A catalyst for preparing 2,5-tetrahydrofuran dimethyl alcohol, a preparation method and application thereof

Abstract

The application discloses a catalyst for preparing 2,5-tetrahydrofuran dimethyl alcohol and a preparation method and application thereof. The catalyst comprises an alumina carrier and an active component nickel, wherein the molar ratio of Ni / NiO in the active component nickel is 1.00-1.80:1. The catalyst has the characteristics of high efficient conversion of 5-hydroxymethylfurfural and high selectivity of the product 2,5-tetrahydrofuran dimethyl alcohol under mild reaction conditions, and outstanding stability of the catalyst in cyclic use.

Description

Technical Field

[0001] This invention relates to the field of catalytic chemistry, specifically to a catalyst for preparing 2,5-tetrahydrofurandiethanol, its preparation method and application, particularly a catalyst for the catalytic conversion of 5-hydroxymethylfurfural to 2,5-tetrahydrofurandiethanol, its preparation method and application. Background Technology

[0002] Biomass resources possess enormous development potential. The rational and efficient conversion of biomass into high-value-added fine chemicals and fuels to alleviate the energy crisis and achieve the phased development of replacing fossil resources with new energy sources is a goal pursued by scientists worldwide and is of great significance to the progress of humankind. 5-Hydroxymethylfurfural (HMF) is a biomass-based platform compound that, after upgrading, can be used to prepare a variety of high-value-added chemicals and fuels. Among them, the hydrogenation product of HMF, 2,5-tetrahydrofurandimethylethanol (THFDM), possesses both a tetrahydrofuran cyclic structure and symmetrical diol functional groups, and can be widely used in adhesives, coatings, resins, and polyesters. It is expected to exhibit unique advantages in barrier properties, dyeability, and degradability, thus becoming a research hotspot in both academia and industry.

[0003] 2,5-Tetrahydrofurandimethylethanol (THFDM) is mainly prepared by hydrogenation of 5-hydroxymethylfurfural (HMF). When hydrogen is used as the hydrogen source, commonly used catalysts include supported noble metals such as ruthenium (Ru), platinum (Pt), and palladium (Pd), as well as transition metals such as nickel (Ni) and copper (Cu). CN 103228626B reports a method using 5% Ru / C as a catalyst and methanol as the reaction solvent, reacting at 5 MPa hydrogen and 75 °C for 1.5 hours, followed by 14 hours at 9 MPa hydrogen and 200 °C, with a THFDM yield of only 30%. CN 113651780A reports a method for preparing 2,5-tetrahydrofurandimethylethanol using Pd / C as a catalyst and ethanol as the reaction solvent, with an initial THFDM selectivity of only 35% under reaction conditions of 1 MPa hydrogen and 90 °C. The THFDM selectivity increases to 99% as the pressure increases to 7.5-9 MPa. In the presence of noble metal catalysts, the production of THFDM from HMF typically achieves high conversion efficiency. However, the low reusability and high cost of noble metals severely hinder their commercial application. Therefore, the use of non-noble metals has gradually gained attention from researchers. For example, Klaus Hellgardt's group (RSC Adv., 2017, 7, 31401) used Raney Cu and Ni bilayer catalysts to achieve a two-stage hydrogenation method. Under reaction conditions of 0.05 mL / min flow rate, 9 MPa hydrogen gas, and 90 °C, the initial THFDM selectivity reached a maximum of 98%. However, the Raney Ni catalyst used in the second stage showed gradual deactivation. In the presence of non-noble metal catalysts, the reaction pressure is usually high, and the loss of active components is significant.

[0004] In summary, existing technologies mainly suffer from problems such as low selectivity of THFDM, harsh reaction conditions, or poor catalyst cycle stability, which pose significant challenges to practical industrial applications. Summary of the Invention

[0005] The technical problem this invention aims to solve is the low selectivity, harsh reaction conditions, or poor catalyst cycling stability of existing technologies for 2,5-tetrahydrofurandiethanol. This invention provides a catalyst for the catalytic conversion of 5-hydroxymethylfurfural to 2,5-tetrahydrofurandiethanol, its preparation method, and its applications. This catalyst exhibits high efficiency in the conversion of 5-hydroxymethylfurfural under mild reaction conditions, high selectivity for the product 2,5-tetrahydrofurandiethanol, and outstanding stability during catalyst cycling.

[0006] The first aspect of the present invention provides a catalyst for preparing 2,5-tetrahydrofurandiethanol, the catalyst comprising an alumina support and an active component nickel, wherein the molar ratio of Ni / NiO in the active component nickel is 1.00 to 1.80:1, preferably 1.10 to 1.40:1.

