Acid-Ni catalyst for hydrogenation rearrangement reaction of 5-hydroxymethylfurfural as well as preparation method and application of acid-Ni catalyst

Abstract

The invention belongs to the technical field of catalyst preparation, and provides an acid-Ni catalyst for a hydrogenation rearrangement reaction of 5-hydroxymethylfurfural and a preparation method and application thereof.The preparation method of the acid-Ni catalyst comprises the following processes that firstly, a Ni multi-element layered material NiM is prepared, and M is Al and / or Mg; then dispersing the Ni multi-element layered material NiM in an organic phosphonic acid solution, and preparing a catalyst precursor PA / NiM through ligand self-assembly; and then carrying out thermal reduction treatment to prepare the acid-Ni catalyst PA-Ni-M. The catalyst shows excellent catalytic activity and selectivity when being used in a reaction for preparing 3-hydroxymethyl cyclopentanone through hydrogenation rearrangement of 5-hydroxymethyl furfural, and realizes control on a 5-hydroxymethyl furfural hydrogenation reaction product.

Description

Technical Field

[0001] The invention belongs to the technical field of catalyst preparation, and in particular relates to an acid-Ni catalyst for 5-hydroxymethylfurfural hydrogenation rearrangement reaction and a preparation method and application thereof. Background Art

[0002] 5-Hydroxymethylfurfural (HMF) is an important raw material for converting biomass platform molecules into high-value chemicals because it contains multiple functional groups (furan ring, carbonyl and hydroxyl) and is easily obtained in large quantities through hydrolysis / dehydration of cellulose and hemicellulose. One of the high-value strategies is to change its furan ring structure and hydrogenate and rearrange it to produce cyclopentanone compounds, which can be used as synthetic drugs, dye intermediates, agricultural chemicals, fragrances or fuel additive precursors.

[0003] The existing cyclopentanone production process is to use petroleum-based 1,6-adipic acid at high temperature (270~400℃) via Ba(OH) 2 It is obtained by decarboxylation and cyclization, with a yield of only 60-80%. Compared with the use of petroleum-based raw materials, the use of bio-based raw materials, such as furfural or HMF, not only has a low carbon footprint and is in line with development prospects, but can also undergo hydrogenation rearrangement reactions at lower reaction temperatures (140-180 °C) to obtain cyclopentanone and its derivative 3-hydroxymethylcyclopentanone (3-hydroxymethylcyclopentanone, HCPN), which have received much attention in academic and industrial fields in recent years.

[0004] The hydrogenation rearrangement reaction of furfural and HMF requires the coupling of hydrogenation, ring opening, and intramolecular aldol condensation steps under a hydrothermal environment. HMF, which has one more hydroxymethyl functional group than furfural, is more reactive and more prone to side reactions under a hydrothermal environment, making the catalyst design more challenging. In this system, metal-acid bifunctional catalysts are often used to couple the activation of H 2 The metal sites of the catalyst and the acid sites for catalytic ring opening and aldol condensation improve the selectivity of the product. In addition, the structural design of the catalyst active site also needs to avoid excessive hydrogenation (such as the formation of tetrahydrofuran dimethanol), hydrodeoxygenation (such as the formation of 2,5-hexanedione) or polymerization of the reaction intermediates to form oligomers. Traditional noble metal-acid support bifunctional catalysts are difficult to obtain ideal results in this system. For example, the journal Chemical Communications. 2014, 50: 5633-5636 reported supported catalysts of noble metals Pt, Pd, Au, and Ru, among which the optimal Au / Nb 2 O 5At a high hydrogen pressure of 8 MPa, the maximum HCPN yield is only 86%. In recent years, the journal ACS Catalysis. 2023, 13(20): 13205-13214 reported a PdZn intermetallic catalyst that can be used to synthesize HCPN by H 2 Heterolytic generation of H + ―H - , providing proton acid and hydrogenation active sites respectively, thereby achieving a HCPN yield of up to 95.8%, reaching the highest level reported in existing literature. However, the 5.4 wt% precious metal Pd content in the catalyst limits its possibility of industrial application. In comparison, the journal ChemSusChem. 2016, 9(5): 521-531 reported 47 wt% Ni / Al 2 O 3 Metal acid catalysts can achieve an 81% HCPN yield at the same temperature. If the interface between metal sites and acid sites can be further optimized, the catalytic activity and selectivity can be improved, and the low cost and easy accessibility of non-precious metals can be utilized, it is expected to promote the industrial application of this HMF high-value route.

[0005] In the prior art, such as the journal Nature Catalysis, 2018, 1, 148-155 and patent CN117019139A, an organic ligand self-assembly method can construct a bifunctional catalyst with a controllable acid-metal interface on a traditional supported metal catalyst. However, the reported method is only applicable to precious metals that are not easy to adsorb P, such as Pt, Ru, etc. When applied to the transition metal Ni, due to the strong coordination between Ni and P elements, and the supported Ni precursor needs to be subjected to high-temperature reduction treatment (>400 ℃), not only will the metal active sites be covered and the catalytic activity will be reduced, but it will also easily form a nickel-phosphorus compound active phase, such as the journal Journal of Catalysis, 2023, 421, 117-133 and Applied Catalysis B: Environment and Energy. 2024, 359:124413. Although nickel-phosphorus compounds have shown excellent catalytic activity in many fields, the highest HCPN yield reported based on nickel-phosphorus compounds is only 72%, which is obviously not conducive to the hydrogenation rearrangement reaction of HMF. Therefore, it is still difficult to construct acid-metal Ni catalysts to catalyze HMF to HCPN with high selectivity without losing catalytic activity.

