Preparation of Ni-Al / HAP-P catalyst and application thereof in furfural hydrogenation reaction

Abstract

The application discloses a kind of Ni-Al / HAP-P catalyst preparation and its application in furfural hydrogenation reaction, belong to catalyst preparation technical field.For the problems existing in the catalyst for preparing cyclopentanone by furfural hydrogenation, the application obtains nanoscale hydroxyapatite (HAP) carrier by reacting calcium metal salt with phosphorus precursor, then mixed with nickel salt and aluminum salt solution, to obtain cation doped modified Ni-Al / HAP-P catalyst.HAP as carrier, can highly disperse anchor active H2 molecule Ni active center;Alkaline Ca ion inhibits furfural self-polymerization and aldehyde ketone condensation side reaction, P atom auxiliary promotes the selectivity of cyclopentanone.The catalyst structure is stable, and has good repeated use performance, can adapt to high concentration furfural reaction system (8~12 wt%), and furfural conversion rate can reach 93.25%~99.31%, and the selectivity of cyclopentanone reaches 90.37%~98.97%.

Description

Technical Field

[0001] This invention belongs to the field of catalyst preparation technology, and specifically relates to a method for preparing a catalyst for the hydrogenation reaction of furfural and its application. Background Technology

[0002] Cyclopentanone is an important organic chemical intermediate with excellent physical and chemical properties. It is widely used in the synthesis of pesticides, pharmaceuticals, fragrances, and electronic products, and has broad applications in organic synthesis and fine chemicals. Market demand is substantial, and its development prospects are very promising. Currently, commonly used methods for preparing cyclopentanone include the adipic acid method, the cyclopentene oxidation method, the cyclopentane method, and the furfural hydrogenation method. The adipic acid method is currently the method for preparing over 90% of cyclopentanone in the market. It has the advantages of simple reaction process and mature technology. However, this method has complex post-processing, generates a large amount of pollutants during the reaction, and the raw material adipic acid depends on fossil fuels, which are expensive and have limited sources. The cyclopentene oxidation method has the advantages of relatively abundant raw material sources and high product selectivity. However, the homogeneous catalytic system increases the difficulty of product separation, and the chloride ions in the system can corrode the reaction equipment, limiting its industrial application. The cyclopentane method has the advantages of relatively mild reaction conditions and no obvious equipment corrosion. However, this method currently has low catalytic efficiency, which is difficult to meet the needs of industrial mass production. As is well known, there are currently more than 100 furfural production enterprises in China. The initial aqueous solution concentration of furfural obtained by hydrolyzing hemicellulose from raw materials such as crop straw and forestry waste with sulfuric acid is 8-12 wt%. The raw materials are widely available and inexpensive. Therefore, the one-step hydration hydrogenation route for preparing bio-based cyclopentanone using high-concentration furfural (8-12 wt%) as a platform compound significantly reduces dependence on fossil resources by relying on the renewability of biomass feedstock and the cleanliness of the hydrogenation process. It also has the advantages of short reaction path, high atom utilization rate and low emissions of waste, making it the green synthesis technology with the most promising prospects for industrial application.

[0003] Currently, catalysts used for the catalytic hydrogenation of furfural to cyclopentanone mainly include noble metal catalysts and non-noble metal catalysts. Patent CN108067253A discloses a Ru-Fe / Zn-Ca / Mg-TiO2 coated film modified supported catalyst for this reaction. Although the cyclopentanone yield is high, the preparation cost of noble metal catalysts is high, thus limiting their widespread industrial application. The literature (Acta Physico-Chimica Sinica, 2025, 41(4)) reports a Rh / HAP noble metal catalyst. Although it can construct stable metal active sites with the O-SMSI effect based on the HAP support, the core active component is the noble metal Rh, which is expensive. Moreover, it must undergo high-temperature oxidation pretreatment at 500 °C to form stable O-SMSI, making the preparation process cumbersome. It is only suitable for the conversion of furfuryl alcohol substrate and cannot be adapted to the efficient conversion of high-concentration furfural raw materials.

[0004] To overcome the aforementioned shortcomings, patent CN120515456A employs a rare-earth basic carbonate (LaCO3(OH))-supported Ni / NiO dual-phase catalyst for the hydrogenation rearrangement of furfural to prepare cyclopentanone. This catalyst uses inexpensive and readily available raw materials, but its yield is low at 88.71%. To further improve the catalytic reaction yield and suppress active site aggregation during long-cycle reactions, as well as stabilize product selectivity, patent CN120586888A discloses a Ni-Ce / SiO2-Al2O3 bimetallic supported catalyst. By constructing a hierarchical porous composite support and introducing Ce promoters to modify and regulate the metal electronic structure and surface acid-base sites, it effectively suppresses side reactions and sintering aggregation of active components, significantly improving the cyclopentanone yield. Simultaneously, it greatly improves the selective decay problem during catalyst recycling, but the concentration of the reaction substrate furfural is only 5%. Patent CN120885224A discloses a nickel-zinc-aluminum three-dimensional flower-like coprecipitation catalyst for the hydrogenation of furfural to cyclopentanone. Although the introduction of Zn element achieves surface acidity regulation and oxygen vacancy construction, this technical route is not the only option for the hydrogenation of furfural to cyclopentanone. The introduction of Zn mainly serves the need for regulating the dispersion of metal particles and the surface acid-base balance in the carrierless LDH coprecipitation process. Moreover, this technical solution also has inherent defects such as complex raw material composition, easy sintering and agglomeration of metal particles, and insufficient long-term cycle stability. Patent CN112194577A discloses a Ni3P-based furfural hydrogenation catalyst. This system requires the addition of hypophosphite and high-temperature phosphating treatment to generate the Ni3P crystal phase to improve hydrogenation activity. However, the support used can only provide a single weakly acidic site, which is only suitable for low-concentration furfural raw materials of 0.5~8 wt%. At the same time, Ni3P particles are prone to sintering and loss at high temperatures, resulting in poor catalyst recycling performance. Meanwhile, based on a review of relevant literature (Chinese Journal of Catalysis, 2021, 42(12):2216-2224, Fuel, 2027, 427:139800, Journal of Catalysis, 2026, 456:116783), it was found that the furfural concentration used in this system was generally 1.88~4.76wt%. Although the cyclopentanone yield was generally greater than 90%, the concentration of furfural aqueous solution in the reaction was relatively low, resulting in high water consumption in industrial production. In the later stage, the low-concentration product was subjected to triple-effect evaporation for water removal, which was energy-intensive and costly, which was not conducive to industrial production. Furthermore, the core problem of easy polymerization of furfural at high concentrations was not solved.

[0005] Existing research indicates that in the hydrogenation of furfural to cyclopentanone, noble metal catalysts are limited in large-scale application due to their high cost, while non-noble metal catalysts generally suffer from problems such as active site aggregation and selective decay during long-cycle processes, resulting in insufficient stability. Furthermore, furfural molecules are highly reactive and prone to self-polymerization or condensation with the product under high concentration conditions. The resulting polymers adsorb onto the active sites, reducing feedstock utilization and accelerating catalyst deactivation. Existing systems often use low-concentration furfural as a feedstock to suppress polymerization, leading to high water consumption and separation costs in industrial production. In addition, the imbalance of acid-base sites on the catalyst surface is a significant issue. Insufficient acidic sites result in low efficiency of furan ring-opening rearrangement, while excessively strong acidity or the absence of basic sites easily triggers polymerization side reactions, making it difficult to simultaneously meet the dual requirements of catalytic reaction and side reaction suppression.

[0006] Against this backdrop, developing a catalyst system that boasts low raw material costs, simple preparation process, uniformly dispersed active sites, excellent thermal stability, and the ability to effectively inhibit polymerization under high-concentration furfural reaction conditions is crucial for advancing the furfural hydrogenation to cyclopentanone process from the laboratory to industrialization. However, currently, there is no solution in the field of catalyst design that can simultaneously overcome these bottlenecks. Summary of the Invention

[0007] To address the aforementioned technical problems, this invention proposes a method for preparing a Ni-Al / HAP-P catalyst and its application in the hydrogenation reaction of furfural. This method effectively solves a series of problems associated with existing catalysts, such as high cost, easy metal agglomeration, inability to adapt to high-concentration furfural feedstocks, numerous side reactions, and poor cycle stability.

[0008] To achieve the above objectives, the technical solution of the present invention is implemented as follows:

[0009] In a first aspect, the present invention provides a Ni-Al / HAP-P catalyst, which mainly consists of a hydroxyapatite (HAP) support and active metal Ni and auxiliary metal Al supported on the surface of the HAP support. The catalyst does not contain Zn or the noble metal Rh; it relies on the in-situ formation of Ni-P coordination bonds between phosphorus atoms in the HAP framework and the Ni active sites, eliminating the need for high-temperature oxidation pretreatment; the Ca of the HAP support... 2+ Basic sites and Al 3+ Acidic sites synergistically inhibit the formation of cyclopentanol byproducts.

[0010] This invention draws upon the excellent intrinsic structure and physicochemical properties of natural hydroxyapatite: the support possesses a unique porous layered structure and good thermal stability. The support framework inherently contains Ca-based basic sites and phosphorus-oxygen acidic sites, achieving high dispersion of active metals, suppressing furfural polymerization side reactions, and electronically modulating the nickel active center without the need for additional Zn, rare earth, or noble metal additives. In contrast, existing technologies using supportless LDH co-precipitation to prepare Ni-Zn-Al catalysts rely on zinc to regulate surface acidity, and the lack of a support to bind metal particles makes them prone to sintering and agglomeration during cycling. Using a noble metal Rh-supported HAP system results in high raw material costs and requires high-temperature oxidation pretreatment at 500 °C to establish stable metal-support interactions, making the preparation process complex and only applicable to furfuryl alcohol substrates.

[0011] Secondly, the present invention provides a method for preparing the Ni-Al / HAP-P catalyst, comprising the following steps:

[0012] (1) Sodium hydroxide and phosphate were dissolved in deionized water, and then added dropwise to deionized water along with a soluble calcium salt solution to obtain mixed solution I. After adjusting the pH of the solution, the mixture was stirred to carry out the reaction. After aging, washing, drying and calcination, hydroxyapatite-based HAP carriers were obtained.

[0013] (2) After dissolving nickel salt and aluminum salt in deionized water to obtain a precursor solution, add the HAP support prepared in step (1), stir at a constant temperature to carry out the reaction, filter, wash and purify and dry the reaction, and then reduce with hydrogen to obtain Ni-Al / HAP-P catalyst.

[0014] In step (1), the phosphate is selected from any one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium hypophosphite and sodium dihydrogen phosphate, preferably sodium dihydrogen phosphate; the soluble calcium salt is selected from any one of calcium nitrate, calcium chloride and calcium acetate, preferably calcium nitrate.

[0015] The molar ratio of phosphate to soluble calcium salt is 1:1.6~1.7, preferably 1:1.62~1.68, and most preferably 1:1.64; the concentration of phosphate in mixed solution I is 0.04~0.07 mol / L, and the molar ratio of phosphate to sodium hydroxide is 1:5.0~5.4, preferably 1:5.2; the pH of the solution is adjusted to 8-10. Sodium hydroxide, on the one hand, stabilizes the pH of the reaction system in the weakly alkaline range of 8~10, and on the other hand, dissociates to provide hydroxyl groups, while promoting the conversion of hydrogen phosphate to phosphate.

[0016] The aging temperature is 40~70 ℃ and the time is 10~20 h; the calcination temperature is 450~650 ℃, preferably 500-600 ℃, and the time is 3~5 h.

