A supported nici cu alloy nanoparticle catalyst, method of preparation and use thereof in the catalytic hydrogenation of alkenes or aldehydes

Abstract

The application belongs to the technical field of hydrogenation catalysts, and discloses a supported NiCu alloy nanoparticle catalyst, a preparation method and application of the catalyst in catalytic hydrogenation of alkenes or aldehydes. The active center of the catalyst is uniformly dispersed NiCu alloy nanoparticles, and the carrier is a P-doped magnesium-aluminum layered double metal oxide with a structural formula of NiCu-MgAl-P-LDO. The molar ratio of divalent metal ions M 2+ and trivalent metal ions Al 3+ in the catalyst is (1-4):1, the molar ratio of Ni 2+ , Cu 2+ , Mg 2+ in the divalent metal ions is (1-4):(1-4):(1-3), and the P element is conducive to the dispersion of the NiCu alloy nanoparticles. The catalyst of the application unexpectedly improves the catalytic performance and stability of the catalyst through double optimization of the structure and composition of the catalyst. The catalyst of the application is used for selective catalytic hydrogenation of alpha-methylstyrene, has low price, high conversion rate and selectivity, and stable performance. The catalyst of the application is used for catalytic hydrogenation of hydroxyl pivalaldehyde, can efficiently and mildly convert the hydroxyl pivalaldehyde into pentyleneglycol, avoid the further reaction of the pentyleneglycol, and has high selectivity. The catalyst of the application can stably catalyze the hydrogenation of isooctene aldehyde into isooctanol under high temperature and high pressure, and has high conversion rate, selectivity and stability.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of hydrogenation catalysts, and particularly relates to a supported NiCu alloy nanoparticle catalyst, a preparation method thereof and use thereof in catalytic hydrogenation of alkenes or aldehydes. BACKGROUND

[0002] Catalytic hydrogenation of alkenes or aldehydes is a basic and key process in organic chemistry, which converts C=C or C=O double bonds into saturated carbon compounds, and has a profound impact on industrial manufacturing. For example, the hydrogenation of α-methylstyrene to produce cumene is a typical catalytic hydrogenation reaction of C=C double bonds. The product not only plays a crucial role in the production of phenol and acetone, but also has a wide range of applications in polycarbonate, epoxy resin, detergent, nylon, plastic, herbicide and other fields. Acetone, as an important industrial solvent, also plays a key role in the industries of explosives, plastics, rubber, fiber, leather making and paint spraying. However, during the hydrogenation of α-methylstyrene, the hydrogenation of aromatic hydrocarbons inevitably occurs as a side reaction, which not only reduces the selectivity of the reaction, but also affects the purity of the product. Therefore, developing a catalyst that can efficiently and selectively hydrogenate while minimizing the loss of aromatic hydrocarbons has become a technical problem that needs to be solved in the chemical industry.

[0003] The process of converting hydroxypivaldehyde into pivalyl alcohol by hydrogenation of the C=O double bond is a key step in the production of polyesters, polyurethanes and alkyd resins, and pivalyl alcohol has significant industrial value in the synthesis of lubricants, hydraulic fluids, pharmaceuticals and other fields. However, existing catalysts have deficiencies in stability and hydrogenation performance, which limit the improvement of pivalyl alcohol purity, directly affecting the quality of the final product.

[0004] Isooctene aldehyde, as a compound containing C=C and C=O double bonds, its full hydrogenation product iso-octanol has a wide range of applications in plasticizers, chemical industry, plastic production, solvent extraction and chemical synthesis. The efficiency of the hydrogenation reaction is directly related to the quality and yield of the product. Currently, noble metal catalysts are commonly used in industry to improve the activity of the hydrogenation reaction, but this method is costly and not conducive to the promotion of large-scale industrial applications.

[0005] In patent document CN109092295A, a catalyst preparation method for loading Pd on alumina is introduced. This method shows extremely high conversion rate and selectivity in the catalytic hydrogenation of α-methylstyrene to produce cumene. However, the limited nature and high cost of noble metal resources are still the main factors that restrict its widespread application.

[0006] Patent document EP394842A1 proposes a Ni-containing catalyst system that provides a new solution for the catalytic hydrogenation of aldehydes by adding elements such as Cu, Zr, Mo, etc. However, the activity of this catalyst system decreases over time, which may affect its efficiency for long-term applications.

[0007] The CuCr catalyst described in patent document RO94237B1 improves the activity of isooctene aldehyde hydrogenation by adding Ni as an auxiliary agent, but the chromium compounds used in this catalyst may cause environmental pollution, which becomes a major obstacle to its application process.

[0008] Although existing catalysts have shown advantages in specific fields, their limitations in terms of cost, activity, stability, and environmental impact, etc. need to be overcome through technological innovation to achieve more extensive, efficient, and environmentally friendly industrial applications. SUMMARY

[0009] To solve the problems of the prior art, the present application provides a supported NiCu alloy nanoparticle hydrogenation catalyst, the active center of which is uniformly dispersed NiCu alloy nanoparticles, and the carrier is P-doped MgAl layered double oxide (Layered Double Oxide, abbreviated as LDO). The uniformly dispersed NiCu alloy nanoparticles not only significantly increase the number of active sites, but also greatly promote the adsorption and activation of reactants, thereby accelerating the speed of chemical reactions; at the same time, the layered structure of MgAl-LDO creates a unique microenvironment, and the interlayer space provides the necessary physical isolation for NiCu nanoparticles, effectively preventing direct contact and agglomeration between particles; further, the P-doped in the carrier not only unpredictably increases the dispersity of NiCu alloy nanoparticles, but also significantly enhances the anti-sintering ability of the active center NiCu nanoparticles. This double optimization of structure and composition ensures that the catalyst of the present application exhibits mild reaction conditions, high catalytic activity, and long service life when catalyzing the hydrogenation of alkenes or aldehydes.

[0010] The catalyst of this invention can stably catalyze the selective hydrogenation of α-methylstyrene to cumene without over-hydrogenation. The conversion rate of α-methylstyrene can reach up to 100%, and the selectivity of cumene can reach up to 99.91%. The catalyst shows no significant deactivation after 8 hours at 120°C and 0.95 MPa. When used in the catalytic hydrogenation of hydroxypentylaldehyde, the catalyst of this invention can yield high-purity neopentyl glycol. At 130°C and 3.5 MPa, the conversion rate of hydroxypentylaldehyde can reach up to 100%, and the selectivity of neopentyl glycol can reach up to 100%. It also exhibits good anti-coking ability, and shows no significant deactivation after 8 hours. In the catalytic hydrogenation of isoocteneal to isooctyl alcohol, the catalyst of this invention can achieve a conversion rate of isoocteneal up to 100% and a selectivity of isooctyl alcohol up to 100% at 130°C and 3.5 MPa. It also exhibits good anti-coking ability, and shows no significant deactivation after 8 hours.

[0011] This invention provides a supported NiCu alloy nanoparticle hydrogenation catalyst, characterized in that the active center of the catalyst is uniformly dispersed NiCu alloy nanoparticles, the support is a magnesium-aluminum layered bimetallic oxide doped with P, with the structural formula NiCu-MgAl-P-LDO, and the catalyst contains divalent metal ions M 2+ and trivalent metal ions Al 3+ The molar ratio is (1-4):1, and the Ni in the divalent metal ions 2+ Cu 2+ Mg 2+ The molar ratio is (1-4):(1-4):(1-3).

