosphere, with the heating rate rising from room temperature to 300°C at a rate of 1°C / min, and reduced at the specified temperature for 2 hours to obtain a regenerated supported catalyst, which was recorded as 1-1-1#.

[0495] Verification reaction of the regenerated catalyst

[0496] (1) Add 30 ml of isopropanol and 0.5 g of HMF to the polytetrafluoroethylene liner and stir thoroughly to make the raw materials dispersed evenly and stably in the reaction system. At this time, the concentration of HMF in the solution system is 132 mM. Take a sample as the concentration of the initial reaction;

[0497] (2) Then, 0.1 g of the regenerated 1-1-1# catalyst was added. At this time, the mass ratio of the substrate HMF and the catalyst was still 5:1, and the mixture was transferred to the hydrogenation reactor. After three nitrogen replacements of the air, hydrogen was introduced to 2 MPa, the speed was adjusted to 800 rpm, and the temperature was programmed to 150°C for 2 h.

[0498] (3) After the reaction was completed, the reaction solution was cooled to room temperature and the contents in the reaction solution were analyzed by LC. The results are shown in Table 30.

[0499] Table 30 Reaction results of Example 65

[0500] Example BHMF yield HMF conversion Catalyst selectivity 65 95 98 97

[0501] It can be seen from this example that the decrease in BHMF yield under the continuous application of the catalyst is caused by the deposited impurities accumulated during the multiple biomass reactions affecting the catalyst. The deposited impurities on the surface of the MOFs carrier are removed by calcination and reduction, and the catalyst restores its excellent hydrogenation catalytic performance. It can be seen that the catalyst prepared by the present invention has good reusability, the loaded metal particles are not easy to fall off, are not easy to deactivate, and have good regeneration.

[0502] Comparative Example 10

[0503] Experimental verification of the reaction of unmodified MOFs carrier after metal loading and regeneration

[0504] (1) Add 30 ml of isopropanol and 0.5 g of HMF to the polytetrafluoroethylene liner and stir thoroughly to make the raw materials dispersed evenly and stably in the reaction system. At this time, the concentration of HMF in the solution system is 132 mM. Take a sample as the concentration of the initial reaction;

[0505] (2) Then, 0.1 g of the prepared 1-4# catalyst was added, and the mass ratio of the substrate HMF to the catalyst was 5:1, and the mixture was transferred to the hydrogenation reactor. After three nitrogen replacements of the air, hydrogen was introduced to 2 MPa, the speed was adjusted to 800 rpm, and the temperature was programmed to 150°C for 2 h.

[0506] (3) After the reaction was completed, the reaction solution was cooled to room temperature and the contents in the reaction solution were analyzed by LC. The results are shown in Table 31.

[0507] Catalyst regeneration

[0508] (4) After the reaction in step (3) is completed, the catalyst is regenerated using the same method as in Example 65.

[0509] Catalyst verification experiment after regeneration

[0510] (5) Add 30 ml of isopropanol and 0.5 g of HMF to the polytetrafluoroethylene liner and stir thoroughly to make the raw materials dispersed evenly and stably in the reaction system. At this time, the concentration of HMF in the solution system is 132 mM. Take a sample as the concentration of the initial reaction;

[0511] (6) Then, the regenerated supported catalyst was added, and the mass ratio of substrate HMF to catalyst was 5:1, and the catalyst was transferred to the hydrogenation reactor. After three times of nitrogen replacement of air, hydrogen was introduced to 2 MPa, the speed was adjusted to 800 rpm, and the temperature was programmed to 150 ° C and the reaction time was 2 h;

[0512] (7) After the reaction was completed, the reaction solution was cooled to room temperature and the contents in the reaction solution were analyzed by LC. The results are shown in Table 31.

[0513] Table 31 Reaction results of Example 66

[0514] Embodiment 66 BHMF yield HMF conversion Catalyst selectivity Control reaction 80 86 93 After catalyst regeneration 62 75 83

[0515] In the process of preparing the carrier of the 1-4# supported catalyst used in this example, no modifier was added to modify the carrier, and the other loading conditions and reaction conditions were not changed. The yield of BHMF prepared was obviously insufficient compared with the effect of Example 64. Compared with Example 65, from the reaction data after catalyst regeneration, it can be seen that the regeneration of the supported catalyst prepared in this example without modifying the carrier is not strong. After high-temperature calcination regeneration, the conversion rate of HMF decreased, which ultimately affected the yield of BHMF.

[0516] In addition, the inventors of this case also referred to the aforementioned embodiments and conducted experiments with other raw materials, process operations, and process conditions described in this specification, and obtained relatively ideal results.

[0517] It should be understood that the technical solution of the present invention is not limited to the above-mentioned specific implementation cases. Any technical deformation made according to the technical solution of the present invention without departing from the scope of protection of the purpose of the present invention and the claims shall fall within the protection scope of the present invention.

Claims

1. A method for preparing a modified MOFs carrier, characterized in that: include: A mixed reaction system including a carboxylate ligand, a zirconium salt, a stabilizer, a modifier and a first organic solvent is subjected to a dynamic crystallization reaction to obtain a modified MOFs precursor, which is then subjected to a vacuum activation treatment to obtain a modified MOFs carrier.