[0017] In step (2), the molar ratio of nickel ions to aluminum ions in the nickel salt and aluminum salt is 1:1 to 1.5, preferably 1:1.15 to 1.3, and most preferably 1:1.3; the molar ratio of nickel ions to phosphorus ions in the HAP carrier is 1:1.5 to 2.5, preferably 1:2 to 2.3, and most preferably 1:2.2; the temperature of the constant temperature stirring is 40 to 60 °C, and the time is 12 to 16 h.

[0018] The nickel salt is selected from any one of nickel nitrate, nickel chloride, and nickel acetate, preferably nickel nitrate; the aluminum salt is selected from any one of aluminum nitrate, aluminum acetate, and aluminum chloride, preferably aluminum nitrate.

[0019] The hydrogen flow rate for the hydrogen reduction is 30-50 mL / min. During the reduction process, the temperature is first increased at a rate of 5-10 °C / min, the reduction temperature is 400-600 °C, and the reduction time is 4-6 h. Preferably, the hydrogen flow rate is 50 mL / min, the temperature is first increased at a rate of 5 °C / min, the reduction temperature is 500 °C, and the reduction time is 5 h.

[0020] In this preparation method, the HAP support forms a stable hydroxyapatite crystal structure by precisely controlling the Ca / P molar ratio (1.6~1.7:1) and calcination process. Its unique layered and porous structure provides ample loading sites for the active components, while its excellent thermal stability effectively inhibits the sintering of active components at high temperatures, ensuring the structural integrity and activity stability of the catalyst during long-term use. During ion exchange, Ni... 2+ Al 3+ With Ca on the surface of HAP carrier 2+ Directional exchange occurs by adjusting the molar ratio of Ni and Al to control the exchange rate of the two metal ions, preventing a single metal from preferentially occupying the pores and achieving uniform co-loading inside and outside the pores. This achieves both uniform loading of the bimetallic active components and retention of some unexchanged Ca. 2+ This invention utilizes the electron-rich properties of phosphorus atoms in the HAP support framework, without adding any external phosphides, relying solely on the inherent phosphate groups in the HAP lattice, to achieve Ni 2+ Reduced to metallic Ni 0 During the process, the spontaneous generation of Ni-P coordination bonds is induced simultaneously, and the atomic-level construction of the active interface is completed directly in the reduced state. No additional high-temperature oxidation pretreatment step is required, which effectively simplifies the catalyst pretreatment process.

[0021] like Figure 2 As shown, Al 3+ As a Lewis acid site, it can efficiently promote the ring-opening rearrangement reaction of the furan ring; Ca 2+Providing moderately basic sites effectively suppresses furfural self-polymerization and aldehyde-ketone condensation side reactions. The acid-base sites synergistically match the multi-step reaction requirements of furfural hydrogenation to cyclopentanone, significantly improving the selectivity of the target product. Furthermore, the phosphorus element of the support itself is used to perform non-metallic coordination modification on the nickel active sites. On the one hand, the coordination effect of phosphorus restricts Ni particle agglomeration, ensuring high dispersion of Ni active sites and enhancing H2 activation and carbonyl hydrogenation efficiency. On the other hand, this strong interaction effectively avoids phosphorus loss during the reaction, ensuring the long-term stability of the catalyst structure and catalytic performance, ultimately achieving a synergistic improvement in catalytic activity, selectivity, and cycle stability. This invention relies on multiple synergistic coupling mechanisms to generate catalytic effects. A single HAP support or a simple Ni-Al bimetallic component cannot simultaneously achieve all three types of synergistic effects. Only by combining a HAP support with a specific Ca / P ratio with an ion-exchange loaded Ni-Al process can excellent catalytic performance be obtained.

[0022] Thirdly, the present invention also provides the application of the Ni-Al / HAP-P catalyst in the hydrogenation of furfural to cyclopentanone.

[0023] In the above reaction of furfural hydrogenation to synthesize cyclopentanone: the mass fraction of furfural is 8%~12%; the hydrogen pressure is 1~3MPa; the mass of Ni-Al / HAP-P catalyst is 12%~16% of the mass of furfural; the reaction temperature is 130~160 ℃, and the time is 1~3 h.

[0024] A method for synthesizing cyclopentanone by catalytic hydrogenation of furfural using the aforementioned Ni-Al / HAP-P catalyst specifically includes: adding a certain amount of furfural and 12-16% by mass of Ni-Al / HAP catalyst under a hydrogen pressure of 1-3 MPa, using deionized water as a solvent, reacting at 130-160 °C for 1-3 h to obtain cyclopentanone, and after the reaction is completed, recovering the catalyst by centrifugation, and then catalyzing the hydrogenation reaction of furfural again.

[0025] The beneficial effects of this invention are:

[0026] 1. This invention achieves a stable hydroxyapatite structure by precisely controlling the Ca / P molar ratio (1.6~1.7:1) of the HAP support, providing sufficient loading sites for Ni and Al active components and significantly improving the dispersion of active components; simultaneously, it utilizes ion exchange to achieve Ni... 2+ Al 3+ Uniform loading, combined with phosphorus ions and Ni 2+ The stable coordination and binding of Ni effectively inhibits Ni particle agglomeration, enhances H2 activation and furfural carbonyl hydrogenation efficiency, and significantly improves the catalytic activity of the catalyst. The HAP support itself possesses excellent thermal stability, effectively inhibiting the sintering of active components at high temperatures and ensuring the structural integrity of the catalyst during long-term use; simultaneously, Ni…2+ The strong interaction with phosphate ions prevents the loss of phosphorus during the reaction, and unexchanged Ca... 2+ It works synergistically with the support framework to maintain structural stability, significantly improves the catalyst's recyclability, and extends its lifespan.

[0027] 2. This invention achieves synergistic regulation of acid-base sites through ion exchange: Al 3+ As a Lewis acid site, it can efficiently promote the furan ring-opening rearrangement reaction; the residual Ca in the HAP support 2+ Providing moderately alkaline sites effectively blocks furfural self-polymerization and aldehyde-ketone condensation side reactions, preventing polymer adsorption from covering active sites. The acid-base synergistic effect meets the multi-step reaction requirements of furfural hydrogenation to cyclopentanone. The Ni-Al / HAP-P catalyst prepared in this invention is suitable for the one-step hydrogenation of furfural aqueous solutions (with a primary concentration of 8-12 wt%, after simple desulfurization and dust removal) produced by current furfural production enterprises to obtain cyclopentanone. The product is then subjected to low-temperature extraction and distillation to obtain high-purity cyclopentanone. The extracted aqueous solution is recycled for the furfural hydration hydrogenation process to produce cyclopentanone. This catalyst is easily separated and recovered from the product by centrifugation, solving the problems of high water consumption and high separation costs caused by low-concentration feed in existing technologies, and has broad industrial application prospects. Attached Figure Description

[0028] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0029] Figure 1 TEM image of the Ni-Al / HAP-P catalyst prepared in Example 1.

[0030] Figure 2 A schematic diagram of the catalytic reaction mechanism for the hydrogenation of furfural to prepare cyclopentanone. Detailed Implementation

[0031] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0032] Example 1

[0033] A method for preparing a Ni-Al / HAP-P catalyst, the specific steps of which are as follows:

[0034] (1) According to the molar ratio of calcium salt to phosphate of 1.64:1 (i.e., Ca / P molar ratio of 1.64:1), weigh 2.979 g of calcium nitrate (Ca(NO3)2·4H2O), 1.200 g of sodium dihydrogen phosphate (NaH2PO4·2H2O) and 1.600 g of sodium hydroxide (NaOH). Dissolve sodium dihydrogen phosphate and sodium hydroxide in 50 mL of deionized water to prepare a mixed alkaline solution; dissolve calcium nitrate in 50 mL of deionized water to prepare a calcium salt solution. Add both solutions slowly dropwise to a beaker containing 20 mL of deionized water, stirring continuously (300 r / min) to maintain the pH of the system at 9. After the addition is complete, age the mixture at 60 °C for 15 h. Wash the resulting solution with deionized water until neutral, dry at 80 °C for 12 h, and finally calcine at 550 °C for 4 h to obtain the HAP carrier.

[0035] (2) Weigh 1.018 g of nickel nitrate (Ni(NO3)2·6H2O) and 1.707 g of aluminum nitrate (Al(NO3)3·9H2O) according to the ratio of Ni / P=1:2.2 (relying on the phosphorus element of the HAP carrier itself) and Ni / Al=1:1.3, and dissolve them in 30 mL of deionized water to prepare a mixed salt solution. Add 1 g of the HAP carrier obtained in step (1) to the solution under stirring, and stir in a constant temperature environment of 50 ℃ for 14 h to allow Ni to precipitate. 2+ Al 3+ Phosphorus in the support is loaded onto the surface of the support through ion exchange, while the phosphorus in the support reacts with Ni. 2+ Coordination bonds are formed. The mixture is then filtered, washed with deionized water, dried at 80 °C for 12 h, and then placed in a tube furnace. Hydrogen gas is introduced (flow rate 50 mL / min), and the temperature is increased to 500 °C at a rate of 5 °C / min. The temperature is maintained for 5 h for reduction, and after natural cooling, the Ni-Al / HAP-P catalyst is obtained.

[0036] The Ni-Al / HAP-P catalyst prepared in this example was characterized by TEM, and the results are as follows: Figure 1 As shown, the catalyst support is composed of nano-spherical hydroxyapatite particles with a particle size of approximately 50 nm. Ni-Al active species are uniformly dispersed on the surface of the support without obvious metal agglomeration. The catalyst has a porous and rough surface, which can provide a large number of active sites for the hydrogenation reaction.

[0037] Example 2

[0038] A method for preparing a Ni-Al / HAP-P catalyst, the specific steps of which are as follows:

[0039] (1) Weigh 2.906 g of calcium nitrate (Ca(NO3)2·4H2O), 1.200 g of sodium dihydrogen phosphate (NaH2PO4·2H2O) and 1.600 g of sodium hydroxide (NaOH) according to the molar ratio of calcium salt to phosphate of 1.60:1 (i.e., Ca / P molar ratio of 1.60:1). Dissolve sodium dihydrogen phosphate and sodium hydroxide in 50 mL of deionized water to prepare a mixed alkaline solution; dissolve calcium nitrate in 50 mL of deionized water to prepare a calcium salt solution. Add both solutions slowly dropwise to a beaker containing 20 mL of deionized water, stirring continuously (300 r / min) to maintain the pH of the system at 9. After the addition is complete, age the mixture at 60 °C for 15 h. Wash the resulting solution with deionized water until neutral, dry at 80 °C for 12 h, and finally calcine at 550 °C for 4 h to obtain the HAP carrier.

[0040] (2) Weigh 1.018 g of nickel nitrate (Ni(NO3)2·6H2O) and 1.707 g of aluminum nitrate (Al(NO3)3·9H2O) according to the ratio of Ni / P=1:2.2 (relying on the phosphorus element of the HAP carrier itself) and Ni / Al=1:1.3, and dissolve them in 30 mL of deionized water to prepare a mixed salt solution. Add 1 g of the HAP carrier obtained in step (1) to the solution under stirring, and stir in a constant temperature environment of 50 ℃ for 14 h to allow Ni to precipitate. 2+ Al 3+ Phosphorus in the support is loaded onto the surface of the support through ion exchange, while the phosphorus in the support reacts with Ni. 2+ Coordination bonds are formed. The mixture is then filtered, washed with deionized water, dried at 80 °C for 12 h, and then placed in a tube furnace. Hydrogen gas is introduced (flow rate 50 mL / min), and the temperature is increased to 500 °C at a rate of 5 °C / min. The temperature is maintained for 5 h for reduction, and after natural cooling, the Ni-Al / HAP-P catalyst is obtained.