[0012] Furthermore, in the XRD pattern, the catalyst clearly showed characteristic diffraction peaks of the NiCu alloy at 2θ angles of 43.5° and 50.9°, which were between the characteristic diffraction peaks of Ni (44.6°, 51.2°) and Cu (43.3°, 50.5°), indicating that NiCu formed an alloy structure. The catalyst also clearly showed characteristic diffraction peaks of the MgAl-LDO composite oxide at 2θ angles of 36.3° and 63.1°, which were between the characteristic diffraction peaks of MgO (37.1°, 62.7°) and Al2O3 (34.9°, 67.3°), indicating that a magnesium-aluminum layered bimetallic oxide structure was formed, with no other peaks.

[0013] Furthermore, transmission electron microscopy revealed that the active centers of the catalyst are uniformly dispersed NiCu alloy nanoparticles with a particle size of 12.4 nm, and these active centers are uniformly dispersed on the MgAl-LDO support.

[0014] Further, the ICP test shows that the content of the active center Cu is 10-60wt% and the content of Ni is 10-60wt% based on the mass of the whole catalyst.

[0015] Further preferably, the content of Cu in the active component is 15-40wt% and the content of elemental Ni is 20-50wt% based on the total weight of the catalyst.

[0016] The present application also provides a preparation method of the aforementioned catalyst, which comprises the following steps:

[0017] Step 1: preparing a P-doped hydrotalcite precursor by using a co-precipitation method

[0018] 5-30mmol of Ni(NO3)2·6H2O, 15-30mmol of Cu(NO3)2·3H2O, 15-50mmol of Mg(NO3)2·6H2O and 10-40mmol of Al(NO3)3·9H2O are weighed and put into a beaker containing 200mL of deionized water, and stirred until completely dissolved to obtain a salt solution A; urea is weighed and put into a beaker containing 200-500mL of deionized water, and stirred until completely dissolved to obtain a urea solution B; a phosphate salt is dissolved in 100-300mL of deionized water to obtain a phosphate salt solution C, which is placed in a 1000mL four-necked flask and stirred at room temperature at a stirring rate of 100-500r / min, the salt solution A and the urea solution B are simultaneously poured into the four-necked flask, 10-50mL of formamide is added first, and then 10-50mL of a methanol solution is added, and after stirring uniformly, the temperature is raised to 70-120℃ at a temperature raising rate of 0.5-1℃ / min, and then crystallized at constant temperature for 12-36h, and then centrifuged to obtain a precipitate D, which is stirred and dissolved and dispersed in 400-800mL of deionized water with a glass rod, the temperature is raised to 60-80℃ at a temperature raising rate of 1-10℃ / min, and then crystallized at constant temperature for 10-30h, and then a solid sample E is obtained by reduced pressure filtration, washed with deionized water until neutral, and then dried in an oven at 70-100℃ for 8-20h, and then ground after cooling to obtain a catalyst precursor, a P-containing copper-nickel-magnesium-aluminum hydrotalcite powder, denoted as NiCuMgAl-P-LDHs, and dried and stored;

[0019] Step 2: preparing a P-doped and uniformly dispersed NiCu alloy nanoparticle catalyst

[0020] The catalyst precursor powder is calcined under nitrogen atmosphere, then switched to hydrogen atmosphere for heat preservation, and then switched to nitrogen atmosphere, and the doped P uniformly dispersed NiCu alloy nanoparticle catalyst, recorded as NiCu-MgAl-P-LDO, is obtained after cooling to room temperature.

[0021] Further, in step 1, the phosphate is disodium hydrogen phosphate, and the concentration of the phosphate solution C is 0.01-0.1 mmol / L.

[0022] Further, in step 1, in the urea solution, the concentration of urea is 0.6-7 mol / L.

[0023] Further, in step 2, during the calcination process, the first time is placed under nitrogen atmosphere at a heating rate of 1-10 ℃ / min from room temperature to 400-800 ℃.

[0024] Further, in step 2, under the hydrogen atmosphere, the temperature is kept at 400-800 ℃ for 2-5 h, and then immediately switched to nitrogen atmosphere to cool to room temperature.

[0025] The application also provides a use of the aforementioned supported NiCu alloy nanoparticle hydrogenation catalyst in the preparation of isopropylbenzene by selective catalytic hydrogenation of alpha-methylstyrene in liquid phase, which specifically comprises the following steps: taking the catalyst, 20-40 mesh granulation, and loading into a reaction tube, the reaction tube is loaded into a high-pressure fixed bed reactor, H2 is introduced for pretreatment, the H2 flow rate is 25-150 mL / min / g, and the temperature is maintained at 200-800 ℃ for 1-3 h; cooling to 50-200 ℃ for catalytic reaction, setting the reaction pressure to 0.1-2 MPa, introducing the reaction liquid into the high-pressure fixed bed reactor, and carrying out catalytic reaction in the catalyst bed, the reaction liquid is a mixture of alpha-methylstyrene and isopropylbenzene, the hydrogen is an equilibrium gas, and the reaction liquid volume space velocity is set to 1-10 h -1 ; using gas chromatography for quantitative analysis of the product, the conversion rate of alpha-methylstyrene can be up to 100%, and the selectivity of isopropylbenzene can be up to 99.91%.

[0026] Further, the volume ratio of alpha-methylstyrene to isopropylbenzene in the reaction liquid is (1-9):1.

[0027] Further, the volume ratio of hydrogen to reaction liquid is (100-150):1.

[0028] Further, the H2 enters the reaction tube through the gas path, and the reaction liquid enters the reaction tube through the liquid path by a high-pressure liquid pump, and finally the gas and liquid converge in one way, flowing through the catalyst bed.

[0029] The application also provides a use of the aforementioned supported NiCu alloy nanoparticle hydrogenation catalyst in a reaction of preparing neopentyl glycol by catalytically hydrogenating hydroxyl neopentanal in a liquid phase, specifically comprising the following steps: taking the catalyst, granulating to 20-40 meshes, loading into a reaction tube, loading the reaction tube into a high-pressure fixed bed reactor, pre-treating by passing H2, H2 flow rate is 25-150 mL / min / g, maintaining at 200-800 DEG C for 1-3 h; cooling to 80-200 DEG C for catalytic reaction, setting the reaction pressure to 0.5-5 MPa, passing the reaction liquid into the high-pressure fixed bed reactor, and performing catalytic reaction in the catalyst bed layer, the reaction liquid is a mixed liquid of hydroxyl neopentanal and neopentyl glycol, the hydrogen is balance gas, and the reaction liquid volume space velocity is set to 1-10 h -1 ; performing quantitative analysis on the product by using gas chromatography, and calculating that the conversion rate of hydroxyl neopentanal is up to 100%, and the selectivity of neopentyl glycol is up to 100%.

[0030] Further, the volume ratio of hydroxyl neopentanal to neopentyl glycol in the reaction liquid is (1-9):1.

[0031] Further, the volume ratio of hydrogen to reaction liquid is (100-150):1.