[0006] Therefore, in order to overcome the current technical defects of Ni and P forming nickel-phosphorus compounds and low selectivity of Ni-based catalysts for hydrogenation rearrangement of HMF, it is very necessary to develop a new preparation strategy for acid-Ni catalysts for hydrogenation rearrangement of 5-hydroxymethylfurfural to 3-hydroxymethylcyclopentanone. Summary of the invention

[0007] In view of this, the present invention provides an acid-Ni catalyst for 5-hydroxymethylfurfural hydrogenation rearrangement reaction and a preparation method thereof, wherein the acid-Ni catalyst is constructed by self-assembling organic phosphonic acid on a Ni-based multi-layered material, thereby achieving the goal of significantly increasing the selectivity of HMF hydrogenation rearrangement to 3-hydroxymethylcyclopentanone while maintaining the catalytic activity without forming a nickel-phosphorus compound.

[0008] To achieve the above object, the technical solution of the present invention is as follows: A method for preparing an acid-Ni catalyst for the hydrogenation and rearrangement of 5-hydroxymethylfurfural to produce 3-hydroxymethylcyclopentanone comprises the following steps: (1) preparing a precipitant of a certain concentration, adding an appropriate amount of nickel salt aqueous solution and aluminum salt aqueous solution under constant temperature stirring conditions, adding or not adding magnesium salt aqueous solution, maintaining the pH of the reaction system at 10±1, and then aging, filtering, washing, heat treating and grinding to obtain a Ni multi-layered material NiM, where M is selected from Mg and / or Al; (2) dispersing the Ni multi-layered material NiM in an organic phosphonic acid solution, and obtaining a catalyst precursor PA / NiM through ligand self-assembly; (3) subjecting the catalyst precursor PA / NiM to thermal reduction treatment to obtain an acid-Ni catalyst PA-Ni-M; Wherein, in step (1), the molar ratio of Ni to Al ions is 1:(5-22); when a magnesium salt solution is added, the molar ratio of the sum of the molar amounts of Ni and Mg ions to Al ions is (0.5-4):1; In step (2), the mass ratio of the Ni multi-layered material NiM to the organic phosphonic acid NiM / PAs is 3 to 8; the self-assembly comprises the following process: the mixed solution after dispersing the Ni multi-layered material NiM in the organic phosphonic acid solution is stirred at room temperature for 16 to 24 hours, and then centrifuged, heat treated under flowing air at 100 to 160°C for 4 to 8 hours, washed, and dried to obtain the catalyst precursor PA / NiM.

[0009] The present invention is further configured such that in step (1), the precipitant is selected from one of sodium carbonate aqueous solution, ammonia water or ammonium carbonate aqueous solution, the temperature of constant temperature stirring is 45-85°C, and the stirring rate is controlled at 400-800 r / min. Preferably, the precipitant is selected from sodium carbonate aqueous solution with a concentration of 0.1 M-1.0 M.

[0010] The present invention is further configured such that, in step (1), a sodium hydroxide solution is used to adjust the pH value of the reaction system, the concentration of the sodium hydroxide solution is 0.5-3.0 M, and the dropping rate of the sodium hydroxide solution is 1.0-2.0 mL / min.

[0011] The present invention is further configured such that in step (1), when a magnesium salt solution is added, the molar ratio of the sum of the molar amounts of Ni and Mg ions to the molar amount of Al ions is (1-3):1, for example, 1:1, 2:1 or 3:1.

[0012] The present invention is further configured that, in step (1), in step (1), the total molar concentration of the metal salt solution is 0.4-2.0 M. The total molar concentration of the metal salt solution is the ratio of the sum of the molar amounts of the nickel salt, the aluminum salt and the magnesium salt to the total volume of the system.

[0013] The present invention is further configured that the nickel salt, aluminum salt and magnesium salt are all nitrates.

[0014] The present invention is further configured that, in step (1), the specific process of aging, filtering, washing and heat treatment is: continuous stirring at 45-85°C for 12-24 hours, followed by filtering and washing with ultrapure water until neutral, and then heat treating at 160-220°C for 6-8 hours.

[0015] The present invention is further configured such that, in step (2), the organic phosphonic acid is selected from one or more of methylphosphonic acid (MPA), dimethylphosphonic acid (DMPA), butylphosphonic acid (BPA) or benzylphosphonic acid (BZPA).

[0016] The present invention is further configured such that, in step (2), the concentration of the organic phosphonic acid solution is 1.5-3.0 g / L; preferably 1.5-2.0 g / L.

[0017] The present invention is further configured such that, in step (2), the mass ratio of the multi-layered material NiM to the organic phosphonic acid NiM / PAs is 4 to 8, for example, the mass ratio is 4, 5, 6, 7 or 8.

[0018] The present invention is further configured that, during the self-assembly process, the drying conditions are: vacuum drying at 60-90°C for 1-6 h, preferably at 70-80°C for 2-3 h.

[0019] Through the self-assembly process, the organic phosphonic acid is effectively modified on the surface of the multi-layered material, so that the organic phosphonic acid does not fall off during the subsequent centrifugal separation, heat treatment or thermal reduction process.

[0020] The present invention is further configured that, in step (3), the thermal reduction temperature is 400-600°C, the residence time at the reduction temperature is 1-4 h, the heating rate is 2-5°C / min, and the atmosphere is H 2 / Ar mixed gas, the gas flow rate was controlled at 50~200 mL / min.

[0021] The present invention provides an acid-Ni catalyst, which is prepared by the above-mentioned preparation method. The "acid" in the acid-Ni catalyst refers to the B acid site that provides protonic acid during the reaction process, and the acid-Ni represents the acid-Ni interface site constructed by the catalyst.

[0022] The present invention is further configured such that the Ni content in the acid-Ni catalyst is 4-10wt%.

[0023] The present invention also provides an application of the acid-Ni catalyst described above, which is used for the reaction of hydrogenating and rearranging 5-hydroxymethylfurfural to prepare 3-hydroxymethylcyclopentanone.