[0041] Example 3

[0042] A method for preparing a Ni-Al / HAP-P catalyst, the specific steps of which are as follows:

[0043] (1) According to the molar ratio of calcium salt to phosphate of 1.68:1 (i.e., Ca / P molar ratio of 1.68:1), weigh 3.052 g of calcium nitrate (Ca(NO3)2·4H2O), 1.200 g of sodium dihydrogen phosphate (NaH2PO4·2H2O) and 1.600 g of sodium hydroxide (NaOH). Dissolve sodium dihydrogen phosphate and sodium hydroxide in 50 mL of deionized water to prepare a mixed alkaline solution; dissolve calcium nitrate in 50 mL of deionized water to prepare a calcium salt solution. Add both solutions slowly dropwise to a beaker containing 20 mL of deionized water, stirring continuously (300 r / min) to maintain the pH of the system at 9. After the addition is complete, age the mixture at 60 °C for 15 h. Wash the resulting solution with deionized water until neutral, dry at 80 °C for 12 h, and finally calcine at 550 °C for 4 h to obtain the HAP carrier.

[0044] (2) Weigh 1.018 g of nickel nitrate (Ni(NO3)2·6H2O) and 1.707 g of aluminum nitrate (Al(NO3)3·9H2O) according to the ratio of Ni / P=1:2.2 (relying on the phosphorus element of the HAP carrier itself) and Ni / Al=1:1.3, and dissolve them in 30 mL of deionized water to prepare a mixed salt solution. Add 1 g of the HAP carrier obtained in step (1) to the solution under stirring, and stir in a constant temperature environment of 50 ℃ for 14 h to allow Ni to precipitate. 2+ Al 3+ Phosphorus in the support is loaded onto the surface of the support through ion exchange, while the phosphorus in the support reacts with Ni. 2+ Coordination bonds are formed. The mixture is then filtered, washed with deionized water, dried at 80 °C for 12 h, and then placed in a tube furnace. Hydrogen gas is introduced (flow rate 50 mL / min), and the temperature is increased to 500 °C at a rate of 5 °C / min. The temperature is maintained for 5 h for reduction, and after natural cooling, the Ni-Al / HAP-P catalyst is obtained.

[0045] Example 4

[0046] A method for preparing a Ni-Al / HAP-P catalyst, the specific steps of which are as follows:

[0047] (1) According to the molar ratio of calcium salt to phosphate of 1.70:1 (i.e., Ca / P molar ratio of 1.70:1), weigh 3.088 g of calcium nitrate (Ca(NO3)2·4H2O), 1.200 g of sodium dihydrogen phosphate (NaH2PO4·2H2O) and 1.600 g of sodium hydroxide (NaOH). Dissolve sodium dihydrogen phosphate and sodium hydroxide in 50 mL of deionized water to prepare a mixed alkaline solution; dissolve calcium nitrate in 50 mL of deionized water to prepare a calcium salt solution. Add both solutions slowly dropwise to a beaker containing 20 mL of deionized water, stirring continuously (300 r / min) to maintain the pH of the system at 9. After the addition is complete, age the mixture at 60 °C for 15 h. Wash the resulting solution with deionized water until neutral, dry at 80 °C for 12 h, and finally calcine at 550 °C for 4 h to obtain the HAP carrier.

[0048] (2) Weigh 1.018 g of nickel nitrate (Ni(NO3)2·6H2O) and 1.707 g of aluminum nitrate (Al(NO3)3·9H2O) according to the ratio of Ni / P=1:2.2 (relying on the phosphorus element of the HAP carrier itself) and Ni / Al=1:1.3, and dissolve them in 30 mL of deionized water to prepare a mixed salt solution. Add 1 g of the HAP carrier obtained in step (1) to the solution under stirring, and stir in a constant temperature environment of 50 ℃ for 14 h to allow Ni to precipitate. 2+ Al 3+ Phosphorus in the support is loaded onto the surface of the support through ion exchange, while the phosphorus in the support reacts with Ni. 2+ Coordination bonds are formed. The mixture is then filtered, washed with deionized water, dried at 80 °C for 12 h, and then placed in a tube furnace. Hydrogen gas is introduced (flow rate 50 mL / min), and the temperature is increased to 500 °C at a rate of 5 °C / min. The temperature is maintained for 5 h for reduction, and after natural cooling, the Ni-Al / HAP-P catalyst is obtained.

[0049] Example 5

[0050] A method for preparing a Ni-Al / HAP-P catalyst, the specific steps of which are as follows:

[0051] (1) According to the molar ratio of calcium salt to phosphate of 1.64:1 (i.e., Ca / P molar ratio of 1.64:1), weigh 2.979 g of calcium nitrate (Ca(NO3)2·4H2O), 0.885 g of ammonium dihydrogen phosphate (NH4H2PO4) and 1.600 g of sodium hydroxide (NaOH). Dissolve sodium dihydrogen phosphate and sodium hydroxide in 50 mL of deionized water to prepare a mixed alkaline solution; dissolve calcium nitrate in 50 mL of deionized water to prepare a calcium salt solution. Add both solutions slowly dropwise to a beaker containing 20 mL of deionized water, stirring continuously (300 r / min) to maintain the pH of the system at 9. After the addition is complete, age the mixture at 60 °C for 15 h. Wash the resulting solution with deionized water until neutral, dry at 80 °C for 12 h, and finally calcine at 550 °C for 4 h to obtain the HAP carrier.

[0052] (2) Weigh 1.018 g of nickel nitrate (Ni(NO3)2·6H2O) and 1.707 g of aluminum nitrate (Al(NO3)3·9H2O) according to the ratio of Ni / P=1:2.2 (relying on the phosphorus element of the HAP carrier itself) and Ni / Al=1:1.3, and dissolve them in 30 mL of deionized water to prepare a mixed salt solution. Add 1 g of the HAP carrier obtained in step (1) to the solution under stirring, and stir in a constant temperature environment of 50 ℃ for 14 h to allow Ni to precipitate. 2+ Al 3+ Phosphorus in the support is loaded onto the surface of the support through ion exchange, while the phosphorus in the support reacts with Ni. 2+ Coordination bonds are formed. The mixture is then filtered, washed with deionized water, dried at 80 °C for 12 h, and then placed in a tube furnace. Hydrogen gas is introduced (flow rate 50 mL / min), and the temperature is increased to 500 °C at a rate of 5 °C / min. The temperature is maintained for 5 h for reduction, and after natural cooling, the Ni-Al / HAP-P catalyst is obtained.

[0053] Example 6

[0054] A method for preparing a Ni-Al / HAP-P catalyst, the specific steps of which are as follows:

[0055] (1) According to the molar ratio of calcium salt to phosphate of 1.64:1 (i.e., Ca / P molar ratio of 1.64:1), weigh 2.979 g of calcium nitrate (Ca(NO3)2·4H2O), 1.016 g of diammonium hydrogen phosphate ((NH4)2HPO4) and 1.600 g of sodium hydroxide (NaOH). Dissolve sodium dihydrogen phosphate and sodium hydroxide in 50 mL of deionized water to prepare a mixed alkaline solution; dissolve calcium nitrate in 50 mL of deionized water to prepare a calcium salt solution. Add both solutions slowly dropwise to a beaker containing 20 mL of deionized water, stirring continuously (300 r / min) to maintain the pH of the system at 9. After the addition is complete, age the mixture at 60 °C for 15 h. Wash the resulting solution with deionized water until neutral, dry at 80 °C for 12 h, and finally calcine at 550 °C for 4 h to obtain the HAP carrier.

[0056] (2) Weigh 1.018 g of nickel nitrate (Ni(NO3)2·6H2O) and 1.707 g of aluminum nitrate (Al(NO3)3·9H2O) according to the ratio of Ni / P=1:2.2 (relying on the phosphorus element of the HAP carrier itself) and Ni / Al=1:1.3, and dissolve them in 30 mL of deionized water to prepare a mixed salt solution. Add 1 g of the HAP carrier obtained in step (1) to the solution under stirring, and stir in a constant temperature environment of 50 ℃ for 14 h to allow Ni to precipitate. 2+ Al 3+ Phosphorus in the support is loaded onto the surface of the support through ion exchange, while the phosphorus in the support reacts with Ni. 2+ Coordination bonds are formed. The mixture is then filtered, washed with deionized water, dried at 80 °C for 12 h, and then placed in a tube furnace. Hydrogen gas is introduced (flow rate 50 mL / min), and the temperature is increased to 500 °C at a rate of 5 °C / min. The temperature is maintained for 5 h for reduction, and after natural cooling, the Ni-Al / HAP-P catalyst is obtained.

[0057] Example 7

[0058] A method for preparing a Ni-Al / HAP-P catalyst, the specific steps of which are as follows:

[0059] (1) According to the molar ratio of calcium salt to phosphate of 1.64:1 (i.e., Ca / P molar ratio of 1.64:1), weigh 2.979 g of calcium nitrate (Ca(NO3)2·4H2O), 0.815 g of sodium hypophosphite (NaH2PO2·H2O) and 1.600 g of sodium hydroxide (NaOH). Dissolve sodium dihydrogen phosphate and sodium hydroxide in 50 mL of deionized water to prepare a mixed alkaline solution; dissolve calcium nitrate in 50 mL of deionized water to prepare a calcium salt solution. Add both solutions slowly dropwise to a beaker containing 20 mL of deionized water, stirring continuously (300 r / min) to maintain the pH of the system at 9. After the addition is complete, age the mixture at 60 °C for 15 h. Wash the resulting solution with deionized water until neutral, dry at 80 °C for 12 h, and finally calcine at 550 °C for 4 h to obtain the HAP carrier.

[0060] (2) Weigh 1.018 g of nickel nitrate (Ni(NO3)2·6H2O) and 1.707 g of aluminum nitrate (Al(NO3)3·9H2O) according to the ratio of Ni / P=1:2.2 (relying on the phosphorus element of the HAP carrier itself) and Ni / Al=1:1.3, and dissolve them in 30 mL of deionized water to prepare a mixed salt solution. Add 1 g of the HAP carrier obtained in step (1) to the solution under stirring, and stir in a constant temperature environment of 50 ℃ for 14 h to allow Ni to precipitate. 2+ Al 3+ Phosphorus in the support is loaded onto the surface of the support through ion exchange, while the phosphorus in the support reacts with Ni. 2+ Coordination bonds are formed. The mixture is then filtered, washed with deionized water, dried at 80 °C for 12 h, and then placed in a tube furnace. Hydrogen gas is introduced (flow rate 50 mL / min), and the temperature is increased to 500 °C at a rate of 5 °C / min. The temperature is maintained for 5 h for reduction, and after natural cooling, the Ni-Al / HAP-P catalyst is obtained.

[0061] Example 8

[0062] A method for preparing a Ni-Al / HAP-P catalyst, the specific steps of which are as follows:

[0063] (1) Weigh out 1.855 g of calcium chloride (CaCl2·2H2O), 1.200 g of sodium dihydrogen phosphate (NaH2PO4·2H2O), and 1.600 g of sodium hydroxide (NaOH) according to the molar ratio of calcium salt to phosphate of 1.64:1 (i.e., Ca / P molar ratio of 1.64:1). Dissolve sodium dihydrogen phosphate and sodium hydroxide in 50 mL of deionized water to prepare a mixed alkaline solution; dissolve calcium nitrate in 50 mL of deionized water to prepare a calcium salt solution. Add both solutions slowly dropwise to a beaker containing 20 mL of deionized water, stirring continuously (300 r / min) to maintain the pH of the system at 9. After the addition is complete, age the mixture at 60 °C for 15 h. Wash the resulting solution with deionized water until neutral, dry at 80 °C for 12 h, and finally calcine at 550 °C for 4 h to obtain the HAP carrier.