[0032] Further, the H2 enters the reaction tube through a gas path, and the reaction liquid enters the reaction tube through a liquid path by using a high-pressure liquid pump, and finally gas and liquid converge in one way and flow through the catalyst bed layer.

[0033] The application also provides a use of the aforementioned supported NiCu alloy nanoparticle hydrogenation catalyst in a reaction of preparing isooctyl alcohol by hydrogenating isooctene aldehyde, specifically comprising the following steps: taking the catalyst, granulating to 20-40 meshes, loading into a reaction tube, loading the reaction tube into a high-pressure fixed bed reactor, pre-treating by passing H2, H2 flow rate is 25-150 mL / min / g, maintaining at 200-800 DEG C for 1-3 h; cooling to 100-200 DEG C for catalytic reaction, setting the reaction pressure to 1-5 MPa, passing the reaction liquid into the high-pressure fixed bed reactor, and performing catalytic reaction in the catalyst bed layer, the reaction liquid is a mixed liquid of isooctene aldehyde and isooctyl alcohol, the hydrogen is balance gas, and the reaction liquid volume space velocity is set to 1-10 h -1 ; performing quantitative analysis on the product by using gas chromatography, and calculating that the conversion rate of isooctene aldehyde is up to 100%, and the selectivity of isooctyl alcohol is up to 100%.

[0034] Further, the volume ratio of isooctene aldehyde to isooctyl alcohol in the reaction liquid is (1-9):1.

[0035] Further, the volume ratio of hydrogen to reaction liquid is (100-150):1.

[0036] Further, the H2 enters the reaction tube through a gas path, and the reaction liquid enters the reaction tube through a liquid path by a high-pressure liquid pump, and finally the gas and liquid converge and flow through the catalyst bed.

[0037] The beneficial effects of the present application are as follows:

[0038] 1. The catalyst of the present application adopts a co-precipitation method, uses uniformly dispersed NiCu alloy nanoparticles as the active component, uses MgAl-LDO as the carrier, and a small amount of P is doped in the carrier, and the catalyst exhibits excellent performance in liquid-phase hydrogenation reaction; the P plays the role of a dispersant, and unexpectedly uniformly disperses the active component NiCu alloy nanoparticles on the surface of the MgAl-LDO carrier, and unexpectedly improves the stability and selectivity of the catalyst.

[0039] 2. The catalyst of the present application also has unexpected technical effects when applied in a specific reaction field, the present application controls the dispersity of the active component NiCu alloy nanoparticles, so that they are uniformly dispersed on the surface of the MgAl-LDO carrier, and unexpectedly improves the conversion rate of the reactants and the selectivity of the main product at high temperature and high pressure, and unexpectedly shows good anti-coking ability, so that the conversion rate and the selectivity can be improved at the same time, and the catalyst also has the excellent quality of not being deactivated by coking with reaction heat.

[0040] 3. The catalyst of the present application can be obtained by directly reducing a hydrotalcite precursor, the preparation method is simple, no noble metal is used, and the raw material source of the catalyst precursor is extensive and low in cost, so that the preparation cost of the catalyst is greatly reduced, and the catalyst has excellent catalytic performance, good economic benefit and social benefit.

[0041] In summary, the catalyst of the present application has the advantages of high activity, high stability, high selectivity and good anti-coking ability, and these advantages make the catalyst of the present application have a wide application prospect in liquid-phase hydrogenation reaction; at the same time, the preparation method of the catalyst of the present application is simple and low in cost, which is beneficial to large-scale production and popularization, therefore, the catalyst of the present application has important significance for the chemical industry and environmental protection industry. BRIEF DESCRIPTION OF DRAWINGS

[0042] Figures 1-3 TEM images of catalysts 1-3 in examples 1-3, respectively

[0043] Figure 4 XRD images of catalysts 1-3 in examples 1-3 DETAILED DESCRIPTION

[0044] The specific embodiments of the present application are described in detail below. It should be understood that the specific embodiments described herein are merely illustrative and explanatory in nature and are not intended to limit the application.

[0045] Example 1

[0046] Step 1: Preparation of a P-doped hydrotalcite precursor by coprecipitation

[0047] Accurately weigh 15 mmol of Ni(NO3)2·6H2O, 15 mmol of Cu(NO3)2·3H2O, 30 mmol of Mg(NO3)2·6H2O and 20 mmol of Al(NO3)3·9H2O into a beaker containing 200 mL of deionized water, stir until completely dissolved to obtain salt solution A; accurately weigh 540 mmol of urea into a beaker containing 200 mL of deionized water, stir until completely dissolved to obtain urea solution B; accurately weigh 0.006 mmol of disodium hydrogen phosphate into 100 mL of deionized water to obtain phosphate solution C, place the phosphate solution C in a 1000 mL four-necked flask, stir at room temperature, the stirring rate is 300 r / min, pour the salt solution A and the urea solution B into the four-necked flask at the same time, first add 50 mL of formamide, then add 50 mL of methanol solution, after stirring uniformly, keep the temperature rising rate at 0.5 ℃ / min to 90 ℃, constant temperature crystallization for 24 h, then centrifuge to obtain precipitate D, stir the precipitate with a glass rod, dissolve and disperse in 600 mL of deionized water, the temperature is raised to 80 ℃, the temperature rising rate is 2 ℃ / min, constant temperature crystallization for 12 h, then obtain solid sample E by reduced pressure filtration, wash with deionized water until neutral, then dry the solid sample E in a 70 ℃ oven for 12 h, cool and grind to obtain a catalyst precursor, P-containing copper-nickel-magnesium-aluminum hydrotalcite powder, marked as Ni1Cu1MgAl-P-LDHs, dry storage;

[0048] Step 2: Preparation of a P-doped and uniformly dispersed NiCu alloy nanoparticle catalyst

[0049] Place the catalyst precursor in a nitrogen atmosphere and heat to 600 ℃ at a temperature rising rate of 2 ℃ / min, then switch to a hydrogen atmosphere and keep for 4 h, then switch to a nitrogen atmosphere, and then cool to room temperature to obtain a uniformly dispersed NiCu alloy nanoparticle catalyst 1, marked as Ni1Cu1-MgAl-P-LDO.

[0050] Example 2

[0051] Step 1: Preparation of a P-doped hydrotalcite precursor by coprecipitation

[0052] Accurately take 6 mmol of Ni(NO3)2·6H2O, 24 mmol of Cu(NO3)2·3H2O, 30 mmol of Mg(NO3)2·6H2O and 20 mmol of Al(NO3)3·9H2O, put them into a beaker containing 200 mL of deionized water, stir until completely dissolved, to obtain salt solution A; accurately take 540 mmol of urea into a beaker containing 200 mL of deionized water, stir until completely dissolved, to obtain urea solution B; accurately take 0.006 mmol of disodium hydrogen phosphate into 100 mL of deionized water to obtain phosphate solution C, put the phosphate solution C into a 1000 mL four-necked flask, stir at room temperature, the stirring rate is 300 r / min, pour the salt solution A and the urea solution B into the four-necked flask at the same time, first add 50 mL of formamide, then add 50 mL of methanol solution, after stirring uniformly, keep the temperature rising rate at 0.5 ℃ / min to 90 ℃, constant temperature crystallization for 24 h, then centrifugation to obtain precipitate D, stir the precipitate with a glass rod, dissolve and disperse in 600 mL of deionized water, the temperature is raised to 80 ℃, the temperature rising rate is 2 ℃ / min, constant temperature crystallization for 12 h, then obtain solid sample E by reduced pressure filtration, wash with deionized water until neutral, then dry the solid sample E in a 70 ℃ oven for 12 h, cool and grind to obtain a catalyst precursor, P-containing copper nickel magnesium aluminum hydrotalcite powder, marked as Ni1Cu4MgAl-P-LDHs, dry storage;

[0053] Step 2: preparation of P-doped uniformly dispersed NiCu alloy nanoparticle catalyst

[0054] Put the catalyst precursor powder into a nitrogen atmosphere, heat to 600 ℃ at a temperature rising rate of 2 ℃ / min, then switch to a hydrogen atmosphere and keep for 4 h, then switch to a nitrogen atmosphere, and after cooling to room temperature, obtain a P-doped uniformly dispersed NiCu alloy nanoparticle catalyst 2, marked as Ni1Cu4-MgAl-P-LDO.