[0024] The present invention is further configured that the reaction conditions for the hydrogenation rearrangement of 5-hydroxymethylfurfural to prepare 3-hydroxymethylcyclopentanone are: a temperature of 120-150° C. and a hydrogen pressure of 2.0-4.0 MPa.

[0025] Compared with the prior art, the present invention has the following beneficial effects: (1) The technical solution of the present invention avoids the strong adsorption of phosphorus on metal Ni and thus inhibits the hydrogen evolution ability of metal Ni by self-assembling organic phosphonic acid in a multi-layered metal material precursor, and also avoids the formation of nickel-phosphorus compounds with uncertain active components, thereby improving the selectivity of the catalyst for hydrogenation rearrangement of 5-hydroxymethylfurfural to 3-hydroxymethylcyclopentanone.

[0026] (2) In the preparation method of the Ni catalyst of the present invention, the alkyl tail of the organic phosphonic acid regulates the molecular layer density of the organic phosphonic acid molecular layer on the catalyst surface through steric hindrance, thereby accurately controlling the construction of acid-metal Ni interface sites of different densities, thereby regulating the reaction ratio between full hydrogenation and hydrogenation rearrangement reaction, and achieving control of the reverse product of 5-hydroxymethylfurfural hydrogenation.

[0027] (3) The acid-Ni catalyst provided by the present invention is suitable for multi-layered metal materials with different compositions, and provides a new idea for the reaction system of other non-precious metals and acid-metal bifunctional catalysis. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 The X-ray diffraction patterns of the acid-Ni catalysts prepared in Examples 1 to 4 and the Ni catalyst prepared in Comparative Example 1 are shown, wherein Al 2 O 3:PDF #10-0425 is the Al corresponding to this group of spectra 2 O 3 Standard card; Ni: PDF #04-0850 is the Ni standard card corresponding to this set of spectra.

[0029] Figure 2 The transmission electron micrographs and particle size distributions of the acid-Ni catalysts prepared in Examples 1 to 4 and the Ni catalyst prepared in Comparative Example 1 are shown; wherein (a) is the Ni catalyst prepared in Comparative Example 1, and (b) to (e) are the acid-Ni catalysts prepared in Examples 1, 2, 3, and 4, respectively.

[0030] Figure 3 The infrared spectra of the acid-Ni catalysts prepared in Examples 1 to 4 and the Ni catalyst prepared in Comparative Example 1 are shown.

[0031] Figure 4 The NH of the acid-Ni catalysts prepared in Examples 1, 3, and 4 and the Ni catalyst prepared in Comparative Example 1 are shown. 3 -TPD graph.

[0032] Figure 5 The EXAFS graphs of the acid-Ni catalysts prepared in Examples 1, 3, and 4, the Ni catalyst prepared in Comparative Example 1, and the Ni standard sheet are shown.

[0033] Figure 6 The X-ray diffraction patterns of the catalyst precursor materials prepared in step (2) of Examples 1 and 5 and the precursor material prepared in Comparative Example 1 are shown; wherein JCPDS#22-0700 is a standard card for multi-layered materials.

[0034] Figure 7 The X-ray diffraction patterns of the acid-Ni catalysts prepared in Examples 5 and 9 and the Ni catalysts prepared in Comparative Examples 2 and 3 are shown; wherein Mg 2 O: PDF#65-0476 is the Mg corresponding to this group of spectra 2 O standard card; Ni: PDF #04-0850 is the Ni standard card corresponding to this set of spectra. DETAILED DESCRIPTION

[0035] The present invention is described in detail and completely with specific embodiments and in conjunction with the accompanying drawings. It should be understood that the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of the present invention. Example 1

[0036] Preparation of MPA-5Ni-Al catalyst comprises the following steps: (1) After 1.018 g of nickel nitrate hexahydrate and 28.697 g of aluminum nitrate nonahydrate were completely dissolved in 100 mL of ultrapure water, 100 mL of 0.4 mol / L Na 2 CO 3 In the flask of the aqueous solution, the temperature is maintained at 65 °C, and the pH value is adjusted to 10.0±0.1 by using 1.2 mol / L NaOH aqueous solution; in order to ensure uniform mixing during the dropwise addition, continuous stirring with a magnetic bar is required; after the dropwise addition is completed, stirring is continued at 65 °C for 16 h, and then filtered, the precipitate is washed to neutrality, and then placed in a 220 °C oven for heat treatment for 8 h, ground to uniformity, and the obtained multi-layered material NiAl is collected.

[0037] (2) Dissolve 250 mg of MPA (methylphosphonic acid, purity ≥ 99%) completely in 125 mL of THF, add 1 g of the multi-layered material NiAl obtained in step (1), and continue stirring at room temperature for 16 h. Then separate by centrifugation and heat treat the remaining solid in a flowing air environment at 160 °C for 6 h. Finally, filter and wash the solid powder obtained by heat treatment with 500 mL of THF, dry it in a vacuum drying oven at 80 °C for 2 h, grind it until it is uniform, and collect the obtained catalyst precursor MPA / NiAl.

[0038] (3) The catalyst precursor MPA / NiAl obtained in step (2) was placed in a tube furnace at 10 vol % H 2 The temperature was raised to 450 °C at 3 °C / min in an Ar atmosphere and maintained constant for 4 h, then switched to inert gas purging and naturally cooled to room temperature to obtain an acid-Ni catalyst MPA-5Ni-Al containing 5 wt% Ni.