[0064] (2) Weigh 1.018 g of nickel nitrate (Ni(NO3)2·6H2O) and 1.707 g of aluminum nitrate (Al(NO3)3·9H2O) according to the ratio of Ni / P=1:2.2 (relying on the phosphorus element of the HAP carrier itself) and Ni / Al=1:1.3, and dissolve them in 30 mL of deionized water to prepare a mixed salt solution. Add 1 g of the HAP carrier obtained in step (1) to the solution under stirring, and stir in a constant temperature environment of 50 ℃ for 14 h to allow Ni to precipitate. 2+ Al 3+ Phosphorus in the support is loaded onto the surface of the support through ion exchange, while the phosphorus in the support reacts with Ni. 2+ Coordination bonds are formed. The mixture is then filtered, washed with deionized water, dried at 80 °C for 12 h, and then placed in a tube furnace. Hydrogen gas is introduced (flow rate 50 mL / min), and the temperature is increased to 500 °C at a rate of 5 °C / min. The temperature is maintained for 5 h for reduction, and after natural cooling, the Ni-Al / HAP-P catalyst is obtained.

[0065] Example 9

[0066] A method for preparing a Ni-Al / HAP-P catalyst, the specific steps of which are as follows:

[0067] (1) Weigh 2.450 g of calcium acetate (Ca(CH3COO)2·H2O), 1.200 g of sodium dihydrogen phosphate (NaH2PO4·2H2O) and 1.600 g of sodium hydroxide (NaOH) according to the molar ratio of calcium salt to phosphate of 1.64:1 (i.e., Ca / P molar ratio of 1.64:1). Dissolve sodium dihydrogen phosphate and sodium hydroxide in 50 mL of deionized water to prepare a mixed alkaline solution; dissolve calcium nitrate in 50 mL of deionized water to prepare a calcium salt solution. Add both solutions slowly dropwise to a beaker containing 20 mL of deionized water, stirring continuously (300 r / min) to maintain the pH of the system at 9. After the addition is complete, age the mixture at 60 °C for 15 h. Wash the resulting solution with deionized water until neutral, dry at 80 °C for 12 h, and finally calcine at 550 °C for 4 h to obtain the HAP carrier.

[0068] (2) Weigh 1.018 g of nickel nitrate (Ni(NO3)2·6H2O) and 1.707 g of aluminum nitrate (Al(NO3)3·9H2O) according to the ratio of Ni / P=1:2.2 (relying on the phosphorus element of the HAP carrier itself) and Ni / Al=1:1.3, and dissolve them in 30 mL of deionized water to prepare a mixed salt solution. Add 1 g of the HAP carrier obtained in step (1) to the solution under stirring, and stir in a constant temperature environment of 50 ℃ for 14 h to allow Ni to precipitate. 2+ Al 3+ Phosphorus in the support is loaded onto the surface of the support through ion exchange, while the phosphorus in the support reacts with Ni. 2+ Coordination bonds are formed. The mixture is then filtered, washed with deionized water, dried at 80 °C for 12 h, and then placed in a tube furnace. Hydrogen gas is introduced (flow rate 50 mL / min), and the temperature is increased to 500 °C at a rate of 5 °C / min. The temperature is maintained for 5 h for reduction, and after natural cooling, the Ni-Al / HAP-P catalyst is obtained.

[0069] Example 10

[0070] A method for preparing a Ni-Al / HAP-P catalyst, the specific steps of which are as follows:

[0071] (1) According to the molar ratio of calcium salt to phosphate of 1.64:1 (i.e., Ca / P molar ratio of 1.64:1), weigh 2.979 g of calcium nitrate (Ca(NO3)2·4H2O), 1.200 g of sodium dihydrogen phosphate (NaH2PO4·2H2O) and 1.600 g of sodium hydroxide (NaOH). Dissolve sodium dihydrogen phosphate and sodium hydroxide in 50 mL of deionized water to prepare a mixed alkaline solution; dissolve calcium nitrate in 50 mL of deionized water to prepare a calcium salt solution. Add both solutions slowly dropwise to a beaker containing 20 mL of deionized water, stirring continuously (300 r / min) to maintain the pH of the system at 9. After the addition is complete, age the mixture at 60 °C for 15 h. Wash the resulting solution with deionized water until neutral, dry at 80 °C for 12 h, and finally calcine at 550 °C for 4 h to obtain the HAP carrier.

[0072] (2) Weigh 1.018 g of nickel nitrate (Ni(NO3)2·6H2O) and 1.313 g of aluminum nitrate (Al(NO3)3·9H2O) according to the ratio of Ni / P=1:2.2 (relying on the phosphorus element of the HAP carrier itself) and Ni / Al=1:1, and dissolve them in 30 mL of deionized water to prepare a mixed salt solution. Add 1 g of the HAP carrier obtained in step (1) to the solution under stirring, and stir in a constant temperature environment of 50 ℃ for 14 h to allow Ni to precipitate. 2+ Al 3+ Phosphorus in the support is loaded onto the surface of the support through ion exchange, while the phosphorus in the support reacts with Ni. 2+ Coordination bonds are formed. The mixture is then filtered, washed with deionized water, dried at 80 °C for 12 h, and then placed in a tube furnace. Hydrogen gas is introduced (flow rate 50 mL / min), and the temperature is increased to 500 °C at a rate of 5 °C / min. The temperature is maintained for 5 h for reduction, and after natural cooling, the Ni-Al / HAP-P catalyst is obtained.

[0073] Example 11

[0074] A method for preparing a Ni-Al / HAP-P catalyst, the specific steps of which are as follows:

[0075] (1) According to the molar ratio of calcium salt to phosphate of 1.64:1 (i.e., Ca / P molar ratio of 1.64:1), weigh 2.979 g of calcium nitrate (Ca(NO3)2·4H2O), 1.200 g of sodium dihydrogen phosphate (NaH2PO4·2H2O) and 1.600 g of sodium hydroxide (NaOH). Dissolve sodium dihydrogen phosphate and sodium hydroxide in 50 mL of deionized water to prepare a mixed alkaline solution; dissolve calcium nitrate in 50 mL of deionized water to prepare a calcium salt solution. Add both solutions slowly dropwise to a beaker containing 20 mL of deionized water, stirring continuously (300 r / min) to maintain the pH of the system at 9. After the addition is complete, age the mixture at 60 °C for 15 h. Wash the resulting solution with deionized water until neutral, dry at 80 °C for 12 h, and finally calcine at 550 °C for 4 h to obtain the HAP carrier.

[0076] (2) Weigh 1.018 g of nickel nitrate (Ni(NO3)2·6H2O) and 1.970 g of aluminum nitrate (Al(NO3)3·9H2O) according to the ratio of Ni / P=1:2.2 (relying on the phosphorus element of the HAP carrier itself) and Ni / Al=1:1.5, and dissolve them in 30 mL of deionized water to prepare a mixed salt solution. Add 1 g of the HAP carrier obtained in step (1) to the solution under stirring, and stir in a constant temperature environment of 50 ℃ for 14 h to allow Ni to precipitate. 2+ Al 3+ Phosphorus in the support is loaded onto the surface of the support through ion exchange, while the phosphorus in the support reacts with Ni. 2+ Coordination bonds are formed. The mixture is then filtered, washed with deionized water, dried at 80 °C for 12 h, and then placed in a tube furnace. Hydrogen gas is introduced (flow rate 50 mL / min), and the temperature is increased to 500 °C at a rate of 5 °C / min. The temperature is maintained for 5 h for reduction, and after natural cooling, the Ni-Al / HAP-P catalyst is obtained.

[0077] Example 12

[0078] A method for preparing a Ni-Al / HAP-P catalyst, the specific steps of which are as follows:

[0079] (1) According to the molar ratio of calcium salt to phosphate of 1.64:1 (i.e., Ca / P molar ratio of 1.64:1), weigh 2.979 g of calcium nitrate (Ca(NO3)2·4H2O), 1.200 g of sodium dihydrogen phosphate (NaH2PO4·2H2O) and 1.600 g of sodium hydroxide (NaOH). Dissolve sodium dihydrogen phosphate and sodium hydroxide in 50 mL of deionized water to prepare a mixed alkaline solution; dissolve calcium nitrate in 50 mL of deionized water to prepare a calcium salt solution. Add both solutions slowly dropwise to a beaker containing 20 mL of deionized water, stirring continuously (300 r / min) to maintain the pH of the system at 9. After the addition is complete, age the mixture at 60 °C for 15 h. Wash the resulting solution with deionized water until neutral, dry at 80 °C for 12 h, and finally calcine at 550 °C for 4 h to obtain the HAP carrier.

[0080] (2) Weigh 1.118 g of nickel nitrate (Ni(NO3)2·6H2O) and 1.707 g of aluminum nitrate (Al(NO3)3·9H2O) according to the ratio of Ni / P=1:2.0 (relying on the phosphorus element of the HAP carrier itself) and Ni / Al=1:1.3, and dissolve them in 30 mL of deionized water to prepare a mixed salt solution. Add 1 g of the HAP carrier obtained in step (1) to the solution under stirring, and stir in a constant temperature environment of 50 ℃ for 14 h to allow Ni to precipitate. 2+ Al 3+ Phosphorus in the support is loaded onto the surface of the support through ion exchange, while the phosphorus in the support reacts with Ni. 2+ Coordination bonds are formed. The mixture is then filtered, washed with deionized water, dried at 80 °C for 12 h, and then placed in a tube furnace. Hydrogen gas is introduced (flow rate 50 mL / min), and the temperature is increased to 500 °C at a rate of 5 °C / min. The temperature is maintained for 5 h for reduction, and after natural cooling, the Ni-Al / HAP-P catalyst is obtained.

[0081] Example 13

[0082] A method for preparing a Ni-Al / HAP-P catalyst, the specific steps of which are as follows:

[0083] (1) According to the molar ratio of calcium salt to phosphate of 1.64:1 (i.e., Ca / P molar ratio of 1.64:1), weigh 2.979 g of calcium nitrate (Ca(NO3)2·4H2O), 1.200 g of sodium dihydrogen phosphate (NaH2PO4·2H2O) and 1.600 g of sodium hydroxide (NaOH). Dissolve sodium dihydrogen phosphate and sodium hydroxide in 50 mL of deionized water to prepare a mixed alkaline solution; dissolve calcium nitrate in 50 mL of deionized water to prepare a calcium salt solution. Add both solutions slowly dropwise to a beaker containing 20 mL of deionized water, stirring continuously (300 r / min) to maintain the pH of the system at 9. After the addition is complete, age the mixture at 60 °C for 15 h. Wash the resulting solution with deionized water until neutral, dry at 80 °C for 12 h, and finally calcine at 550 °C for 4 h to obtain the HAP carrier.

[0084] (2) Weigh 0.895 g of nickel nitrate (Ni(NO3)2·6H2O) and 1.707 g of aluminum nitrate (Al(NO3)3·9H2O) according to the ratio of Ni / P=1:2.5 (relying on the phosphorus element of the HAP carrier itself) and Ni / Al=1:1.3, and dissolve them in 30 mL of deionized water to prepare a mixed salt solution. Add 1 g of the HAP carrier obtained in step (1) to the solution under stirring, and stir in a constant temperature environment of 50 ℃ for 14 h to allow Ni to precipitate. 2+ Al 3+ Phosphorus in the support is loaded onto the surface of the support through ion exchange, while the phosphorus in the support reacts with Ni. 2+ Coordination bonds are formed. The mixture is then filtered, washed with deionized water, dried at 80 °C for 12 h, and then placed in a tube furnace. Hydrogen gas is introduced (flow rate 50 mL / min), and the temperature is increased to 500 °C at a rate of 5 °C / min. The temperature is maintained for 5 h for reduction, and after natural cooling, the Ni-Al / HAP-P catalyst is obtained.