[0055] Example 3

[0056] Step 1: preparation of P-doped hydrotalcite precursor by coprecipitation method

[0057] Accurately take 10 mmol of Ni(NO3)2·6H2O, 20 mmol of Cu(NO3)2·3H2O, 30 mmol of Mg(NO3)2·6H2O and 20 mmol of Al(NO3)3·9H2O, put them into a beaker containing 200 mL of deionized water, stir until completely dissolved, to obtain salt solution A; accurately take 540 mmol of urea into a beaker containing 200 mL of deionized water, stir until completely dissolved, to obtain urea solution B; accurately take 0.006 mmol of disodium hydrogen phosphate into 100 mL of deionized water to obtain phosphate solution C, put the phosphate solution C into a 1000 mL four-necked flask, stir at room temperature, the stirring rate is 300 r / min, pour the salt solution A and the urea solution B into the four-necked flask at the same time, first add 50 mL of formamide, then add 50 mL of methanol solution, after stirring uniformly, keep the temperature rising rate at 0.5 ℃ / min to 90 ℃, constant temperature crystallization for 24 h, then centrifugation to obtain precipitate D, stir the precipitate with a glass rod, dissolve and disperse in 600 mL of deionized water, the temperature is raised to 80 ℃, the temperature rising rate is 2 ℃ / min, constant temperature crystallization for 12 h, then obtain solid sample E by reduced pressure filtration, wash with deionized water until neutral, then dry the solid sample E in a 70 ℃ oven for 12 h, cool and grind to obtain a catalyst precursor, P-containing copper nickel magnesium aluminum hydrotalcite powder, marked as Ni1Cu2MgAl-P-LDHs, dry storage;

[0058] Step 2: Preparation of P-doped uniformly dispersed NiCu alloy nanoparticle catalyst

[0059] Put the catalyst precursor powder into a nitrogen atmosphere, heat to 600 ℃ at a temperature rising rate of 2 ℃ / min, then switch to a hydrogen atmosphere and keep for 4 h, then switch to a nitrogen atmosphere, and after cooling to room temperature, obtain a P-doped uniformly dispersed NiCu alloy nanoparticle catalyst 3, marked as Ni1Cu2-MgAl-P-LDO.

[0060] Comparative Example 1

[0061] Step 1: Preparation of hydrotalcite precursor by coprecipitation method

[0062] Accurately weigh 15 mmol of Ni(NO3)2·6H2O, 15 mmol of Cu(NO3)2·3H2O, 30 mmol of Mg(NO3)2·6H2O and 20 mmol of Al(NO3)3·9H2O, put them into a beaker containing 200 mL of deionized water, stir until completely dissolved to obtain salt solution A; accurately weigh 540 mmol of urea into a beaker containing 200 mL of deionized water, stir until completely dissolved to obtain urea solution B; pour the salt solution A and the urea solution B into a 1000 mL four-necked flask at the same time and add 100 mL of deionized water, first add 50 mL of formamide, then add 50 mL of methanol solution, stir uniformly, then raise the temperature to 90℃ at a rate of 0.5℃ / min, keep constant temperature for 24 h, then centrifuge to obtain precipitate D, stir the precipitate with a glass rod, dissolve and disperse in 600 mL of deionized water, raise the temperature to 80℃ at a rate of 2℃ / min, keep constant temperature for 12 h, then obtain solid sample E by reduced pressure suction filtration, wash with deionized water until neutral, then dry the solid sample E in a 70℃ oven for 12 h, cool and grind to obtain a catalyst precursor, copper nickel magnesium aluminum hydrotalcite powder, marked as Ni1Cu1MgAl-LDHs, dry storage;

[0063] Step 2: Preparation of NiCu alloy nanoparticle catalyst

[0064] Put the catalyst precursor powder into a nitrogen atmosphere and raise the temperature to 600℃ at a rate of 2℃ / min, then switch to a hydrogen atmosphere and keep for 4 h, then switch to a nitrogen atmosphere, and then reduce to room temperature to obtain a catalyst 4 loaded with NiCu alloy nanoparticles, marked as Ni1Cu1-MgAl-LDO.

[0065] Comparative Example 2

[0066] Step 1: Preparation of hydrotalcite precursor by coprecipitation method

[0067] Accurately weigh 6 mmol of Ni(NO3)2·6H2O, 24 mmol of Cu(NO3)2·3H2O, 30 mmol of Mg(NO3)2·6H2O and 20 mmol of Al(NO3)3·9H2O, put them into a beaker containing 200 mL of deionized water, stir until completely dissolved, to obtain salt solution A; accurately weigh 540 mmol of urea into a beaker containing 200 mL of deionized water, stir until completely dissolved, to obtain urea solution B; pour the salt solution A and the urea solution B into a 1000 mL four-necked flask at the same time and add 100 mL of deionized water, first add 50 mL of formamide, then add 50 mL of methanol solution, stir uniformly, then raise the temperature to 90℃ at a rate of 0.5℃ / min, keep constant temperature for 24 h, then centrifuge to obtain precipitate D, stir the precipitate with a glass rod, dissolve and disperse in 600 mL of deionized water, raise the temperature to 80℃ at a rate of 2℃ / min, keep constant temperature for 12 h, then obtain solid sample E by reduced pressure suction filtration, wash with deionized water until neutral, then dry the solid sample E in a 70℃ oven for 12 h, cool and grind to obtain a catalyst precursor, copper nickel magnesium aluminum hydrotalcite powder, marked as Ni1Cu4MgAl-LDHs, dry storage;

[0068] Step 2: Preparation of NiCu alloy nanoparticle catalyst

[0069] Put the catalyst precursor powder into a nitrogen atmosphere and raise the temperature to 600℃ at a rate of 2℃ / min, then switch to a hydrogen atmosphere and keep for 4 h, then switch to a nitrogen atmosphere, and after cooling to room temperature, obtain a catalyst loaded with NiCu alloy nanoparticles 5, marked as Ni1Cu4-MgAl-LDO.