[0039] The MPA-5Ni-Al catalyst prepared in this example was characterized, wherein the X-ray diffraction pattern is as follows: Figure 1 The transmission electron microscopy image and particle size distribution of the catalyst are shown in Figure 2 As shown by Figure 2 It can be seen that the Ni particles in the catalyst are evenly dispersed, with an average particle size of 5.5 nm; the infrared spectrum is shown in Figure 3 As shown, the MPA-5Ni-Al catalyst has a wavelength of 2920-2930 cm -1 The characteristic peaks of CH stretching vibration appeared on the left and right, proving the effective modification of methylphosphonic acid; NH 3 -TPD picture Figure 4 As shown in FIG. 1 , the total acid content is reduced compared with that of Comparative Example 1; the EXAFS diagram is shown in FIG. Figure 5As shown, it shows that there is a Ni-Ni bond but no Ni-P bond; the X-ray diffraction pattern of the catalyst precursor material MPA / NiAl obtained in step (2) is as follows Figure 7 shown. Example 2

[0040] The DMPA-5Ni-Al catalyst was prepared. The preparation steps were basically the same as those in Example 1, except that the organic phosphonic acid MPA in Example 1 was replaced by DMPA.

[0041] The DMPA-5Ni-Al catalyst prepared in this example was characterized, wherein the X-ray diffraction pattern is as follows: Figure 1 As shown, it is basically the same as the MPA-5Ni-Al catalyst prepared in Example 1; the transmission electron microscope image and particle size distribution of the catalyst are shown in Figure 2 As shown by Figure 2 It can be seen that the Ni particles in the catalyst are evenly dispersed, with an average particle size of 5.4 nm. The morphology and average particle size are basically the same as those in Example 1; the infrared spectrum is shown in FIG. Figure 3 As shown in the figure, the DMPA-5Ni-Al catalyst has a wavelength of 2920~2930 cm -1 The characteristic peaks of CH stretching vibration also appear on the left and right, proving the effective modification of dimethylphosphonic acid. Example 3

[0042] The BPA-5Ni-Al catalyst was prepared by the same preparation steps as those in Example 1, except that the organic phosphonic acid MPA in Example 1 was replaced by BPA.

[0043] The BPA-5Ni-Al catalyst prepared in this example was characterized, wherein the X-ray diffraction pattern is as follows: Figure 1 As shown, it is basically the same as the MPA-5Ni-Al catalyst prepared in Example 1; the transmission electron microscope image and particle size distribution of the catalyst are shown in Figure 2 As shown by Figure 2 It can be seen that the Ni particles in the catalyst are evenly dispersed, with an average particle size of 5.0 nm, and their morphology and average particle size are basically the same as those in Example 1; the infrared spectrum is shown in Figure 3 As shown in the figure, the DMPA-5Ni-Al catalyst has a wavelength of 2910~2940 cm -1 The characteristic peaks of CH stretching vibration appeared on the left and right, proving the effective modification of butylphosphonic acid; NH 3 -TPD picture Figure 4 As shown in FIG. 1 , the total acid content of the catalyst is increased compared with the MPA-5Ni-Al catalyst modified by MPA (Example 1). Figure 5As shown, it is also shown that Ni-Ni bonds exist but Ni-P bonds do not exist, indicating that nickel-phosphorus compounds will not be generated by using the preparation method of the present invention when different organic phosphonic acids are replaced. Example 4

[0044] The BZPA-5Ni-Al catalyst was prepared. The preparation steps were basically the same as those in Example 1, except that the organic phosphonic acid MPA in Example 1 was replaced by BZPA (benzylphosphonic acid, purity ≥ 99.97%).

[0045] The BZPA-5Ni-Al catalyst prepared in this example was characterized, wherein the X-ray diffraction pattern is as follows: Figure 1 As shown, it is basically the same as the MPA-5Ni-Al catalyst prepared in Example 1; the transmission electron microscope image and particle size distribution of the catalyst are shown in Figure 2 As shown by Figure 2 It can be seen that the Ni particles in the catalyst are evenly dispersed, with an average particle size of 4.4 nm. The morphology and average particle size are basically the same as those in Example 1; the infrared spectrum is shown in FIG. Figure 3 As shown, the BZPA-5Ni-Al catalyst has a peak at 3000-3100 cm -1 The stretching vibration characteristic peaks of aromatic hydrocarbons appeared on the left and right, proving the effective modification of benzylphosphonic acid; NH 3 -TPD picture Figure 4 As shown in FIG. 1 , the number of acid sites is further reduced compared with the BPA-5Ni-Al catalyst modified with BPA (Example 3). Figure 5 As shown, there is a Ni-Ni bond but no Ni-P bond, which once again proves that the preparation method described in the invention will not generate nickel-phosphorus compounds when different organic phosphonic acids are replaced. Example 5

[0046] The MPA-5Ni-MgAl-3 catalyst was prepared by the same preparation steps as in Example 1, except that magnesium nitrate hexahydrate was further added in step (1), specifically: After 0.8607 g of nickel nitrate hexahydrate, 7.503 g of aluminum nitrate nonahydrate, and 14.626 g of magnesium nitrate hexahydrate were completely dissolved in 100 ml of ultrapure water, 100 mL of 0.4 mol / L Na 2 CO 3In the flask of the aqueous solution, the temperature is maintained at 65 °C, and the pH value is adjusted to 10.0±0.1 by using 1.2 mol / L NaOH aqueous solution; in order to ensure uniform mixing during the dropwise addition, continuous stirring with a magnetic bar is required; after the dropwise addition is completed, stirring is continued at 65 °C for 16 h, filtered, and then the precipitate is washed to neutrality and placed in a 220 °C oven to dry for 8 h, ground to uniformity, and the obtained material NiMgAl is collected.