[0085] Example 14

[0086] A method for preparing a Ni-Al / HAP-P catalyst, the specific steps of which are as follows:

[0087] (1) According to the molar ratio of calcium salt to phosphate of 1.64:1 (i.e., Ca / P molar ratio of 1.64:1), weigh 2.979 g of calcium nitrate (Ca(NO3)2·4H2O), 1.200 g of sodium dihydrogen phosphate (NaH2PO4·2H2O) and 1.600 g of sodium hydroxide (NaOH). Dissolve sodium dihydrogen phosphate and sodium hydroxide in 50 mL of deionized water to prepare a mixed alkaline solution; dissolve calcium nitrate in 50 mL of deionized water to prepare a calcium salt solution. Add both solutions slowly dropwise to a beaker containing 20 mL of deionized water, stirring continuously (300 r / min) to maintain the pH of the system at 9. After the addition is complete, age the mixture at 60 °C for 15 h. Wash the resulting solution with deionized water until neutral, dry at 80 °C for 12 h, and finally calcine at 550 °C for 4 h to obtain the HAP carrier.

[0088] (2) Weigh 0.832 g of nickel chloride (NiCl2·6H2O) and 1.707 g of aluminum nitrate (Al(NO3)3·9H2O) according to the ratio of Ni / P=1:2.2 (relying on the phosphorus element of the HAP carrier itself) and Ni / Al=1:1.3, and dissolve them in 30 mL of deionized water to prepare a mixed salt solution. Add 1 g of the HAP carrier obtained in step (1) to the solution under stirring, and stir in a constant temperature environment of 50 ℃ for 14 h to allow Ni to... 2+ Al 3+ Phosphorus in the support is loaded onto the surface of the support through ion exchange, while the phosphorus in the support reacts with Ni. 2+ Coordination bonds are formed. After filtration and washing with deionized water, the catalyst is dried at 80 °C for 12 h and then placed in a tube furnace. Hydrogen gas is introduced (flow rate 50 mL / min), and the temperature is increased to 500 °C at a rate of 5 °C / min. The temperature is maintained for 5 h for reduction, and after natural cooling, the Ni-Al / HAP-P catalyst is obtained.

[0089] Example 15

[0090] A method for preparing a Ni-Al / HAP-P catalyst, the specific steps of which are as follows:

[0091] (1) According to the molar ratio of calcium salt to phosphate of 1.64:1 (i.e., Ca / P molar ratio of 1.64:1), weigh 2.979 g of calcium nitrate (Ca(NO3)2·4H2O), 1.200 g of sodium dihydrogen phosphate (NaH2PO4·2H2O) and 1.600 g of sodium hydroxide (NaOH). Dissolve sodium dihydrogen phosphate and sodium hydroxide in 50 mL of deionized water to prepare a mixed alkaline solution; dissolve calcium nitrate in 50 mL of deionized water to prepare a calcium salt solution. Add both solutions slowly dropwise to a beaker containing 20 mL of deionized water, stirring continuously (300 r / min) to maintain the pH of the system at 9. After the addition is complete, age the mixture at 60 °C for 15 h. Wash the resulting solution with deionized water until neutral, dry at 80 °C for 12 h, and finally calcine at 550 °C for 4 h to obtain the HAP carrier.

[0092] (2) Weigh 0.871 g of nickel acetate (Ni(CH3COO)2·4H2O) and 1.707 g of aluminum nitrate (Al(NO3)3·9H2O) according to the ratio of Ni / P=1:2.2 (relying on the phosphorus element of the HAP carrier itself) and Ni / Al=1:1.3, and dissolve them in 30 mL of deionized water to prepare a mixed salt solution. Add 1 g of the HAP carrier obtained in step (1) to the solution under stirring, and stir in a constant temperature environment of 50 ℃ for 14 h to allow Ni to... 2+ Al 3+ Phosphorus in the support is loaded onto the surface of the support through ion exchange, while the phosphorus in the support reacts with Ni. 2+ Coordination bonds are formed. The mixture is then filtered, washed with deionized water, dried at 80 °C for 12 h, and then placed in a tube furnace. Hydrogen gas is introduced (flow rate 50 mL / min), and the temperature is increased to 500 °C at a rate of 5 °C / min. The temperature is maintained for 5 h for reduction, and after natural cooling, the Ni-Al / HAP-P catalyst is obtained.

[0093] Example 16

[0094] A method for preparing a Ni-Al / HAP-P catalyst, the specific steps of which are as follows:

[0095] (1) According to the molar ratio of calcium salt to phosphate of 1.64:1 (i.e., Ca / P molar ratio of 1.64:1), weigh 2.979 g of calcium nitrate (Ca(NO3)2·4H2O), 1.200 g of sodium dihydrogen phosphate (NaH2PO4·2H2O) and 1.600 g of sodium hydroxide (NaOH). Dissolve sodium dihydrogen phosphate and sodium hydroxide in 50 mL of deionized water to prepare a mixed alkaline solution; dissolve calcium nitrate in 50 mL of deionized water to prepare a calcium salt solution. Add both solutions slowly dropwise to a beaker containing 20 mL of deionized water, stirring continuously (300 r / min) to maintain the pH of the system at 9. After the addition is complete, age the mixture at 60 °C for 15 h. Wash the resulting solution with deionized water until neutral, dry at 80 °C for 12 h, and finally calcine at 550 °C for 4 h to obtain the HAP carrier.

[0096] (2) Weigh 1.018 g of nickel nitrate (Ni(NO3)2·6H2O) and 0.918 g of aluminum acetate (Al(CH3COO)3) according to the ratio of Ni / P=1:2.2 (relying on the phosphorus element of the HAP carrier itself) and Ni / Al=1:1.3, and dissolve them in 30 mL of deionized water to prepare a mixed salt solution. Add 1 g of the HAP carrier obtained in step (1) to the solution under stirring, and stir in a constant temperature environment of 50 ℃ for 14 h to allow Ni to precipitate. 2+ Al 3+ Phosphorus in the support is loaded onto the surface of the support through ion exchange, while the phosphorus in the support reacts with Ni. 2+ Coordination bonds are formed. After filtration and washing with deionized water, the catalyst is dried at 80 °C for 12 h and then placed in a tube furnace. Hydrogen gas is introduced (flow rate 50 mL / min), and the temperature is increased to 500 °C at a rate of 5 °C / min. The temperature is maintained for 5 h for reduction, and after natural cooling, the Ni-Al / HAP-P catalyst is obtained.

[0097] Example 17

[0098] A method for preparing a Ni-Al / HAP-P catalyst, the specific steps of which are as follows:

[0099] (1) According to the molar ratio of calcium salt to phosphate of 1.64:1 (i.e., Ca / P molar ratio of 1.64:1), weigh 2.979 g of calcium nitrate (Ca(NO3)2·4H2O), 1.200 g of sodium dihydrogen phosphate (NaH2PO4·2H2O) and 1.600 g of sodium hydroxide (NaOH). Dissolve sodium dihydrogen phosphate and sodium hydroxide in 50 mL of deionized water to prepare a mixed alkaline solution; dissolve calcium nitrate in 50 mL of deionized water to prepare a calcium salt solution. Add both solutions slowly dropwise to a beaker containing 20 mL of deionized water, stirring continuously (300 r / min) to maintain the pH of the system at 9. After the addition is complete, age the mixture at 60 °C for 15 h. Wash the resulting solution with deionized water until neutral, dry at 80 °C for 12 h, and finally calcine at 550 °C for 4 h to obtain the HAP carrier.

[0100] (2) Weigh 1.018 g of nickel nitrate (Ni(NO3)2·6H2O) and 0.607 g of aluminum chloride (AlCl3) according to the ratio of Ni / P=1:2.2 (relying on the phosphorus element of the HAP carrier itself) and Ni / Al=1:1.3, and dissolve them in 30 mL of deionized water to prepare a mixed salt solution. Add 1 g of the HAP carrier obtained in step (1) to the solution under stirring, and stir in a constant temperature environment of 50 ℃ for 14 h to allow Ni to... 2+ Al 3+ Phosphorus in the support is loaded onto the surface of the support through ion exchange, while the phosphorus in the support reacts with Ni. 2+ Coordination bonds are formed. The mixture is then filtered, washed with deionized water, dried at 80 °C for 12 h, and then placed in a tube furnace. Hydrogen gas is introduced (flow rate 50 mL / min), and the temperature is increased to 500 °C at a rate of 5 °C / min. The temperature is maintained for 5 h for reduction, and after natural cooling, the Ni-Al / HAP-P catalyst is obtained.

[0101] Example 18

[0102] A method for preparing a Ni-Al / HAP-P catalyst, the specific steps of which are as follows:

[0103] (1) According to the molar ratio of calcium salt to phosphate of 1.64:1 (i.e., Ca / P molar ratio of 1.64:1), weigh 2.979 g of calcium nitrate (Ca(NO3)2·4H2O), 1.200 g of sodium dihydrogen phosphate (NaH2PO4·2H2O) and 1.600 g of sodium hydroxide (NaOH). Dissolve sodium dihydrogen phosphate and sodium hydroxide in 50 mL of deionized water to prepare a mixed alkaline solution; dissolve calcium nitrate in 50 mL of deionized water to prepare a calcium salt solution. Add both solutions slowly dropwise to a beaker containing 20 mL of deionized water, stirring continuously (300 r / min) to maintain the pH of the system at 9. After the addition is complete, age the mixture at 60 °C for 15 h. Wash the resulting solution with deionized water until neutral, dry at 80 °C for 12 h, and finally calcine at 550 °C for 4 h to obtain the HAP carrier.

[0104] (2) Weigh 1.018 g of nickel nitrate (Ni(NO3)2·6H2O) and 1.707 g of aluminum nitrate (Al(NO3)3·9H2O) according to the ratio of Ni / P=1:2.2 (relying on the phosphorus element of the HAP carrier itself) and Ni / Al=1:1.3, and dissolve them in 30 mL of deionized water to prepare a mixed salt solution. Add 1 g of the HAP carrier obtained in step (1) to the solution under stirring, and stir in a constant temperature environment of 50 ℃ for 14 h to allow Ni to precipitate. 2+ Al 3+ Phosphorus in the support is loaded onto the surface of the support through ion exchange, while the phosphorus in the support reacts with Ni. 2+ Coordination bonds are formed. The mixture is then filtered, washed with deionized water, dried at 80 °C for 12 h, and then placed in a tube furnace. Hydrogen gas is introduced (flow rate 30 mL / min), and the temperature is increased to 500 °C at a rate of 5 °C / min. The temperature is maintained for 5 h for reduction, and after natural cooling, the Ni-Al / HAP-P catalyst is obtained.