[0070] Comparative Example 3

[0071] Step 1: Preparation of hydrotalcite precursor by coprecipitation method

[0072] Accurately weigh 10 mmol of Ni(NO3)2·6H2O, 20 mmol of Cu(NO3)2·3H2O, 30 mmol of Mg(NO3)2·6H2O and 20 mmol of Al(NO3)3·9H2O into a beaker containing 200 mL of deionized water, stir until completely dissolved to obtain salt solution A; accurately weigh 540 mmol of urea into a beaker containing 200 mL of deionized water, stir until completely dissolved to obtain urea solution B; pour the salt solution A and the urea solution B into a 1000 mL four-necked flask at the same time and add 100 mL of deionized water, first add 50 mL of formamide, then add 50 mL of methanol solution, stir uniformly, then raise the temperature to 90℃ at a rate of 0.5℃ / min, keep constant temperature for 24 h, then centrifuge to obtain precipitate D, stir the precipitate with a glass rod, dissolve and disperse in 600 mL of deionized water, raise the temperature to 80℃ at a rate of 2℃ / min, keep constant temperature for 12 h, then obtain solid sample E by reduced pressure suction filtration, wash with deionized water until neutral, then dry the solid sample E in a 70℃ oven for 12 h, cool and grind to obtain a catalyst precursor, copper nickel magnesium aluminum hydrotalcite powder, marked as Ni1Cu2MgAl-LDHs, dry storage;

[0073] Step 2: Preparation of NiCu alloy nanoparticle catalyst

[0074] The catalyst precursor powder is placed in a nitrogen atmosphere and heated to 600℃ at a rate of 2℃ / min, then switched to a hydrogen atmosphere for 4 h, then switched to a nitrogen atmosphere, and then cooled to room temperature to obtain a catalyst loaded with NiCu alloy nanoparticles, marked as Ni1Cu2-MgAl-LDO.

[0075] Comparative Example 4

[0076] Step 1: Preparation of phosphate aqueous solution impregnated hydrotalcite precursor by coprecipitation method

[0077] Accurately weigh 15 mmol of Ni(NO3)2·6H2O, 15 mmol of Cu(NO3)2·3H2O, 30 mmol of Mg(NO3)2·6H2O and 20 mmol of Al(NO3)3·9H2O, and put them into a beaker containing 200 mL of deionized water, and stir until completely dissolved to obtain a salt solution A; accurately weigh 540 mmol of urea into a beaker containing 200 mL of deionized water, and stir until completely dissolved to obtain a urea solution B; pour the salt solution A and the urea solution B into a 1000 mL four-necked flask at the same time, and add 100 mL of deionized water, first add 50 mL of formamide, then add 50 mL of methanol solution, stir uniformly, and then heat to 90℃ at a heating rate of 0.5℃ / min, and then keep constant temperature for 24 h, and then centrifuge to obtain a precipitate D, and then stir the precipitate with a glass rod, and dissolve and disperse it in 600 mL of deionized water, and then heat to 80℃ at a heating rate of 2℃ / min, and then keep constant temperature for 12 h, and then obtain a solid sample E by reduced pressure filtration, and then wash it with deionized water until neutral, and then dry the solid sample E in a 70℃ oven for 12 h, and then grind after cooling to obtain a copper-nickel-magnesium-aluminum hydrotalcite powder; accurately weigh 0.006 mmol of disodium hydrogen phosphate into 100 mL of deionized water to obtain a phosphate solution C, and then immerse the phosphate solution C in the copper-nickel-magnesium-aluminum hydrotalcite powder by a preliminary wetting method to obtain an immersion product, which is recorded as Ni1Cu1MgAl / P-LDHs, and then dry and store;

[0078] Step 2: Preparation of P-impregnated NiCu alloy nanoparticle catalyst

[0079] Put the immersion product into a nitrogen atmosphere, heat to 600℃ at a heating rate of 2℃ / min, then switch to a hydrogen atmosphere and keep constant temperature for 4 h, and then switch to a nitrogen atmosphere, and then obtain a catalyst 7 loaded with NiCu alloy nanoparticles after cooling to room temperature, which is recorded as Ni1Cu1-MgAl / P-LDO.

[0080] Comparative Example 5

[0081] Step 1: Preparation of hydrotalcite precursor impregnated with aqueous phosphate solution by coprecipitation method

[0082] Accurately weigh 6 mmol of Ni(NO3)2·6H2O, 24 mmol of Cu(NO3)2·3H2O, 30 mmol of Mg(NO3)2·6H2O and 20 mmol of Al(NO3)3·9H2O, put them into a beaker containing 200 mL of deionized water, stir until completely dissolved to obtain salt solution A; accurately weigh 540 mmol of urea into a beaker containing 200 mL of deionized water, stir until completely dissolved to obtain urea solution B; pour the salt solution A and the urea solution B into a 1000 mL four-necked flask at the same time and add 100 mL of deionized water, first add 50 mL of formamide, then add 50 mL of methanol solution, stir uniformly, then heat to 90℃ at a rate of 0.5℃ / min, keep constant temperature for 24 h, then centrifuge to obtain precipitate D, stir the precipitate with a glass rod, dissolve and disperse in 600 mL of deionized water, heat to 80℃ at a rate of 2℃ / min, keep constant temperature for 12 h, then obtain solid sample E by reduced pressure filtration, wash with deionized water until neutral, then dry the solid sample E in a 70℃ oven for 12 h, cool and grind to obtain copper nickel magnesium aluminum hydrotalcite powder; accurately weigh 0.006 mmol of disodium hydrogen phosphate into 100 mL of deionized water to obtain phosphate solution C, immerse the phosphate solution C in the copper nickel magnesium aluminum hydrotalcite powder by the initial wet impregnation method to obtain an impregnated product, which is recorded as Ni1Cu4MgAl / P-LDHs, and dry storage;

[0083] Step 2: Preparation of P-impregnated NiCu alloy nanoparticle catalyst

[0084] Put the catalyst precursor powder into a nitrogen atmosphere and heat to 600℃ at a rate of 2℃ / min, then switch to a hydrogen atmosphere and keep for 4 h, then switch to a nitrogen atmosphere, and then cool to room temperature to obtain a catalyst 8 loaded with NiCu alloy nanoparticles, which is recorded as Ni1Cu4-MgAl / P-LDO.

[0085] Comparative Example 6

[0086] Step 1: Preparation of hydrotalcite precursor impregnated with aqueous phosphate solution by coprecipitation method

[0087] Accurately weigh 10 mmol of Ni(NO3)2·6H2O, 20 mmol of Cu(NO3)2·3H2O, 30 mmol of Mg(NO3)2·6H2O and 20 mmol of Al(NO3)3·9H2O into a beaker containing 200 mL of deionized water, stir until completely dissolved to obtain salt solution A; accurately weigh 540 mmol of urea into a beaker containing 200 mL of deionized water, stir until completely dissolved to obtain urea solution B; pour the salt solution A and the urea solution B into a 1000 mL four-necked flask at the same time and add 100 mL of deionized water, first add 50 mL of formamide, then add 50 mL of methanol solution, stir uniformly, then heat to 90℃ at a rate of 0.5℃ / min, keep constant temperature for 24 h, then centrifuge to obtain precipitate D, stir the precipitate with a glass rod, dissolve and disperse in 600 mL of deionized water, heat to 80℃ at a rate of 2℃ / min, keep constant temperature for 12 h, then obtain solid sample E by reduced pressure filtration, wash with deionized water until neutral, then dry the solid sample E in a 70℃ oven for 12 h, cool and grind to obtain copper nickel magnesium aluminum hydrotalcite powder; accurately weigh 0.006 mmol of disodium hydrogen phosphate into 100 mL of deionized water to obtain phosphate solution C, immerse the phosphate solution C in the copper nickel magnesium aluminum hydrotalcite powder by the initial wet impregnation method to obtain an impregnated product, denoted as Ni1Cu2MgAl / P-LDHs, and dry for storage;

[0088] Step 2: Preparation of P-impregnated NiCu alloy nanoparticle catalyst

[0089] Place the catalyst precursor powder in a nitrogen atmosphere and heat to 600℃ at a rate of 2℃ / min, then switch to a hydrogen atmosphere and keep for 4 h, then switch to a nitrogen atmosphere, and then cool to room temperature to obtain a catalyst loaded with NiCu alloy nanoparticles, denoted as Ni1Cu2-MgAl / P-LDO.