[0007] According to the present invention, the catalyst is represented by Ni@Al2O3, wherein Ni represents the active component nickel. The active component nickel includes metallic nickel and nickel oxide, wherein the molar ratio of metallic nickel to nickel oxide is expressed as Ni / NiO.

[0008] According to the present invention, the catalyst, based on the mass of the alumina support, has a nickel content (calculated as Ni) of 2 wt% to 30 wt%; preferably, the catalyst, based on the mass of the alumina support, has a nickel content (calculated as Ni) of 4 wt% to 15 wt%.

[0009] According to the present invention, the total acidity of the catalyst is 50 to 200 μmol / g, preferably 60 to 150 μmol / g.

[0010] According to the present invention, the specific surface area of ​​the catalyst is 30-150 m². 2 / g, preferably 35-100m 2 / g; pore volume is 0.02~0.12cm³ 3 / g, preferably 0.05~0.10cm 3 / g.

[0011] A second aspect of the present invention provides a method for preparing the above-mentioned catalyst, comprising the following steps:

[0012] The catalyst is obtained by foaming a nickel metal precursor, an aluminum metal precursor, water, a foaming agent, a foaming aid, and an organic solvent, followed by drying, calcining, and reduction of the foamed material.

[0013] According to the present invention, the mass ratio of the nickel metal precursor (calculated by the mass of Ni), the aluminum metal precursor (calculated by the mass of Al2O3), water, foaming agent, co-foaming agent and organic solvent is 0.02-0.20:1:3-50:0.2-2:0.2-20:1-20, preferably 0.04-0.17:1:5-30:0.5-1:3-10:2-10.

[0014] According to the present invention, the nickel metal precursor includes one or more of nickel nitrate, nickel acetate, nickel chloride, nickel acetylacetonate, and nickel sulfate, preferably at least one of nickel nitrate and nickel acetate.

[0015] According to the present invention, the aluminum metal precursor includes one or more of aluminum nitrate, aluminum chloride, aluminum sulfate, aluminum isopropoxide, and aluminum acetylacetonate, preferably at least one of aluminum nitrate and aluminum acetylacetonate.

[0016] According to the present invention, the foaming agent is at least one of N,N'-dimethyl-N,N'-dinitrosoterephthalamide (NTA), N,N'-dinitrosopentamethylenetetramine (DPT), diazoaminobenzene (DAB), azodicarbonamide (AC), and azobisisobutyronitrile (AIBN), preferably at least one of N,N'-dimethyl-N,N'-dinitrosoterephthalamide (NTA) or azodicarbonamide (AC).

[0017] According to the present invention, the organic solvent is one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, and isobutanol, preferably at least one of methanol and ethanol.

[0018] According to the present invention, the foaming agent is a mixture of organic acid and polyol, wherein the mass ratio of organic acid to polyol is 0.2 to 5:1, preferably 0.5 to 2:1.

[0019] According to the present invention, the organic acid is one or more selected from citric acid, lauric acid, salicylic acid, oxalic acid, and acetic acid, preferably citric acid.

[0020] According to the present invention, the polyol is one or more of glycerol, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, and diethylene glycol, preferably at least one of glycerol and ethylene glycol.

[0021] According to the present invention, the foaming temperature is 20-160°C, preferably 50-100°C; the foaming time is 2-20 hours, preferably 6-12 hours.

[0022] According to the present invention, the drying temperature is 50-200°C, preferably 60-150°C; the drying time is 2-30 hours, preferably 3-24 hours.

[0023] According to the present invention, the calcination temperature is 300-650°C; the calcination time is 1-12 hours; and the calcination atmosphere is an oxygen-containing gas.

[0024] According to the present invention, the reduction temperature is 400–1000°C, preferably 600–900°C; the reduction time is 2–10 hours, preferably 3–6 hours. The reduction atmosphere is hydrogen or a hydrogen-argon mixture, wherein the volume fraction of hydrogen in the hydrogen-argon mixture is not less than 10%, preferably 10%–50%.

[0025] A third aspect of the present invention provides the application of the above-described catalyst or the catalyst prepared by the above-described method in the catalytic conversion of 5-hydroxymethylfurfural to 2,5-tetrahydrofurandiethanol.

[0026] According to the present invention, the method of application includes: reacting 5-hydroxymethylfurfural in the presence of the above catalyst, using hydrogen as a hydrogen source, to obtain 2,5-tetrahydrofurandiethanol.