[0105] Example 19

[0106] A method for preparing a Ni-Al / HAP-P catalyst, the specific steps of which are as follows:

[0107] (1) According to the molar ratio of calcium salt to phosphate of 1.64:1 (i.e., Ca / P molar ratio of 1.64:1), weigh 2.979 g of calcium nitrate (Ca(NO3)2·4H2O), 1.200 g of sodium dihydrogen phosphate (NaH2PO4·2H2O) and 1.600 g of sodium hydroxide (NaOH). Dissolve sodium dihydrogen phosphate and sodium hydroxide in 50 mL of deionized water to prepare a mixed alkaline solution; dissolve calcium nitrate in 50 mL of deionized water to prepare a calcium salt solution. Add both solutions slowly dropwise to a beaker containing 20 mL of deionized water, stirring continuously (300 r / min) to maintain the pH of the system at 9. After the addition is complete, age the mixture at 60 °C for 15 h. Wash the resulting solution with deionized water until neutral, dry at 80 °C for 12 h, and finally calcine at 550 °C for 4 h to obtain the HAP carrier.

[0108] (2) Weigh 1.018 g of nickel nitrate (Ni(NO3)2·6H2O) and 1.707 g of aluminum nitrate (Al(NO3)3·9H2O) according to the ratio of Ni / P=1:2.2 (relying on the phosphorus element of the HAP carrier itself) and Ni / Al=1:1.3, and dissolve them in 30 mL of deionized water to prepare a mixed salt solution. Add 1 g of the HAP carrier obtained in step (1) to the solution under stirring, and stir in a constant temperature environment of 50 ℃ for 14 h to allow Ni to precipitate. 2+ Al 3+ Phosphorus in the support is loaded onto the surface of the support through ion exchange, while the phosphorus in the support reacts with Ni. 2+ Coordination bonds are formed. The mixture is then filtered, washed with deionized water, dried at 80 °C for 12 h, and then placed in a tube furnace. Hydrogen gas is introduced (flow rate 40 mL / min), and the temperature is increased to 500 °C at a rate of 5 °C / min. The temperature is maintained for 5 h for reduction, and after natural cooling, the Ni-Al / HAP-P catalyst is obtained.

[0109] Example 20

[0110] A method for preparing a Ni-Al / HAP-P catalyst, the specific steps of which are as follows:

[0111] (1) According to the molar ratio of calcium salt to phosphate of 1.64:1 (i.e., Ca / P molar ratio of 1.64:1), weigh 2.979 g of calcium nitrate (Ca(NO3)2·4H2O), 1.200 g of sodium dihydrogen phosphate (NaH2PO4·2H2O) and 1.600 g of sodium hydroxide (NaOH). Dissolve sodium dihydrogen phosphate and sodium hydroxide in 50 mL of deionized water to prepare a mixed alkaline solution; dissolve calcium nitrate in 50 mL of deionized water to prepare a calcium salt solution. Add both solutions slowly dropwise to a beaker containing 20 mL of deionized water, stirring continuously (300 r / min) to maintain the pH of the system at 9. After the addition is complete, age the mixture at 60 °C for 15 h. Wash the resulting solution with deionized water until neutral, dry at 80 °C for 12 h, and finally calcine at 550 °C for 4 h to obtain the HAP carrier.

[0112] (2) Weigh 1.018 g of nickel nitrate (Ni(NO3)2·6H2O) and 1.707 g of aluminum nitrate (Al(NO3)3·9H2O) according to the ratio of Ni / P=1:2.2 (relying on the phosphorus element of the HAP carrier itself) and Ni / Al=1:1.3, and dissolve them in 30 mL of deionized water to prepare a mixed salt solution. Add 1 g of the HAP carrier obtained in step (1) to the solution under stirring, and stir in a constant temperature environment of 50 ℃ for 14 h to allow Ni to precipitate. 2+ Al 3+ Phosphorus in the support is loaded onto the surface of the support through ion exchange, while the phosphorus in the support reacts with Ni. 2+ Coordination bonds are formed. The mixture is then filtered, washed with deionized water, dried at 80 °C for 12 h, and then placed in a tube furnace. Hydrogen gas is introduced (flow rate 50 mL / min), and the temperature is increased to 400 °C at a rate of 5 °C / min. The temperature is maintained for 5 h for reduction, and after natural cooling, the Ni-Al / HAP-P catalyst is obtained.

[0113] Example 21

[0114] A method for preparing a Ni-Al / HAP-P catalyst, the specific steps of which are as follows:

[0115] (1) According to the molar ratio of calcium salt to phosphate of 1.64:1 (i.e., Ca / P molar ratio of 1.64:1), weigh 2.979 g of calcium nitrate (Ca(NO3)2·4H2O), 1.200 g of sodium dihydrogen phosphate (NaH2PO4·2H2O) and 1.600 g of sodium hydroxide (NaOH). Dissolve sodium dihydrogen phosphate and sodium hydroxide in 50 mL of deionized water to prepare a mixed alkaline solution; dissolve calcium nitrate in 50 mL of deionized water to prepare a calcium salt solution. Add both solutions slowly dropwise to a beaker containing 20 mL of deionized water, stirring continuously (300 r / min) to maintain the pH of the system at 9. After the addition is complete, age the mixture at 60 °C for 15 h. Wash the resulting solution with deionized water until neutral, dry at 80 °C for 12 h, and finally calcine at 550 °C for 4 h to obtain the HAP carrier.

[0116] (2) Weigh 1.018 g of nickel nitrate (Ni(NO3)2·6H2O) and 1.707 g of aluminum nitrate (Al(NO3)3·9H2O) according to the ratio of Ni / P=1:2.2 (relying on the phosphorus element of the HAP carrier itself) and Ni / Al=1:1.3, and dissolve them in 30 mL of deionized water to prepare a mixed salt solution. Add 1 g of the HAP carrier obtained in step (1) to the solution under stirring, and stir in a constant temperature environment of 50 ℃ for 14 h to allow Ni to precipitate. 2+ Al 3+ Phosphorus in the support is loaded onto the surface of the support through ion exchange, while the phosphorus in the support reacts with Ni. 2+ Coordination bonds are formed. The mixture is then filtered, washed with deionized water, dried at 80 °C for 12 h, and then placed in a tube furnace. Hydrogen gas is introduced (flow rate 50 mL / min), and the temperature is increased to 600 °C at a rate of 5 °C / min. The temperature is maintained for 5 h for reduction, and after natural cooling, the Ni-Al / HAP-P catalyst is obtained.

[0117] Comparative Example 1

[0118] A method for preparing a catalyst for the hydrogenation of furfural to cyclopentanone, the specific steps of which are as follows:

[0119] (1) According to the molar ratio of calcium salt to phosphate of 1.64:1 (i.e., Ca / P molar ratio of 1.64:1), weigh 2.979 g of calcium nitrate (Ca(NO3)2·4H2O), 1.200 g of sodium dihydrogen phosphate (NaH2PO4·2H2O) and 1.600 g of sodium hydroxide (NaOH). Dissolve sodium dihydrogen phosphate and sodium hydroxide in 50 mL of deionized water to prepare a mixed alkaline solution; dissolve calcium nitrate in 50 mL of deionized water to prepare a calcium salt solution. Add both solutions slowly dropwise to a beaker containing 20 mL of deionized water, stirring continuously (300 r / min) to maintain the pH of the system at 9. After the addition is complete, age the mixture at 60 °C for 15 h. Wash the resulting solution with deionized water until neutral, dry at 80 °C for 12 h, and finally calcine at 550 °C for 4 h to obtain the HAP carrier.

[0120] (2) Weigh 1.018 g of nickel nitrate (Ni(NO3)2·6H2O) according to the Ni / P ratio of 1:2.2 (based on the phosphorus element of the HAP carrier itself), dissolve it in 30 mL of deionized water to prepare a salt solution. Add 1 g of the HAP carrier obtained in step (1) to the solution under stirring, and stir in a constant temperature environment of 50 ℃ for 14 h to allow Ni to precipitate. 2+ Phosphorus in the support is loaded onto the surface of the support through ion exchange, while the phosphorus in the support reacts with Ni. 2+ Coordination bonds are formed. The mixture is then filtered, washed with deionized water, dried at 80 °C for 12 h, and then placed in a tube furnace. Hydrogen gas is introduced (flow rate 50 mL / min), and the temperature is increased to 500 °C at a rate of 5 °C / min. The temperature is maintained for 5 h for reduction, and after natural cooling, the desired catalyst is obtained.

[0121] Comparative Example 2

[0122] A method for preparing a catalyst for the hydrogenation of furfural to cyclopentanone, the specific steps of which are as follows:

[0123] (1) According to the molar ratio of calcium salt to phosphate of 1.64:1 (i.e., Ca / P molar ratio of 1.64:1), weigh 2.979 g of calcium nitrate (Ca(NO3)2·4H2O), 1.200 g of sodium dihydrogen phosphate (NaH2PO4·2H2O) and 1.600 g of sodium hydroxide (NaOH). Dissolve sodium dihydrogen phosphate and sodium hydroxide in 50 mL of deionized water to prepare a mixed alkaline solution; dissolve calcium nitrate in 50 mL of deionized water to prepare a calcium salt solution. Add both solutions slowly dropwise to a beaker containing 20 mL of deionized water, stirring continuously (300 r / min) to maintain the pH of the system at 9. After the addition is complete, age the mixture at 60 °C for 15 h. Wash the resulting solution with deionized water until neutral, dry at 80 °C for 12 h, and finally calcine at 550 °C for 4 h to obtain the HAP carrier.

[0124] (2) Weigh 1.707 g of aluminum nitrate (Al(NO3)3·9H2O), dissolve it in 30 mL of deionized water to prepare a salt solution. Add 1 g of the HAP carrier obtained in step (1) to this solution while stirring, and stir at 50 ℃ for 14 h to allow the Al... 3+ The catalyst was loaded onto the support surface via ion exchange. After filtration and washing with deionized water, it was dried at 80 °C for 12 h and then placed in a tube furnace. Hydrogen gas was introduced (flow rate 50 mL / min), and the temperature was increased to 500 °C at a rate of 5 °C / min. The temperature was maintained for 5 h for reduction, and after natural cooling, the desired catalyst was obtained.

[0125] Comparative Example 3

[0126] A method for preparing a catalyst for the hydrogenation of furfural to cyclopentanone, the specific steps of which are as follows:

[0127] (1) According to the molar ratio of calcium salt to phosphate of 1.64:1 (i.e., Ca / P molar ratio of 1.64:1), weigh 2.979 g of calcium nitrate (Ca(NO3)2·4H2O), 1.200 g of sodium dihydrogen phosphate (NaH2PO4·2H2O) and 1.600 g of sodium hydroxide (NaOH). Dissolve sodium dihydrogen phosphate and sodium hydroxide in 50 mL of deionized water to prepare a mixed alkaline solution; dissolve calcium nitrate in 50 mL of deionized water to prepare a calcium salt solution. Add both solutions slowly dropwise to a beaker containing 20 mL of deionized water, stirring continuously (300 r / min) to maintain the pH of the system at 9. After the addition is complete, age the mixture at 60 °C for 15 h. Wash the resulting solution with deionized water until neutral, dry at 80 °C for 12 h, and finally calcine at 550 °C for 4 h to obtain the HAP carrier.

[0128] (2) Weigh 1.018 g of nickel nitrate (Ni(NO3)2·6H2O) and 3.937 g of aluminum nitrate nonahydrate (Al(NO3)3·9H2O) according to the ratio of Ni / P=1:2.2 (relying on the phosphorus element of the HAP carrier itself) and Ni / Al=1:3.0, and dissolve them in 30 mL of deionized water to prepare a mixed salt solution. Add 1 g of the HAP carrier obtained in step (1) to the solution under stirring, and stir in a constant temperature environment of 50 ℃ for 14 h to allow Ni to precipitate. 2+ Al 3+ Phosphorus in the support is loaded onto the surface of the support through ion exchange, while the phosphorus in the support reacts with Ni. 2+ Coordination bonds are formed. The mixture is then filtered, washed with deionized water, dried at 80 °C for 12 h, and then placed in a tube furnace. Hydrogen gas is introduced (flow rate 50 mL / min), and the temperature is increased to 500 °C at a rate of 5 °C / min. The temperature is maintained for 5 h for reduction, and after natural cooling, the desired catalyst is obtained.