[0090] Comparative Example 7

[0091] Step 1: Preparation of P-doped NiMgAl-P-LDHs precursor by coprecipitation method

[0092] Accurately weigh 30 mmol of Ni(NO3)2·6H2O, 30 mmol of Mg(NO3)2·6H2O and 20 mmol of Al(NO3)3·9H2O, and put them into a beaker containing 200 mL of deionized water, and stir until completely dissolved to obtain a salt solution A; accurately weigh 540 mmol of urea into a beaker containing 200 mL of deionized water, and stir until completely dissolved to obtain a urea solution B; accurately weigh 0.006 mmol of disodium hydrogen phosphate into 100 mL of deionized water to obtain a phosphate solution C; place the phosphate solution C in a 1000 mL four-necked flask, and stir at room temperature at a stirring rate of 300 r / min; pour the salt solution A and the urea solution B into the four-necked flask at the same time, first add 50 mL of formamide, and then add 50 mL of methanol solution; after stirring uniformly, increase the temperature to 90℃ at a rate of 0.5℃ / min, and then maintain the temperature for crystallization for 24 h; then centrifuge to obtain a precipitate D; stir the precipitate with a glass rod, and dissolve and disperse it in 600 mL of deionized water; increase the temperature to 80℃ at a rate of 2℃ / min, and then maintain the temperature for crystallization for 12 h; then perform reduced pressure suction filtration to obtain a solid sample E; wash the solid sample E with deionized water until neutral; then dry the solid sample E in a 70℃ oven for 12 h; after cooling, grind to obtain a catalyst precursor, a P-containing nickel-magnesium-aluminum hydrotalcite powder, which is recorded as NiMgAl-P-LDHs, and store in a dry state;

[0093] Step 2: Preparation of a P-doped and uniformly dispersed Ni nanoparticle catalyst

[0094] Place the catalyst precursor powder in a nitrogen atmosphere, and increase the temperature to 600℃ at a rate of 2℃ / min; then switch to a hydrogen atmosphere and maintain the temperature for 4 h; then switch to a nitrogen atmosphere, and then decrease the temperature to room temperature to obtain a P-doped and uniformly dispersed Ni nanoparticle catalyst 10, which is recorded as Ni-MgAl-P-LDO.

[0095] Comparative Example 8

[0096] Step 1: Preparation of a CuMgAl-P-LDHs precursor doped with P elements by a coprecipitation method

[0097] Accurately weigh 30 mmol of Cu(NO3)2·3H2O, 30 mmol of Mg(NO3)2·6H2O and 20 mmol of Al(NO3)3·9H2O into a beaker containing 200 mL of deionized water, stir until completely dissolved to obtain salt solution A; accurately weigh 540 mmol of urea into a beaker containing 200 mL of deionized water, stir until completely dissolved to obtain urea solution B; accurately weigh 0.006 mmol of disodium hydrogen phosphate into 100 mL of deionized water to obtain phosphate solution C, place the phosphate solution C in a 1000 mL four-necked flask, stir at room temperature, the stirring rate is 300 r / min, pour the salt solution A and the urea solution B into the four-necked flask at the same time, first add 50 mL of formamide, then add 50 mL of methanol solution, after stirring uniformly, keep the temperature rising rate at 0.5 ℃ / min to 90 ℃, constant temperature crystallization for 24 h, then centrifugation to obtain precipitate D, stir the precipitate with a glass rod, dissolve and disperse in 600 mL of deionized water, the temperature is raised to 80 ℃, the temperature rising rate is 2 ℃ / min, constant temperature crystallization for 12 h, then obtain solid sample E by reduced pressure suction filtration, wash with deionized water until neutral, then dry the solid sample E in a 70 ℃ oven for 12 h, cool and grind to obtain a catalyst precursor, a P-containing copper magnesium aluminum hydrotalcite powder, marked as CuMgAl-P-LDHs, dry storage;

[0098] Step 2: preparation of P-doped uniformly dispersed Ni nanoparticle catalyst

[0099] Place the catalyst precursor powder in a nitrogen atmosphere and heat to 600 ℃ at a temperature rising rate of 2 ℃ / min, then switch to a hydrogen atmosphere and keep for 4 h, then switch to a nitrogen atmosphere, and then cool to room temperature to obtain a P-doped uniformly dispersed Cu nanoparticle catalyst 11, marked as Cu-MgAl-P-LDO.

[0100] Use the foregoing catalysts 1-11 in the preparation of isopropylbenzene in the reaction of selective catalytic hydrogenation of α-methylstyrene in liquid phase, the specific steps are as follows:

[0101] Tablet the foregoing catalysts 1-11, 20 mesh granulation, accurately weigh 2 g of the granular catalyst and load into a reaction tube, load the reaction tube into a high-pressure fixed bed reactor, pre-treat by passing H2 through the gas path, the H2 flow rate is 25 mL / min / g, maintain at 600 ℃ for 1 h; cool to 120 ℃ for catalytic reaction, set the reaction pressure to 0.95 MPa, pass the reaction liquid through the liquid path by a high-pressure liquid pump, the reaction liquid is a mixture of α-methylstyrene and isopropylbenzene, the reaction liquid feed space velocity is 4.5 h -1, the volume ratio of α-methyl styrene, cumene in the reaction solution is 3:1; quantitative analysis is carried out by using gas chromatography, and the conversion rate of α-methyl styrene and the selectivity of cumene are calculated, and the specific reaction catalytic performance is shown in Table 1.

[0102] Table 1, the conversion rate of α-methyl styrene and the selectivity of cumene.

[0103]

[0104] It can be seen from Table 1 that in the reaction of preparing cumene by liquid phase selective catalytic hydrogenation of α-methyl styrene, the catalyst of Ni1Cu1-MgAl-P-LDO obtained by doping P by co-precipitation method has higher selectivity and better stability, and the hydrogenation performance of the catalyst containing NiCu bimetal is better than that of the single metal Ni or Cu catalyst, further, when the content ratio of Ni and Cu is 1:1, the catalytic activity and stability of the catalyst are the best. Specifically, the hydrogenation activity of catalyst 1 is higher than that of catalysts 2 and 3, and the conversion rate can reach 100%, which indicates that when Ni:Cu=1:1, it is more suitable for α-methyl styrene hydrogenation reaction; the selectivity of cumene of catalyst 1 remains stable after 8h of reaction, which has good stability, indicating that doping P element in the co-precipitation synthesis process is more conducive to the stability of the catalyst; catalyst 1 has excellent α-methyl styrene conversion rate and cumene selectivity compared with single metal catalysts 10 and 11, indicating that the bimetallic NiCu alloy nanoparticle active center is more conducive to α-methyl styrene hydrogenation. In summary, using the catalyst 1 of the application, the highly dispersed NiCu alloy nanoparticles can stably catalyze the hydrogenation of α-methyl styrene to prepare cumene, and have good conversion rate, selectivity and stability without excessive hydrogenation to form isopropyl cyclohexane.