[0027] According to the present invention, preferably, 5-hydroxymethylfurfural is dissolved in an organic solvent. More preferably, the organic solvent includes one or more of methanol, ethanol, n-butanol, tetrahydrofuran, 1,4-dioxane, and methyl isobutyl ketone, preferably at least one of n-butanol and tetrahydrofuran.

[0028] According to the present invention, the mass ratio of 5-hydroxymethylfurfural to catalyst is 0.2 to 10:1, preferably 0.5 to 5.0:1.

[0029] According to the present invention, the mass ratio of the organic solvent to 5-hydroxymethylfurfural is 20 to 300:1, preferably 30 to 200:1.

[0030] According to the present invention, hydrogen gas is introduced into the reaction system to adjust the reaction pressure. The reaction pressure is 0.2 to 5 MPa, preferably 0.5 to 3 MPa.

[0031] According to the present invention, the reaction conditions are as follows: the reaction temperature is 60-200°C, preferably 100-180°C; and / or the reaction time is 2-48 h, preferably 4-24 h.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] (1) The catalyst of the present invention includes an alumina support and an active component nickel. The molar ratio of Ni / NiO in the active component nickel is controlled. The catalyst has the characteristics of high efficiency in the conversion of 5-hydroxymethylfurfural under mild reaction conditions, high selectivity of the product 2,5-tetrahydrofurandimethyl, and outstanding stability in the recycling of the catalyst.

[0034] (2) In this invention, the catalyst is prepared by in-situ synthesis. In particular, the combined use of a foaming agent and a co-foaming agent in the preparation method results in a more uniform distribution of the active component, nickel, making it relatively easier to reduce. Further control of the reduction temperature allows the prepared catalyst to efficiently convert 5-hydroxymethylfurfural to 2,5-tetrahydrofurandiethanol under mild reaction conditions, significantly improving both substrate conversion and product selectivity. Furthermore, the prepared catalyst exhibits good stability; no significant change in catalyst performance was observed after four cycles of use.

[0035] (3) The catalyst of the present invention is suitable for the catalytic conversion of 5-hydroxymethylfurfural to 2,5-tetrahydrofurandimethylmethanol. It has the characteristics of high efficiency of 5-hydroxymethylfurfural conversion under mild reaction conditions, high selectivity of product 2,5-tetrahydrofurandimethylmethanol (THFDM), and outstanding stability of catalyst recycling. Attached Figure Description

[0036] Figure 1 The image shows the XRD pattern of the Ni@Al2O3 catalyst obtained in Example 1.

[0037] Figure 2 The image shows the NH3-TPD of the Ni@Al2O3 catalyst obtained in Example 1.

[0038] Figure 3 The image shows the XPS plot of the Ni@Al2O3 catalyst obtained in Example 1.

[0039] Figure 4 The HMF conversion and THFDM selectivity are given under the recycling conditions of the Ni@Al2O3 catalyst obtained in Example 1. Detailed Implementation

[0040] In this invention, the reaction product 2,5-tetrahydrofurandiethanol (THFDM) was qualitatively analyzed by gas chromatography-mass spectrometry (GC-MS), and the conversion rate of the substrate 5-hydroxymethylfurfural (HMF) and the yield of the reaction product THFDM were analyzed by gas chromatography (GC). The GC-MS system was an Agilent 7890A from Agilent Technologies, USA, with an HP-5 nonpolar capillary column (30m, 0.53mm). The gas chromatograph was an Agilent 7890B, with a flame ionization detector (FID) and an SE-54 capillary column (30m, 0.53mm).

[0041] In this invention, the XRD measurement method for molecular sieve products is as follows: the phase composition of the sample is analyzed using a Rigaku Ultima IV X-ray powder diffractometer (Japan), with a CuKα ray source. Nickel filter, 2θ scanning range 2°-50°, operating voltage 35kV, current 25mA, scanning rate 10° / min.

[0042] In this invention, an inductively coupled plasma atomic emission spectrometer (ICP) of model Varian 725-ES is used to dissolve the analytical sample in hydrofluoric acid to detect the content of metal elements.

[0043] In this invention, the element binding energy on the catalyst surface was measured on a Thermo X-ray photoelectron spectrometer (ESCA LAB-250), and the measured element signal was corrected using C1s = 284.6 eV as an internal standard.

[0044] In this invention, the NH3 temperature-programmed desorption (NH3-TPD) experiment was conducted on a TPD / TPR Altamira AMI-3300 instrument, and the total acid content was calculated by fitting and peaking the obtained spectrum.