[0129] Comparative Example 4

[0130] A method for preparing a catalyst for the hydrogenation of furfural to cyclopentanone, the specific steps of which are as follows:

[0131] (1) Weigh 2.979 g of calcium nitrate (Ca(NO3)2·4H2O), 1.200 g of sodium dihydrogen phosphate (NaH2PO4·2H2O), and 1.600 g of sodium hydroxide (NaOH) according to the molar ratio of calcium salt to phosphate of 1.64:1 (i.e., Ca / P molar ratio of 1.64:1). Dissolve sodium dihydrogen phosphate and sodium hydroxide in 50 mL of deionized water to prepare a mixed alkaline solution; dissolve calcium nitrate in 50 mL of deionized water to prepare a calcium salt solution. Add both solutions slowly dropwise to a beaker containing 20 mL of deionized water, stirring continuously (300 r / min) to maintain the pH of the system at 9. After the addition is complete, age the mixture at 60 °C for 15 h. Wash the resulting solution with deionized water until neutral, dry at 80 °C for 12 h, and finally calcine at 550 °C for 4 h to obtain the HAP support, which is the desired catalyst.

[0132] Comparative Example 5

[0133] A method for preparing a catalyst for the hydrogenation of furfural to cyclopentanone, the specific steps of which are as follows:

[0134] (1) 2.0 g of pseudoboehmite was calcined at 550 °C for 4 h to obtain γ-Al2O3 support;

[0135] (2) Weigh 1.018 g of nickel nitrate (Ni(NO3)2·6H2O) and 1.707 g of aluminum nitrate (Al(NO3)3·9H2O) according to the ratio of Ni / P=1:2.2 (relying on the phosphorus element of the HAP support itself) and Ni / Al=1:1.3, and dissolve them in 30 mL of deionized water to prepare a mixed salt solution. Add 1 g of the γ-Al2O3 support obtained in step (1) to the solution under stirring, and stir in a constant temperature environment of 50 ℃ for 14 h. Then filter and wash with deionized water, dry at 80 ℃ for 12 h, and place in a tube furnace, introduce hydrogen (flow rate 50 mL / min), heat to 500 ℃ at a rate of 5 ℃ / min, keep at the temperature for 5 h for reduction, and after natural cooling, obtain the desired catalyst.

[0136] Comparative Example 6

[0137] A method for preparing a catalyst for the hydrogenation of furfural to cyclopentanone, the specific steps of which are as follows:

[0138] (1) According to the molar ratio of calcium salt to phosphate of 1.64:1 (i.e., Ca / P molar ratio of 1.64:1), weigh 2.979 g of calcium nitrate (Ca(NO3)2·4H2O), 1.200 g of sodium dihydrogen phosphate (NaH2PO4·2H2O) and 1.600 g of sodium hydroxide (NaOH). Dissolve sodium dihydrogen phosphate and sodium hydroxide in 50 mL of deionized water to prepare a mixed alkaline solution; dissolve calcium nitrate in 50 mL of deionized water to prepare a calcium salt solution. Add both solutions slowly dropwise to a beaker containing 20 mL of deionized water, stirring continuously (300 r / min) to maintain the pH of the system at 9. After the addition is complete, age the mixture at 60 °C for 15 h. Wash the resulting solution with deionized water until neutral, dry at 80 °C for 12 h, and finally calcine at 550 °C for 4 h to obtain the HAP carrier.

[0139] (2) According to the ratio of Ni / P=1:2.2 (relying on the phosphorus element of the HAP support itself) and Ni / Al=1:1.3, 1.018 g of nickel nitrate (Ni(NO3)2·6H2O) and 1.707 g of aluminum nitrate (Al(NO3)3·9H2O) were weighed and dissolved in 30 mL of deionized water to prepare two salt solutions. The HAP support was first impregnated with nickel nitrate solution, dried, and then impregnated with aluminum nitrate solution. After the two impregnation steps, the catalyst was obtained by drying and reduction.

[0140] Comparative Example 7

[0141] A method for preparing a catalyst for the hydrogenation of furfural to cyclopentanone, the specific steps of which are as follows:

[0142] (1) Weigh 3.267 g of calcium nitrate tetrahydrate, 1.200 g of sodium dihydrogen phosphate dihydrate and 1.600 g of sodium hydroxide according to the molar ratio of calcium salt to phosphate salt of 1.80:1 (i.e., Ca / P molar ratio of 1.80:1). Dissolve sodium dihydrogen phosphate dihydrate and sodium hydroxide in 50 mL of deionized water to prepare a mixed alkaline solution; dissolve calcium nitrate tetrahydrate in 50 mL of deionized water to prepare a calcium salt solution. Add both solutions slowly dropwise to a beaker containing 20 mL of deionized water, stirring continuously (300 r / min) to maintain the pH of the system at 9. After the addition is complete, age the mixture at 60 °C for 15 h. Wash the resulting solution with deionized water until neutral, dry at 80 °C for 12 h, and finally calcine at 550 °C for 4 h to obtain the HAP carrier.

[0143] (2) Weigh 1.018 g of nickel nitrate (Ni(NO3)2·6H2O) and 1.707 g of aluminum nitrate (Al(NO3)3·9H2O) according to the ratio of Ni / P=1:2.2 (relying on the phosphorus element of the HAP carrier itself) and Ni / Al=1:1.3, and dissolve them in 30 mL of deionized water to prepare a mixed salt solution. Add 1 g of the HAP carrier obtained in step (1) to the solution under stirring, and stir in a constant temperature environment of 50 ℃ for 14 h to allow Ni to precipitate. 2+ Al 3+ Phosphorus in the support is loaded onto the surface of the support through ion exchange, while the phosphorus in the support reacts with Ni. 2+ Coordination bonds are formed. The mixture is then filtered, washed with deionized water, dried at 80 °C for 12 h, and then placed in a tube furnace. Hydrogen gas is introduced (flow rate 50 mL / min), and the temperature is increased to 500 °C at a rate of 5 °C / min. The temperature is maintained for 5 h for reduction, and after natural cooling, the desired catalyst is obtained.

[0144] Comparative Example 8

[0145] A method for preparing a catalyst for the hydrogenation of furfural to cyclopentanone, the specific steps of which are as follows:

[0146] (1) Weigh 2.722 g of calcium nitrate tetrahydrate, 1.200 g of sodium dihydrogen phosphate dihydrate and 1.600 g of sodium hydroxide according to the molar ratio of calcium salt to phosphate salt of 1.50:1 (i.e., Ca / P molar ratio of 1.50:1). Dissolve sodium dihydrogen phosphate dihydrate and sodium hydroxide in 50 mL of deionized water to prepare a mixed alkaline solution; dissolve calcium nitrate tetrahydrate in 50 mL of deionized water to prepare a calcium salt solution. Add both solutions slowly dropwise to a beaker containing 20 mL of deionized water, stirring continuously (300 r / min) to maintain the pH of the system at 9. After the addition is complete, age the mixture at 60 °C for 15 h. Wash the resulting solution with deionized water until neutral, dry at 80 °C for 12 h, and finally calcine at 550 °C for 4 h to obtain the HAP carrier.

[0147] (2) Weigh 1.018 g of nickel nitrate (Ni(NO3)2·6H2O) and 1.707 g of aluminum nitrate (Al(NO3)3·9H2O) according to the ratio of Ni / P=1:2.2 (relying on the phosphorus element of the HAP carrier itself) and Ni / Al=1:1.3, and dissolve them in 30 mL of deionized water to prepare a mixed salt solution. Add 1 g of the HAP carrier obtained in step (1) to the solution under stirring, and stir in a constant temperature environment of 50 ℃ for 14 h to allow Ni to precipitate. 2+ Al 3+ Phosphorus in the support is loaded onto the surface of the support through ion exchange, while the phosphorus in the support reacts with Ni. 2+ Coordination bonds are formed. The mixture is then filtered, washed with deionized water, dried at 80 °C for 12 h, and then placed in a tube furnace. Hydrogen gas is introduced (flow rate 50 mL / min), and the temperature is increased to 500 °C at a rate of 5 °C / min. The temperature is maintained for 5 h for reduction, and after natural cooling, the desired catalyst is obtained.

[0148] Comparative Example 9

[0149] A method for preparing a catalyst for the hydrogenation of furfural to cyclopentanone, the specific steps of which are as follows:

[0150] (1) According to the molar ratio of calcium salt to phosphate of 1.64:1 (i.e., Ca / P molar ratio of 1.64:1), weigh 2.979 g of calcium nitrate (Ca(NO3)2·4H2O), 1.200 g of sodium dihydrogen phosphate (NaH2PO4·2H2O) and 1.600 g of sodium hydroxide (NaOH). Dissolve sodium dihydrogen phosphate and sodium hydroxide in 50 mL of deionized water to prepare a mixed alkaline solution; dissolve calcium nitrate in 50 mL of deionized water to prepare a calcium salt solution. Add both solutions slowly dropwise to a beaker containing 20 mL of deionized water, stirring continuously (300 r / min) to maintain the pH of the system at 9. After the addition is complete, age the mixture at 60 °C for 15 h. Wash the resulting solution with deionized water until neutral, dry at 80 °C for 12 h, and finally calcine at 550 °C for 4 h to obtain the HAP carrier.

[0151] (2) Take 1 g of the HAP carrier obtained in step (1), treat it with 0.1 mol / L dilute hydrochloric acid at 60 ℃ for 2 h to remove phosphorus, wash until neutral and dry; weigh 1.018 g of nickel nitrate (Ni(NO3)2·6H2O) and 1.707 g of aluminum nitrate (Al(NO3)3·9H2O) according to the ratio of Ni / P=1:2.2 (relying on the phosphorus element of the HAP carrier itself) and Ni / Al=1:1.3, dissolve them in 30 mL of deionized water to prepare a mixed salt solution, and add 0.128 g of diammonium hydrogen phosphate to the mixed salt solution. Add the treated HAP carrier to the solution under stirring, and stir in a constant temperature environment of 50 ℃ for 14 h to allow Ni to precipitate. 2+ Al 3+ Phosphorus in the support is loaded onto the surface of the support through ion exchange, while the phosphorus in the support reacts with Ni. 2+ Coordination bonds are formed. After filtration and washing with deionized water, the product is dried at 80 °C for 12 h and then placed in a tube furnace. Hydrogen gas is introduced (flow rate 50 mL / min), and the temperature is increased to 500 °C at a rate of 5 °C / min. The temperature is maintained for 5 h for reduction, and after natural cooling, the desired Ni-Al / HAP-P(O) catalyst is obtained.

[0152] Comparative Example 10

[0153] A method for preparing a catalyst for the hydrogenation of furfural to cyclopentanone, the specific steps of which are as follows:

[0154] (1) According to the molar ratio of calcium salt to phosphate of 1.64:1 (i.e., Ca / P molar ratio of 1.64:1), weigh 2.979 g of calcium nitrate (Ca(NO3)2·4H2O), 1.200 g of sodium dihydrogen phosphate (NaH2PO4·2H2O) and 1.600 g of sodium hydroxide (NaOH). Dissolve sodium dihydrogen phosphate and sodium hydroxide in 50 mL of deionized water to prepare a mixed alkaline solution; dissolve calcium nitrate in 50 mL of deionized water to prepare a calcium salt solution. Add both solutions slowly dropwise to a beaker containing 20 mL of deionized water, stirring continuously (300 r / min) to maintain the pH of the system at 9. After the addition is complete, age the mixture at 60 °C for 15 h. Wash the resulting solution with deionized water until neutral, dry at 80 °C for 12 h, and finally calcine at 900 °C for 4 h to obtain the HAP carrier.