[0105] The use of the aforementioned catalysts 1-11 in the liquid phase catalytic hydrogenation of hydroxyl pivalaldehyde to prepare pentaerythritol is as follows:

[0106] The aforementioned catalysts 1-11 are pressed into tablets, 20 mesh granulation, and 2g of the granular catalyst is accurately weighed and loaded into the reaction tube, and the reaction tube is loaded into a high-pressure fixed bed reactor, pretreated by passing H2 through the gas path, the H2 flow rate is 25mL / min / g, and maintained at 600℃ for 1h; cool to 130℃ for catalytic reaction, set the reaction pressure to 3.5MPa, pass the reaction liquid through the liquid path into the reaction tube by a high-pressure liquid pump, the reaction liquid is a mixture of hydroxyl pivalaldehyde and pentaerythritol, the liquid feed space velocity is 4.5h -1 , the volume ratio of hydroxyl pivalaldehyde and pentaerythritol in the reaction solution is 9:1, quantitative analysis is carried out by using gas chromatography, and the conversion rate of hydroxyl pivalaldehyde and the selectivity of pentaerythritol are calculated, and the specific reaction catalytic performance is shown in Table 2.

[0107] Table 2, conversion rate of hydroxypivalaldehyde and selectivity of pivalol.

[0108]

[0109] From Table 2, in the reaction of preparing pivalol by catalytic hydrogenation of hydroxypivalaldehyde, the catalyst of Ni1Cu4-MgAl-P-LDO prepared by co-precipitation method doped with P has higher selectivity and better stability, and the hydrogenation performance of the catalyst containing NiCu bimetal is better than that of single metal Ni or Cu catalyst. Further, when the content ratio of Ni and Cu is 1:4, the catalyst has the best catalytic activity and stability. Specifically, compared with catalysts 1 and 3, catalyst 2 has high hydrogenation activity of hydroxypivalaldehyde, and the conversion rate can reach 100%, which indicates that Ni:Cu = 1:4 is more suitable for the hydrogenation reaction of hydroxypivalaldehyde; compared with catalysts 5 and 8, after 8h of reaction, the conversion rate of hydroxypivalaldehyde and the selectivity of pivalol do not decrease, which indicates that the doping of P element in the co-precipitation process is more conducive to the efficient hydrogenation of hydroxypivalaldehyde; compared with single metal catalysts 10 and 11, catalyst 2 has excellent conversion rate of hydroxypivalaldehyde and selectivity of pivalol, which indicates that the bimetallic NiCu alloy nanoparticle active center is more conducive to the hydrogenation of hydroxypivalaldehyde. In summary, the highly dispersed NiCu alloy nanoparticles of the catalyst 2 of the present application can stably catalyze the hydrogenation of hydroxypivalaldehyde to prepare pivalol, and have good conversion rate of hydroxypivalaldehyde and selectivity of pivalol, avoiding the occurrence of side reactions.

[0110] The use of the aforementioned catalysts 1-11 in the catalytic hydrogenation of isooctene aldehyde to prepare isooctanol is as follows:

[0111] The aforementioned catalysts 1-11 were pressed into tablets, 20 mesh granulation was performed, 2g of the granular catalyst was accurately weighed and loaded into a reaction tube, the reaction tube was loaded into a high-pressure fixed bed reactor, pretreatment was performed by passing H2 through the gas path at a flow rate of 25mL / min / g, and the temperature was maintained at 600℃ for 1h; the reaction was carried out at a temperature of 130℃, the reaction pressure was set to 3.5MPa, the reaction liquid was passed through the liquid path by a high-pressure liquid pump, the reaction liquid was a mixture of isooctanol and isooctene aldehyde, the feed space velocity of the reaction liquid was 4.5h-1, the volume ratio of isooctene aldehyde to isooctanol in the reaction liquid was 8:1, and quantitative analysis was performed by gas chromatography to calculate the conversion rate of isooctene aldehyde and the selectivity of isooctanol. The specific reaction catalytic performance is shown in Table 3. -1

[0112] Table 3, conversion rate of isooctene aldehyde and selectivity of isooctanol.

[0113] ​

[0114]

[0115] From Table 3, in the reaction of preparing isooctanol by catalytic hydrogenation of isooctenal, the catalyst of Ni1Cu2-MgAl-P-LDO prepared by co-precipitation method doped with P has higher selectivity and better stability, and the hydrogenation performance of the catalyst containing NiCu bimetal is better than that of single metal Ni or Cu catalyst, further, when the content ratio of Ni and Cu is 1:2, the catalytic activity and stability of the catalyst are the best. Specifically, the catalyst 3 has higher isooctenal hydrogenation activity than the catalysts 1 and 2, the conversion rate can reach 100%, and the selectivity of isooctanol is higher and can reach 100%, which indicates that Ni:Cu = 1:2 is more suitable for isooctenal hydrogenation reaction; compared with the comparative examples 6 and 9, the isooctenal conversion rate and the selectivity of isooctanol of the catalyst 3 do not decrease after 8h reaction, and the catalyst has good stability, which indicates that doping P element in the co-precipitation synthesis process is more conducive to efficient hydrogenation of isooctenal; compared with the single metal catalysts of the comparative examples 10 and 11, the catalyst 3 has excellent isooctenal conversion rate and isooctanol selectivity, which indicates that the bimetallic NiCu alloy nanoparticle active center is more conducive to the hydrogenation of hydroxypivalaldehyde. In summary, using the catalyst 3 of the present application, the highly dispersed NiCu alloy nanoparticles can efficiently catalyze the hydrogenation of isooctenal to prepare isooctanol, and the catalyst coking caused by the simultaneous hydrogenation of carbon-carbon double bond and carbon-oxygen double bond to release a large amount of heat is avoided.

[0116] The above has described various embodiments of the present application, and the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and changes are obvious to those skilled in the art without departing from the scope and spirit of the described embodiments.

Claims

1. A supported NiCu alloy nanoparticle catalyst for catalyzing the hydrogenation of alkenes or aldehydes, characterized in that, The active component of the catalyst is uniformly dispersed NiCu alloy nanoparticles, the carrier is P-doped MgAl layered double metal oxide, the structural formula is NiCu-MgAl-P-LDO, the molar ratio of divalent metal ions M 2+ and trivalent metal ions Al 3+ in the catalyst is (1-4):1, the molar ratio of Ni 2+ , Cu 2+ , Mg 2+ in the divalent metal ions is (1-4):(1-4):(1-3); in the XRD pattern of the catalyst, the characteristic diffraction peaks of NiCu alloy are observed at 2θ angles of 43.5° and 50.9°, the characteristic diffraction peaks of MgAl-LDO are observed at 36.3° and 63.1°, and there are no other peaks.