2. The preparation method according to claim 1, characterized in that: The carboxylate ligand includes at least any one of terephthalic acid, trimesic acid, naphthalene dicarboxylic acid, and biphenyl-4,4-dicarboxylic acid; And / or, the zirconium salt comprises an organic solvent-soluble zirconium salt; the zirconium salt comprises any one or a combination of two or more of zirconium chloride, zirconium nitrate, and zirconium sulfate; and / or, the molar ratio of zirconium ions contained in the zirconium salt to terephthalic acid is 1:0.1 to 1:5; And / or, the concentration of zirconium ions contained in the zirconium salt in the mixed reaction system is 0.1 to 100 mmol / L; And / or, the stabilizer includes any one or a combination of two or more of acetic acid, citric acid, oxalic acid, ethylenediaminetetraacetic acid, and phosphoric acid; and / or, the volume of the stabilizer accounts for 0.01% to 15% of the total volume of the mixed reaction system; And / or, the modifier includes any one or a combination of two or more of aluminum salt, tin salt, chromium salt, zinc salt, and silicate; and / or, the molar ratio of the modifier to terephthalic acid is 1:0.1 to 1:20; And / or, the first organic solvent includes any one of N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, and acetone, or a combination of two or more thereof.

3. The preparation method according to claim 1, characterized in that: The dynamic crystallization reaction comprises: heating the mixed reaction system from room temperature to a specified crystallization reaction temperature at a heating rate of 0.5 to 10°C / min for a dynamic crystallization reaction; wherein the specified crystallization reaction temperature is 80 to 160°C, the dynamic crystallization reaction time is 6 to 96 hours, and the mechanical turning speed is 10 to 60 rpm; And / or, the preparation method further comprises: filtering the modified MOFs precursor obtained by the dynamic crystallization reaction after centrifugation, washing and drying to obtain a dried modified MOFs precursor; wherein the speed of the centrifugation is 700-1200 rpm, and the centrifugation time is 5-30 min; the washing comprises washing with DMF for 3-5 times, and then washing with acetone for 3-5 times; the drying temperature is 60-80° C., and the time is 6-12 h; And / or, the vacuum activation treatment is carried out under vacuum conditions, the temperature of the vacuum activation treatment is 80 to 200° C., the time is 6 to 96 hours, and the activation vacuum degree is -0.01 to -0.1 MPa.

4. A modified MOFs carrier prepared by the preparation method according to any one of claims 1 to 3; Preferably, the particle size of the modified MOFs carrier is 200nm-250nm, and the specific surface area is 1200-1300m 2 / g, the crystal form is octahedral.

5. A method for preparing a supported catalyst, characterized in that: include: Prepare a modified MOFs carrier according to the preparation method described in any one of claims 1 to 3; The metal element is loaded on the modified MOFs carrier, and then calcined and reduced in sequence to obtain a loaded catalyst.

6. The preparation method according to claim 5, characterized in that: The metal element includes a transition metal element, and the transition metal element includes any one or a combination of two or more of Cu, Ni, Co, and Fe; And / or, the preparation method comprises: fully immersing the modified MOFs carrier in a metal salt solution, so that the metal element is loaded on the modified MOFs carrier; the metal salt comprises any one of transition metal element sulfate, transition metal element nitrate, transition metal element acetate, transition metal element phosphate, and transition metal element chloride, or a combination of two or more thereof; And / or, the preparation method comprises: gradually heating the modified MOFs carrier loaded with metal elements to a calcination temperature in an inert atmosphere, and performing the calcination treatment; preferably, the inert atmosphere comprises a nitrogen atmosphere; And / or, the preparation method comprises: heating from room temperature to a calcination temperature of 200 to 500° C. at a heating rate of 0.5 to 10° C. / min, the calcination time being 1 to 20 hours; And / or, the preparation method comprises: performing the reduction treatment on the calcined product in a reducing atmosphere; preferably, the reducing atmosphere comprises a hydrogen atmosphere; And / or, the preparation method comprises: heating from room temperature to a reduction temperature of 100 to 600° C. at a heating rate of 0.5 to 10° C. / min, and the reduction treatment time is 1 hour to 30 hours.

7. A supported catalyst prepared by the preparation method according to any one of claims 5 to 6; Preferably, the supported catalyst comprises a modified MOFs support and metal nanoparticles uniformly supported on the modified MOFs support; Preferably, the loading amount of the metal nanoparticles on the modified MOFs carrier is 0.1 wt% to 20 wt%.

8. Use of the supported catalyst according to claim 7 in the preparation of 2,5-furan dimethanol; preferably, the use comprises use of the supported catalyst in the preparation of 2,5-furan dimethanol by hydrogenation of 5-hydroxymethylfurfural.

9. A method for preparing 2,5-furan dimethanol, characterized in that: include: Providing the supported catalyst according to claim 7; Under hydrogen atmosphere and selected pressure conditions, 5-hydroxymethylfurfural is catalyzed by the supported catalyst to undergo catalytic hydrogenation reaction to obtain 2,5-furan dimethanol.

10. The preparation method according to claim 9, characterized in that: include: Mixing the supported catalyst, 5-hydroxymethylfurfural and a second organic solvent to form a reaction solution; The concentration of 5-hydroxymethylfurfural in the reaction solution is 0.1 to 3000 mmol / L; And / or, the second organic solvent includes any one of methanol, ethanol, n-propanol, isopropanol, and n-butanol, or a combination of two or more thereof; and / or, the selected pressure condition refers to a pressure of 0.1 MPa to 8 MPa; and / or, the temperature of the catalytic hydrogenation reaction is 80 to 200° C., and the time is 0.5 to 10 h; And / or, the mass ratio of the 5-hydroxymethylfurfural to the supported catalyst is 1:1 to 30:1.

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