[0155] (2) Weigh 1.018 g of nickel nitrate (Ni(NO3)2·6H2O) and 1.707 g of aluminum nitrate (Al(NO3)3·9H2O) according to the ratio of Ni / P=1:2.2 (relying on the phosphorus element of the HAP carrier itself) and Ni / Al=1:1.3, and dissolve them in 30 mL of deionized water to prepare a mixed salt solution. Add 1 g of the HAP carrier obtained in step (1) to the solution under stirring, and stir in a constant temperature environment of 50 ℃ for 14 h to allow Ni to precipitate. 2+ Al 3+ Phosphorus in the support is loaded onto the surface of the support through ion exchange, while the phosphorus in the support reacts with Ni. 2+ Coordination bonds are formed. The mixture is then filtered, washed with deionized water, dried at 80 °C for 12 h, and then placed in a tube furnace. Hydrogen gas is introduced (flow rate 50 mL / min), and the temperature is increased to 500 °C at a rate of 5 °C / min. The temperature is maintained for 5 h for reduction, and after natural cooling, the desired catalyst is obtained.

[0156] Example of implementation effect 1

[0157] The catalytic hydrogenation of cyclopentanone was performed using the Ni-Al / HAP-P catalyst prepared in Example 1, as detailed below:

[0158] First, the optimal reaction conditions for the catalytic reaction were investigated for different catalyst dosages, reaction temperatures, pressures, and times, as detailed below:

[0159] 1) The effect of different catalyst dosages on the reaction activity is shown in Table 1:

[0160] Table 1. Effect of different dosages of the Ni-Al / HAP-P catalyst prepared in Example 1 on the reaction activity.

[0161]

[0162] As shown in Table 1, there is an optimal catalyst dosage of 0.39 g, at which the product yield is the highest. Too low a dosage results in insufficient reaction activity, while too high a dosage leads to poor mass transfer and aggravated side reactions, both of which will reduce the yield of the target product.

[0163] 2) The effect of different reaction temperatures on the reactivity is shown in Table 2:

[0164] Table 2. Effect of different temperatures on the reaction activity of the Ni-Al / HAP-P catalyst prepared in Example 1.

[0165]

[0166] As shown in Table 2, the product yield first increases and then decreases with increasing reaction temperature, and 150 °C is the optimal reaction temperature for this system. The reaction rate is limited at low temperatures and side reactions increase at high temperatures, both of which are unfavorable for the formation of cyclopentanone.

[0167] 3) The effect of different reaction pressures on the reaction activity is shown in Table 3:

[0168] Table 3. Effect of different pressures on the reaction activity of the Ni-Al / HAP-P catalyst prepared in Example 1.

[0169]

[0170] As shown in Table 3, the product yield first increases significantly and then decreases slightly with increasing hydrogen pressure. 2 MPa is the optimal hydrogen pressure for this reaction. Low pressure results in insufficient hydrogen supply and limited conversion, while high pressure easily generates byproducts, both of which are unfavorable for the formation of cyclopentanone.

[0171] 4) The effect of different reaction times on the reactivity is shown in Table 4:

[0172] Table 4. Effect of different reaction times on the reaction activity of the Ni-Al / HAP-P catalyst prepared in Example 1.

[0173]

[0174] As shown in Table 4, the product yield first increases and then decreases with the extension of reaction time, with 2 h being the optimal reaction time. Too short a reaction time results in insufficient conversion of raw materials, while too long a reaction time increases the number of side reactions, both of which will reduce the yield of cyclopentanone.

[0175] Therefore, the optimal reaction conditions were determined to be 150℃, 2MPa, 2h, and catalyst dosage of 13% of the raw material.

[0176] The specific steps are as follows: Weigh 3 g of furfural, 27 g of deionized water, and 0.39 g (13 wt% furfural) catalyst and add them to a 70 mL reactor (with a magnetic stir bar already placed). Seal the apparatus, purge with hydrogen three times, and then purge with 2 MPa of hydrogen gas. Allow the temperature to rise to 150 ℃ and react for 2 h. After the reaction is complete, remove the reaction product and analyze its composition using gas chromatography. The conversion rate of furfural is 99.31%, and the selectivity of cyclopentanone is 98.97%.

[0177] Example 2 of implementation results

[0178] The Ni-Al / HAP-P catalysts prepared in Examples 1-21 and the catalysts prepared in Comparative Examples 1-11 were used to synthesize cyclopentanone via catalytic hydrogenation. The specific results are shown in Table 5.

[0179] Table 5 Catalytic results of the catalysts prepared in Examples 1-21 and Comparative Examples 1-11

[0180]

[0181] As shown in Table 5, compared to methods involving single active metals Ni or Al, replacing the HAP support with γ-Al₂O₃ to eliminate phosphorus coordination, using a stepwise impregnation method to load bimetals, deviating the preferred Ca / P molar ratio, using an external phosphorus source to replace the in-situ coordination of phosphorus in the support itself, employing a post-phosphorus treatment process, and high-temperature calcination of the support, this invention achieves simultaneous Ni / P coordination by precisely controlling the Ca / P molar ratio of the HAP support and the calcination process, combined with a one-step ion exchange method. 2+ Al 3+ The uniform loading of the bimetallic component and the in-situ coordination modification of the Ni active sites by the phosphorus element of the support enable the catalyst to have a triple synergistic effect: Lewis acid sites promote furan ring opening and rearrangement, moderate basic sites inhibit furfural self-polymerization and aldehyde-ketone condensation side reactions, and phosphorus coordination stabilizes Ni nanoparticles to inhibit their thermal aggregation. This allows for high-precision control of the reaction pathway and the stability of the active sites, significantly improving the selectivity of cyclopentanone and the structural stability of the catalyst. The yield of cyclopentanone from furfural hydrogenation is as high as 98.29%.

[0182] Example of implementation effect 3

[0183] The Ni-Al / HAP-P catalyst prepared in Example 1 was used to test its catalytic cycle performance, as detailed below:

[0184] (1) Catalyst recovery and treatment

[0185] Add 30 mL of ethanol to the reaction product mixture in Example 1, mix well, centrifuge and wash 3 times, and dry in an oven at 80 °C for 12 h to obtain the recovered Ni-Al / HAP-P catalyst.

[0186] (2) Cyclic performance test of the recovered catalyst

[0187] The recovered catalyst was used to repeat the experiment of catalytic hydrogenation of furfural to cyclopentanone five times, with the reaction conditions being the same as in Example 1. The performance of the catalyst in the five cycles is shown in Table 6.

[0188] Table 6. Results of the cycle performance test of the recovered catalyst

[0189]

[0190] As shown in Table 6, the Ni-Al / HAP-P catalyst provided by this invention can maintain a cyclopentanone yield of over 93% after 5 cycles in the catalytic hydrogenation of furfural to cyclopentanone. This demonstrates that the bimetallic hydroxyapatite-supported nickel-based catalyst prepared by this invention, which utilizes the in-situ coordination modification of the support's own phosphorus element, has excellent cycle life.

[0191] In summary, the Ni-Al / HAP-P catalyst prepared in this invention for the catalytic hydrogenation of furfural to cyclopentanone utilizes phosphorus from the HAP support framework for non-metallic in-situ coordination modification of the nickel active sites. On one hand, the coordination effect of phosphorus restricts the thermal aggregation of Ni particles during high-temperature reduction and the reaction process, ensuring high dispersion of the Ni active sites and enhancing H2 dissociation activation and carbonyl hydrogenation efficiency. On the other hand, the strong electronic interaction between phosphorus and nickel effectively inhibits the loss of phosphorus species under reaction conditions, maintaining the long-term stability of the active center structure and significantly improving the catalyst's cycle life. Simultaneously, Al is introduced through ion exchange. 3+ As a Lewis acid site, it efficiently promotes the ring-opening rearrangement reaction of the furan ring; the Ca retained in the support 2 + The catalyst provides moderately basic sites, effectively suppressing furfural self-polymerization and aldehyde-ketone condensation side reactions. The bimetallic acid-base sites synergistically match the multi-step reaction requirements of furfural hydrogenation to cyclopentanone, significantly improving the selectivity of the target product. The catalyst prepared in this invention exhibits excellent activity and stability under mild reaction conditions, is easy to separate, and has good reusability, showing promising application prospects in industry.

[0192] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A Ni-Al / HAP-P catalyst, characterized in that: The Ni-Al / HAP-P catalyst mainly consists of a hydroxyapatite HAP support, and active metal Ni and auxiliary metal Al supported on the surface of the HAP support.

2. The method for preparing the Ni-Al / HAP-P catalyst according to claim 1, characterized in that, Includes the following steps: (1) Sodium hydroxide and phosphate were dissolved in deionized water, and then added dropwise to deionized water along with a soluble calcium salt solution to obtain mixed solution I. After adjusting the pH of the solution, the mixture was stirred to carry out the reaction. After aging, washing, drying and calcination, hydroxyapatite-based HAP carriers were obtained. (2) After dissolving nickel salt and aluminum salt in deionized water to obtain a precursor solution, add the HAP support prepared in step (1), stir at a constant temperature to carry out the reaction, filter, wash and purify and dry the reaction, and then reduce with hydrogen to obtain Ni-Al / HAP-P catalyst.

3. The preparation method according to claim 2, characterized in that: In step (1), the phosphate is selected from any one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium hypophosphite, and sodium dihydrogen phosphate; the soluble calcium salt is selected from any one of calcium nitrate, calcium chloride, and calcium acetate.

4. The preparation method according to claim 3, characterized in that: In step (1), the molar ratio of phosphate to soluble calcium salt is 1:1.6~1.7, the concentration of phosphate in mixed solution I is 0.04~0.07 mol / L, and the molar ratio of phosphate to sodium hydroxide is 1:5.0~5.4; the pH of the solution is adjusted to 8-10.

5. The preparation method according to claim 4, characterized in that: In step (1), the aging temperature is 40~70℃ and the time is 10~20 h; the calcination temperature is 450~650℃ and the time is 3~5 h.

6. The preparation method according to claim 5, characterized in that: In step (2), the molar ratio of nickel ions to aluminum ions in the nickel salt and aluminum salt is 1:1 to 1.5, and the molar ratio of nickel ions to phosphorus ions in the HAP carrier is 1:1.5 to 2.5; the temperature of the constant temperature stirring is 40 to 60 ℃, and the time is 12 to 16 h.

7. The preparation method according to claim 6, characterized in that: In step (2), the nickel salt is selected from any one of nickel nitrate, nickel chloride, and nickel acetate; the aluminum salt is selected from any one of aluminum nitrate, aluminum acetate, and aluminum chloride.

8. The preparation method according to claim 7, characterized in that: In step (2), the reduction temperature of hydrogen reduction is 400~600 ℃ and the reduction time is 4~6 h.

9. The application of the Ni-Al / HAP-P catalyst according to claim 1 in the hydrogenation of furfural to cyclopentanone.

10. The application according to claim 9, characterized in that: In the above reaction of furfural hydrogenation to cyclopentanone, the mass fraction of furfural is 8%~12%; the hydrogen pressure is 1~3 MPa; the mass of Ni-Al / HAP-P catalyst is 12%~16% of the mass of furfural; the reaction temperature is 130~160 ℃; and the reaction time is 1~3 h.

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