[0047] The catalyst precursor material obtained in step (2) of this embodiment and the MPA-5Ni-MgAl-3 catalyst obtained in this embodiment were characterized, wherein the X-ray diffraction pattern of the catalyst precursor material MPA / NiMgAl-3 obtained in step (2) is as follows: Figure 6 As shown, the structures are similar to those of Comparative Example 1 and Example 1, and both are multi-layered metal materials; the X-ray diffraction pattern of MPA-Ni-MgAl-3 is as follows Figure 7 As shown, the structure is similar to that of Comparative Example 2. Example 6

[0048] The DMPA-5Ni-MgAl-3 catalyst was prepared. The preparation steps were basically the same as those in Example 5, except that the organic phosphonic acid MPA in Example 5 was replaced by DMPA. Example 7

[0049] The BPA-5Ni-MgAl-3 catalyst was prepared. The preparation steps were basically the same as those in Example 5, except that the organic phosphonic acid MPA in Example 5 was replaced by BPA. Example 8

[0050] The BZPA-5Ni-MgAl-3 catalyst was prepared, and its preparation steps were basically the same as those in Example 5, except that the organic phosphonic acid MPA in Example 5 was replaced by BZPA. Example 9

[0051] The MPA-5Ni-MgAl-1 catalyst was prepared in the same steps as in Example 5, except that the amounts of nickel nitrate hexahydrate, aluminum nitrate nonahydrate and magnesium nitrate hexahydrate added in step (1) were different. In this example, 0.9305 g of nickel nitrate hexahydrate, 15.005 g of aluminum nitrate nonahydrate and 9.436 g of magnesium nitrate hexahydrate were added in step (1).

[0052] The MPA-5Ni-MgAl-1 catalyst obtained in this example was characterized, and its X-ray diffraction pattern was as follows: Figure 7 As shown, the structure is similar to that of Comparative Example 3. Example 10

[0053] The DMPA-5Ni-MgAl-1 catalyst was prepared. The preparation steps were basically the same as those in Example 9, except that the organic phosphonic acid MPA in Example 5 was replaced by DMPA. Embodiment 11

[0054] The BPA-5Ni-MgAl-1 catalyst was prepared. The preparation steps were basically the same as those in Example 9, except that the organic phosphonic acid MPA in Example 5 was replaced by BPA. Example 12

[0055] The BZPA-5Ni-MgAl-1 catalyst was prepared. The preparation steps were basically the same as those in Example 9, except that the organic phosphonic acid MPA in Example 5 was replaced by BZPA.

[0056] Comparative Example 1 Preparation of 5Ni-Al catalyst comprises the following steps: (1) After 1.018 g of nickel nitrate hexahydrate and 28.697 g of aluminum nitrate nonahydrate were completely dissolved in 100 mL of ultrapure water, the mixture was gradually added dropwise to a 100 mL 0.4 mol / L sodium hydroxide solution at a flow rate of 0.8 mL / min. 2 CO 3 In the flask of the aqueous solution, the temperature is maintained at 65 °C, and the pH value is adjusted to 10.0±0.1 by using 1.2 mol / L NaOH aqueous solution; in order to ensure uniform mixing during the dropwise addition, continuous stirring with a magnetic bar is required; after the dropwise addition is completed, stirring is continued at 65 °C for 16 h, and then the precipitate is washed to neutrality by filtration and then dried in a 220 °C oven for 8 h, and the obtained material NiAl is ground to be uniform and collected.

[0057] (2) Place the NiAl material obtained in step (1) in a tube furnace and heat it in 10% H 2 The temperature was raised to 450 °C at 3 °C / min in a / Ar atmosphere and maintained constant for 4 h, then the inert gas was switched to purge and naturally cooled to room temperature to obtain a 5Ni-Al catalyst containing 5 wt% metallic Ni.

[0058] The 5Ni-Al catalyst prepared in this comparative example was characterized, wherein the X-ray diffraction pattern is as follows Figure 1 As shown, it is basically the same as the MPA-5Ni-Al catalyst prepared in Example 1; the transmission electron microscope image and particle size distribution of the catalyst are shown in Figure 2 As shown by Figure 2 It can be seen that the average particle size is 5.8nm, and its morphology and average particle size are basically the same as those in Example 1; the infrared spectrum is as shown in Figure 3 As shown in Figure 2, compared with Example 1, the -1There is no characteristic peak of CH stretching vibration on the left and right sides; NH 3 -TPD picture Figure 4 As shown in Figure 2, the catalyst has more weak acid sites compared to the comparative example. Figure 5 shown.

[0059] Comparative Example 2 Preparation of 5Ni-MgAl-3 catalyst The preparation steps of this comparative example are basically the same as those of comparative example 1, except that the amount of metal salt added in step (1) is changed to: 0.8607 g of nickel nitrate hexahydrate, 7.503 g of aluminum nitrate nonahydrate and 14.626 g of magnesium nitrate hexahydrate.

[0060] The 5Ni-MgAl-3 catalyst prepared in this comparative example was characterized, wherein the X-ray diffraction pattern is as follows Figure 7 shown.

[0061] Comparative Example 3 Preparation of 5Ni-MgAl-1 Catalyst The preparation steps of this comparative example are basically the same as those of comparative example 1, except that the amount of metal salt added in step (1) is changed to: 0.9305 g of nickel nitrate hexahydrate, 15.005 g of aluminum nitrate nonahydrate and 9.436 g of magnesium nitrate hexahydrate.

[0062] The 5Ni-MgAl-1 catalyst prepared in this comparative example was characterized, wherein the X-ray diffraction pattern is as follows Figure 7 shown.

[0063] Comparative Example 4 Preparation of 5Ni / Al 2 O 3 The catalyst comprises the following steps: (1) Prepare 0.45 mol / L nickel nitrate ethanol solution and quickly add it dropwise to a flask containing 1 g Al 2 O 3 The carrier was placed in a small glass bottle, and then the glass house was placed on an oscillator for rapid oscillation for 30 minutes, left to stand at room temperature for 16 hours, and then heat-treated in an oven at 120°C for 8 hours. The solid was taken out and ground to obtain a catalyst precursor.

[0064] (2) The catalyst precursor obtained in step (1) was placed in a tube furnace and heated at 10% H 2 The temperature was raised to 450 °C at 3 °C / min in an Ar atmosphere and maintained constant for 4 h, then switched to inert gas purging and naturally cooled to room temperature to obtain 5Ni / Al containing 5wt% Ni. 2 O 3 catalyst.