2. The supported NiCu alloy nanoparticle catalyst of claim 1, wherein, The ICP test shows that the content of Cu in the active component is 10-60 wt% and the content of Ni is 10-60 wt% based on the total weight of the catalyst.

3. The supported NiCu alloy nanoparticle catalyst according to claim 1, characterized in that, The transmission electron microscopy shows that the active component of the catalyst is uniformly dispersed NiCu alloy nanoparticles with a particle size of 12.4 nm, and the active component is uniformly dispersed on the MgAl-LDO carrier.

4. A process for the preparation of a catalyst as claimed in any one of claims 1 to 3, characterized in that The preparation method comprises the following steps: Step 1: preparing copper-nickel-magnesium-aluminum hydrotalcite powder doped with P by using a coprecipitation method 5-30 mmol of Ni(NO3)2·6H2O, 15-30 mmol of Cu(NO3)2·3H2O, 15-50 mmol of Mg(NO3)2·6H2O and 10-40 mmol of Al(NO3)3·9H2O are weighed and put into a beaker containing 200 mL of deionized water, and stirred until completely dissolved to obtain a salt solution A; urea is weighed and put into a beaker containing 200-500 mL of deionized water, and stirred until completely dissolved to obtain a urea solution B; a phosphate is weighed and dissolved in 100-300 mL of deionized water to obtain a phosphate solution C; the phosphate solution C is placed in a 1000 mL four-necked flask, and stirred at room temperature at a stirring rate of 100-500 r / min; the salt solution A and the urea solution B are simultaneously poured into the four-necked flask, 10-50 mL of formamide is first added, and then 10-50 mL of a methanol solution is added; after being uniformly stirred, the temperature is raised to 70-120 ℃ at a temperature raising rate of 0.5-1 ℃ / min, and then crystallized at constant temperature for 12-36 h; then the precipitate D is obtained by centrifugation; the precipitate is stirred with a glass rod, and dissolved and dispersed in 400-800 mL of deionized water; the temperature is raised to 60-80 ℃ at a temperature raising rate of 1-10 ℃ / min, and then crystallized at constant temperature for 10-30 h; then the solid sample E is obtained by reduced-pressure suction filtration; the solid sample E is washed to neutral with deionized water; then the solid sample E is dried in an oven at 70-100 ℃ for 8-20 h; after being cooled, the catalyst precursor, i.e., the copper-nickel-magnesium-aluminum hydrotalcite powder doped with P, is obtained by grinding, and is stored after being dried; Step 2: preparing a P-doped NiCu alloy nanoparticle catalyst with uniform dispersion The catalyst precursor powder is calcined under a nitrogen atmosphere, then switched to a hydrogen atmosphere and kept warm for 2-5 h, and then switched to a nitrogen atmosphere; after being cooled to room temperature, the P-doped NiCu alloy nanoparticle catalyst with uniform dispersion is obtained.

5. The preparation method according to claim 4, characterized in that, In step 1, the molar concentration of urea in the urea solution is 0.6-7 mol / L.

6. The preparation method according to claim 4, in step 1, the phosphate is disodium hydrogen phosphate, and the concentration of the phosphate solution C is 0.01-0.1 mmol / L.

7. The preparation method according to claim 4, in step 2, in the calcination process, the first time is to place the sample in a nitrogen atmosphere, and the temperature is raised to 400-800 ℃ at a temperature raising rate of 1-10 ℃ / min from room temperature.

8. A process for the production of cumene by the liquid phase selective catalytic hydrogenation of α-methylstyrene, characterized in that, The catalyst of any one of claims 1-3 is used, and specifically includes the following steps: taking the catalyst, granulating to 20-40 mesh, loading into a reaction tube, loading the reaction tube into a high-pressure fixed-bed reactor, pre-treating by passing H2 through a gas path, H2 flow rate is 25-150 mL / min / g, maintaining at 200-800℃ for 1-3 h; cooling to 50-200℃ for catalytic reaction, setting the reaction pressure to 0.1-2 MPa; passing the reaction liquid through a liquid path into the reaction tube by a high-pressure liquid pump, finally gas and liquid converge in one way, flowing through the catalyst bed, and performing catalytic reaction in the catalyst bed; the reaction liquid is a mixed liquid of α-methyl styrene and cumene, the volume ratio of α-methyl styrene and cumene in the mixed liquid is (1-9):1; using hydrogen as the balancing gas, the reaction liquid volume space velocity is set to 1-10 h -1 ; the volume ratio of hydrogen and reaction liquid is (100-150):1; using gas chromatography for quantitative analysis of the product, the conversion rate of α-methyl styrene is up to 100%, and the selectivity of cumene is up to 99.91%.

9. A reaction for the catalytic hydrogenation of hydroxypivalaldehyde to produce neopentyl glycol, characterized in that, The catalyst according to any one of claims 1-3 is used, specifically including the following steps: taking the catalyst, 20-40 mesh granulation, loaded into the reaction tube, the reaction tube is loaded into the high-pressure fixed bed reactor, through the gas path into H2 pretreatment, H2 flow rate is 25-150 mL / min / g, at 200-800 DEG C for 1-3 h; cooling to 80-200 DEG C for catalytic reaction, set the reaction pressure is 0.5-5 MPa, the reaction liquid through high-pressure liquid pump via liquid path into the reaction tube, eventually gas-liquid convergence a road, flow through the catalyst bed, in the catalyst bed for catalytic reaction; the reaction liquid is a mixture of hydroxyl pivaldehyde and pentaerythritol, the volume ratio of hydroxyl pivaldehyde, pentaerythritol in the mixture is (1-9): 1; using hydrogen as the balance gas, the reaction liquid volume space velocity is set to 1-10 h -1 ; the volume ratio of hydrogen, reaction liquid is (100-150): 1; using gas chromatography for quantitative analysis of the product, the conversion rate of hydroxyl pivaldehyde is up to 100%, the selectivity of pentaerythritol is up to 100%.

10. A process for the hydrogenation of iso-octene aldehyde to iso-octanol, characterized in that, The catalyst according to any one of claims 1-3 is used, specifically including the following steps: taking the catalyst, 20-40 mesh granulation, loaded into the reaction tube, the reaction tube is loaded into the high-pressure fixed bed reactor, through the gas path into H2 pretreatment, H2 flow rate is 25-150 mL / min / g, maintained at 200-800 DEG C for 1-3 h; cooling to 100-200 DEG C for catalytic reaction, set the reaction pressure is 1-5 MPa, the reaction liquid through high-pressure liquid pump via liquid path into the reaction tube, eventually gas-liquid convergence a road, flow through the catalyst bed, catalytic reaction in the catalyst bed; the reaction liquid is a mixture of isooctene aldehyde and isooctanol, the volume ratio of isooctene aldehyde, isooctanol in the mixture is (1-9): 1; using hydrogen as the balance gas, the reaction liquid volume space velocity is set to 1-10 h -1 ; the volume ratio of hydrogen, reaction liquid is (100-150): 1; using gas chromatography for quantitative analysis of the product, the conversion of isooctene aldehyde is up to 100%, the selectivity of isooctanol is up to 100%.

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