[0065] Comparative Example 5 Preparation of MPA / 5Ni / Al 2 O 3 The catalyst comprises the following steps: (1) Prepare 0.45 mol / L nickel nitrate ethanol solution and quickly add it dropwise to a flask containing 1 g Al 2 O 3 The carrier was placed in a small glass bottle, and then the glass house was placed on an oscillator for rapid oscillation for 30 minutes, left to stand at room temperature for 16 hours, and then heat-treated in an oven at 120°C for 8 hours. The solid was taken out and ground to obtain a catalyst precursor.

[0066] (2) Dissolve 250 mg of MPA completely in 125 mL of THF, add 1 g of the catalyst precursor obtained in step (1), and continue stirring at room temperature for 16 h. Then separate by centrifugation and heat treat the remaining solid in a flowing air environment at 160 °C for 6 h. Finally, filter and wash the solid powder obtained by heat treatment with 500 mL of THF, dry it in a vacuum drying oven at 80 °C for 2 h, grind it until it is uniform, and collect the obtained precursor material.

[0067] (3) Place the precursor material obtained in step (2) in a tube furnace and heat at 10% H 2 The temperature was raised to 450 °C at 3 °C / min in an Ar atmosphere and maintained constant for 4 h, then switched to an inert gas purge and naturally cooled to room temperature to obtain MPA / 5Ni / Al containing 5 wt% Ni and MPA modified 2 O 3 catalyst.

[0068] Comparative Example 6 Preparation of MPA-5Ni-Al: 20 catalyst The preparation steps of this comparative example are basically the same as those of Example 1, except that the amount of MPA added in step (2) of Example 1 is different. The amount of MPA added in this example is 0.05 g.

[0069] Comparative Example 7 Preparation of MPA-5Ni-Al: 1 catalyst The preparation steps of this comparative example are basically the same as those of Example 1, except that the amount of MPA added in step (2) of Example 1 is different. The amount of MPA added in this example is 1 g. Embodiment 13

[0070] Performance evaluation of catalysts in the hydrogenation rearrangement of HMF to HCPN The organic phosphonic acid-Ni catalysts prepared in Examples 1 to 12 and the Ni catalysts prepared in Comparative Examples 1 to 5 were used to evaluate the HMF hydrogenation rearrangement reaction at different temperatures and hydrogen pressures; the hydrogenation rearrangement reaction performance evaluation of 5-hydroxymethylfurfural was carried out on a YZPR-650 reactor of Shanghai Yanzheng Instrument Co., Ltd. After the reaction was completed, the reactor body was placed in an ice water bath to quickly quench and stop the reaction, the reaction liquid was collected, and then N,N-dimethylformamide was added as an internal standard. Finally, 1.5 ml of the reaction liquid was drawn with a syringe and transferred into a gas chromatography bottle through a 0.22 μm nylon filter membrane for analysis.

[0071] Distribution of reactants and products An Agilent 8860 gas chromatograph equipped with a DB-WAX UI capillary column (30 m in length, 0.32 mm in inner diameter, and 0.25 μm in film thickness) and a FID (Flame Ionization Detector) was used to quantitatively analyze the products of the hydrogenation rearrangement reaction of HMF.

[0072] Evaluation conditions: Before each catalyst evaluation, 20 mg of catalyst that has not been exposed to air in the tubular furnace is sealed with an aqueous solution and completely transferred to the reactor to prevent the catalyst from being oxidized during the removal process. Then 10 mL of aqueous solution and 30-80 mg of reactant (HMF) are filled into the reactor. After filling, argon is used to replace the gas in the reactor three times to remove the original air in the reactor, and then the reactor is heated to the required temperature (120-140 °C). When the reactor reaches the set temperature, the argon in the reactor is replaced with hydrogen 5 times and the hydrogen pressure is controlled to the required size (2-4 MPa) at the end, and then the stirring is turned on to start the reaction, and the stirring rate is 900 r / min.

[0073] The catalytic performance of the catalyst of the present invention for the hydrogenation rearrangement of HMF to HCPN was evaluated by testing the HMF conversion rate and HCPN selectivity of the organophosphonic acid-Ni catalysts prepared in Examples 1 to 12 and the Ni catalysts prepared in Comparative Examples 1 to 7, wherein:

[0074] The results are shown in Table 1.

[0075] Table 1 Evaluation results of organophosphoric acid-Ni catalyst PAs-5Ni-Al in hydrogenation rearrangement HMF system

[0076] It can be seen from the data in Table 1 that this example selects the reaction of 5-hydroxymethylfurfural hydrogenation rearrangement to produce 3-hydroxymethylcyclopentanone to examine the Ni-based catalysts without phosphonic acid modification (Comparative Examples 1 to 7) and Ni-based catalysts modified with different organic phosphonic acids (Examples 1 to 12). After the reaction of Comparative Example 1 (5Ni-Al) and Examples 1 to 4 (MPA-5Ni-Al, DMPA-5Ni-Al, BPA-5Ni-Al and BZPA-5Ni-Al) for 4 h at 120 °C and 4 MPa in the aqueous phase, the conversion rate and selectivity are not ideal. This is because the reaction temperature is low at this time, and most of the HMF reacted is still in the intermediate product, such as furan dimethanol BHF. When the reaction time is extended and the reaction depth is further deepened, it can be seen that the HCPN selectivity of Examples 1 and 2 modified with organic phosphonic acid has increased. In contrast, in Comparative Example 1, the unmodified 5Ni-Al tends to generate the hydrogenation product BHTF. With the increase of reaction temperature and hydrogen pressure, the conversion rate of all catalysts has increased and the selectivity has also changed. As the temperature rises, the selectivity of HCPN on the comparative example (5Ni-Al) increases more than the selectivity of BHTF, and as the hydrogen pressure increases, the reaction proceeds in the direction of BHTF. This is because the hydrogenation rearrangement reaction of HMF often requires a higher activation energy than full hydrogenation, and increasing the temperature is thermodynamically more favorable to hydrogenation rearrangement; secondly, full hydrogenation of HMF requires a large amount of H2, and increasing the hydrogen pressure is conducive to increasing the H concentration in the solution and promoting the full hydrogenation reaction.

[0077] In general, in the unmodified acid comparative example 1, the reaction does not mainly tend to the hydrogenation rearrangement reaction, and a large amount of BHTF by-products are still produced. In contrast, all of Examples 1 to 4 are more inclined to hydrogenation rearrangement to generate HCPN under the same conditions, and the selectivity of HCPN can be increased by up to 1.8 times. It should be noted that the catalyst modified with the strong steric hindrance group BZPA (Example 4) has a large number of macromolecules on the support surface, which forms a repulsive force with the reactant molecules, reducing the rate of diffusion of the reactant HMF from the solution to the support surface, so the conversion rate is slightly reduced. Secondly, Examples 1 and 2 modified with MPA and DMPA have the highest HCPN selectivity, while Examples 3 and 4 modified with BPA and BZPA are second. This is because the former two have the smallest steric hindrance and thus have the highest density of acid-metal Ni interfaces, which is conducive to the reaction intermediate BHF to generate HCPN in the direction of ring-opening rearrangement. It should be noted that if a traditional impregnated Ni-based catalyst (Comparative Example 4, Ni / Al 2 O 3 ) and the impregnated Ni-based catalyst modified with MPA (Comparative Example 5, MPA / Ni / Al 2 O 3), the organic phosphonic acid will be directly adsorbed on the metal Ni and shield the reaction active sites. For example, the reaction result of Comparative Example 5 under the same conditions has a conversion rate of only 34.8%.

[0078] In addition, according to the above experimental results, the metal of the Ni-based multi-layered material was replaced, and Mg ions were introduced to form the NiMgAl ternary layered material. With the introduction of Mg, the Lewis acid sites on the surface of the alumina support were neutralized, the ring-opening rearrangement reaction was inhibited, and the BHTF selectivity was as high as 99%. Similar to the previous results, HMF is more inclined to generate HCPN after the organic phosphonic acid modified PAs-5Ni-MgAl.

[0079] The above results show that the organophosphonic acid-Ni catalyst has good catalytic activity for the hydrogenation rearrangement of 5-hydroxymethylfurfural to 3-hydroxymethylcyclopentanone, which provides a good way to high-value utilization of biomass platform molecule 5-hydroxymethylfurfural. Embodiment 14

[0080] Initial Reaction Kinetics of BHF Hydrogenation Rearrangement to HCPN over Organophosphonic Acid-Ni Catalyst The Ni-based catalysts prepared in Example 1, Example 3 and Comparative Example 1 were used to evaluate the initial reaction rate with 5-hydroxymethylfurfural (HMF), furandimethanol (BHF, a carbonyl hydrogenation product of HMF and also a key intermediate product of the reaction) and 1-hydroxy-2,5-hexanedione (HHD, a ring-opening product of BHF, HCPN can be obtained by intramolecular aldol condensation) as reactants, and the initial kinetics of BHF as a reactant were evaluated.

[0081] The above reactions were all carried out on a YZPR-650 reactor from Shanghai Yanzheng Instrument Co., Ltd. After the reaction was completed, the reactor was placed in an ice-water bath to quickly quench and stop the reaction. The reaction liquid was collected, and then N,N-dimethylformamide was added as an internal standard. Finally, 1.5 mL of the reaction liquid was drawn with a syringe and transferred into a gas chromatography bottle through a 0.22 μm nylon filter membrane for analysis.

[0082] Distribution of reactants and products An Agilent 8860 gas chromatograph equipped with a DB-WAX UI capillary column (30 m in length, 0.32 mm in inner diameter, and 0.25 μm in film thickness) and a FID (Flame Ionization Detector) was used to quantitatively analyze the products of the hydrogenation rearrangement reaction of HMF.

[0083] Evaluation conditions: Similar to Example 13, except that the reaction conversion rate needs to be controlled to be ≤20% to avoid the influence of mass transfer.

[0084] The conversion rate C of the reaction substrate of the catalyst under testi , the yield of the product of each reaction step Y j , to evaluate the initial reaction rate TOF of different reaction paths:

[0085] The reaction order n and the reaction activation energy Ea are obtained by linear fitting from the following equations:

[0086] Among them, C and B represent constant terms, and R represents the gas constant, which is 8.314 J·mol -1 ·K -1 The results are shown in Tables 2 and 3 below.

[0087] Table 2 Initial reaction rate of acid-Ni catalyst in the hydrogenation rearrangement HMF system

[0088] From the data in Table 2, it can be seen that in Comparative Example 1 with unmodified organic phosphonic acid, the ring-opening rearrangement reaction of the reaction intermediate BHF is the slowest step among all the reaction steps, which also means that it is the rate-determining step of the reaction. In Example 1 modified with MPA, the initial reaction rate of this step increased by an order of magnitude to 561.1 h -1 Such a fast ring-opening rearrangement rate allows BHF to be quickly converted into a ring-opening rearrangement intermediate product, and thus cannot generate the ring hydrogenation product BHTF that cannot be converted into HCPN. Therefore, the HCPN selectivity is much higher than that of Comparative Example 1.

[0089] The above results show that the acid-Ni catalyst MPA-5Ni-Al prepared in Example 1 has good HCPN selectivity and catalytic activity. This improvement in selectivity is due to the fact that it greatly accelerates the conversion rate of the rate-determining step of the reaction compared with 5Ni-Al of unmodified organic phosphonic acid (Comparative Example 1).

[0090] Table 3 Initial reaction kinetic parameters of acid-Ni catalyst in BHF reaction system

[0091] From the data in Table 3, it can be seen that the reaction order of the intermediate product BHF undergoing ring hydrogenation and ring-opening rearrangement on the acid-metal Ni catalyst (Example 1 and Example 3) modified with organic phosphonic acid is reduced, which means that the adsorption of BHF on the acid-metal Ni catalyst modified with organic phosphonic acid is stronger than that on Comparative Example 1 (5Ni-Al), indicating that BHF is more easily adsorbed on the active site of the catalyst and then reacts. Secondly, while the activation energy of BHF ring hydrogenation does not change significantly, the activation energy of BHF ring-opening rearrangement is greatly reduced in Examples 1 and 3 modified with organic phosphonic acid. Lower activation energy means that thermodynamically, the BHF ring-opening rearrangement reaction is more likely to occur on the acid-metal Ni catalyst modified with organic phosphonic acid.

[0092] The above results show that the acid-Ni catalysts MPA-5Ni-Al and BPA-5Ni-Al prepared in Example 1 and Example 3 have lower BHF ring-opening activation energy and stronger adsorption of reactants, thereby greatly increasing the reaction activity and HCPN selectivity. Embodiment 15

[0093] Stability Evaluation of Organic Phosphonic Acid-Ni Catalyst Example 1, Example 5, and Example 9 were selected, and the hydrothermal stability of the catalysts was evaluated according to the catalytic performance test method of Example 13, wherein: Y(HCPN) = *100%. The results are shown in Table 4 below.

[0094] Table 4 Hydrothermal stability evaluation of acid-Ni catalyst

[0095] It can be seen from the data in Table 4 that, compared with the MPA-5Ni-Al acid-Ni catalyst prepared in Example 1, the MPA-5Ni-MgAl catalyst (Example 5, Example 9) still maintained a HMF conversion rate of more than 99.8% after 4 cycles, and the selectivity and yield of HCPN were both maintained at more than 90.0%. The above results show that the acid-Ni catalysts prepared in Examples 5 and 9 have good hydrothermal stability.

[0096] It can be seen from the above stability test that in the technical solution of the present invention, by adjusting the composition of the multi-layered material, the hydrothermal stability of the catalyst can be further optimized, thereby optimizing the application of the catalyst in process production.

[0097] Obviously, the above embodiments of the present invention are only examples for clearly illustrating the present invention, and are not limitations on the implementation methods of the present invention. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made on the basis of the above description. It is impossible to list all the implementation methods here. All obvious changes or modifications derived from the technical solution of the present invention are still within the scope of protection of this patent.

Claims

1. A method for preparing an acid-Ni catalyst for the hydrogenation and rearrangement of 5-hydroxymethylfurfural to produce 3-hydroxymethylcyclopentanone, characterized in that: The steps include: (1) preparing a precipitant of a certain concentration, adding an appropriate amount of nickel salt aqueous solution and aluminum salt aqueous solution under constant temperature stirring conditions, adding or not adding magnesium salt aqueous solution, maintaining the pH of the reaction system at 10±1, and then aging, filtering, washing, heat treating and grinding to obtain a Ni multi-layered material NiM, where M is selected from Mg and / or Al; (2) dispersing the Ni multi-layered material NiM in an organic phosphonic acid solution, and obtaining a catalyst precursor PA / NiM through ligand self-assembly; (3) subjecting the catalyst precursor PA / NiM to thermal reduction treatment to obtain an acid-Ni catalyst PA-Ni-M; Wherein, in step (1), the molar ratio of Ni to Al ions is 1:(5-22); when a magnesium salt solution is added, the molar ratio of the sum of the molar amounts of Ni and Mg ions to Al ions is (0.5-4):1; In step (2), the mass ratio of the Ni multi-layered material NiM to the organic phosphonic acid NiM / PAs is 3-8; the self-assembly comprises the following process: the mixed solution after dispersing the Ni multi-layered material NiM in the organic phosphonic acid solution is stirred at room temperature for 16-24 h, then centrifuged, heat treated at 100-160 ° C in flowing air for 4-8 h, washed and dried to obtain the catalyst precursor PA / NiM.

2. The preparation method according to claim 1, characterized in that: In step (1), the precipitant is selected from one of sodium carbonate aqueous solution, ammonia water or ammonium carbonate aqueous solution.

3. The preparation method according to claim 1, characterized in that In step (1), the specific process of aging, filtering, washing and heat treatment is: stirring continuously at 45-85°C for 12-24 hours, then filtering and washing with ultrapure water until neutral, and heat treating for 6-8 hours, wherein the heat treatment temperature is 160-220°C.

4. The preparation method according to claim 1, characterized in that: In step (1), the total molar concentration of the metal brine is 0.4-2.0M.

5. The preparation method according to claim 1, characterized in that: In step (2), the organic phosphonic acid is selected from one or more of methylphosphonic acid, dimethylphosphonic acid, butylphosphonic acid or benzylphosphonic acid.

6. The preparation method according to claim 1, characterized in that In step (2), the concentration of the organic phosphonic acid solution is 1.5-3.0 g / L.

7. The preparation method according to claim 1, characterized in that In step (3), the thermal reduction temperature is 400-600°C, and the residence time at the reduction temperature is 1-4 h.

8. An acid-Ni catalyst, characterized in that The method is prepared by any one of claims 1 to 7.

9. The acid-Ni catalyst according to claim 8, characterized in that In the acid-Ni catalyst, the Ni content is 4-10 wt%.

10. Use of the acid-Ni catalyst as claimed in claim 8 or 9, characterized in that: Used for the hydrogenation and rearrangement of 5-hydroxymethylfurfural to produce 3-hydroxymethylcyclopentanone.

Images