[0045] In this invention, the physical adsorption instrument is a Micromeretic ASAP2020M. The test conditions are: measurement temperature -169℃, molecular sieve pre-treated in vacuum at 300℃ for 10 hours before measurement, and parameters such as pore volume and specific surface area are calculated using the BET method and t-plot method.

[0046] In this invention, the conversion formula for 5-hydroxymethylfurfural is:

[0047] HMF conversion % = (molar amount of HMF participating in the reaction) / (molar amount of HMF substrate) × 100%.

[0048] In this invention, the formula for calculating the selectivity of the product THFDM is as follows:

[0049] The selectivity % of the product THFDM = (molar amount of THFDM produced in the reaction) / (molar amount of HMF reacted) × 100%.

[0050] To facilitate understanding of the present invention, the following embodiments are provided. However, these embodiments are merely for the purpose of helping to understand the present invention and should not be regarded as specific limitations of the present invention.

[0051] Example 1

[0052] Nickel nitrate was used as the nickel source, aluminum nitrate as the aluminum source, N,N'-dimethyl-N,N'-dinitrosoterephthalamide (NTA) as the blowing agent, a mixture of citric acid and glycerol as the co-blowing agent, and ethanol as the organic solvent. The mass ratio of nickel metal precursor (based on the mass of Ni), aluminum metal precursor (based on the mass of Al2O3), water, blowing agent, co-blowing agent, and organic solvent was 0.10:1:10:0.5:4:10. The mass ratio of citric acid to glycerol in the co-blowing agent was 1:1.

[0053] The specific synthesis steps are as follows: 0.31g of nickel nitrate and 4.18g of aluminum nitrate were weighed and dissolved in 10g of water. Then, 0.5g of foaming agent NTA, 2g of citric acid, 2g of glycerol and 10g of ethanol were added and stirred evenly. The mixture was heated and stirred in an 80℃ water bath for 8 hours until it became gel-foamed. The mixture was then transferred to a 120℃ oven and dried for 12 hours. After that, it was calcined at 550℃ for 6 hours and reduced at 800℃ for 4 hours under a hydrogen atmosphere to obtain the Ni@Al2O3 catalyst.

[0054] The specific surface area of ​​the sample was calculated to be 40 m² using the BET and t-plot methods. 2 / g, pore volume 0.08cm 3 / g. Inductively coupled plasma atomic emission spectrometry (ICP) was used to determine the Ni content relative to the Al2O3 mass; the Ni content was 10wt%, and the catalyst was named 10Ni@Al2O3. The XRD pattern of the sample is shown below. Figure 1 As shown; the NH3-TPD of the sample is as follows Figure 2 As shown, the total acid content calculated from this is 73 μmol·g. -1 The XPS values ​​of the sample are as follows: Figure 3 As shown, a binding energy of 852.6 eV corresponds to the metallic element Ni(2p) 3 / 2 The peak), with a binding energy of 855.4 eV, corresponds to divalent nickel (2). + The molar ratio of metallic Ni to oxidized NiO is calculated using the ratio of the two peak areas (Ni / NiO ratio) and is 1.26.

[0055] Example 2

[0056] Nickel nitrate was used as the nickel source, aluminum nitrate as the aluminum source, azodicarbonamide (AC) as the blowing agent, a mixture of citric acid and glycerol as the co-blowing agent, and ethanol as the organic solvent. The mass ratio of nickel metal precursor (based on Ni mass), aluminum metal precursor (based on Al2O3 mass), water, blowing agent, co-blowing agent, and organic solvent was 0.08:1:20:0.7:5:8. The mass ratio of citric acid to glycerol in the co-blowing agent was 1.5:1.

[0057] The specific synthesis steps are as follows: 0.25g of nickel nitrate and 4.18g of aluminum nitrate were weighed and dissolved in 20g of water. Then, 0.7g of foaming agent AC, 3g of citric acid, 2g of glycerol and 8g of ethanol were added and stirred evenly. The mixture was heated and stirred in a 90℃ water bath for 4 hours until it became gel-foamed. The mixture was then transferred to a 100℃ oven and dried for 12 hours. After that, it was calcined at 550℃ for 6 hours and reduced at 700℃ for 5 hours under a hydrogen atmosphere to obtain the Ni@Al2O3 catalyst.

[0058] The specific surface area of ​​the sample was calculated to be 42 m² using the BET and t-plot methods. 2 / g, pore volume 0.07cm 3 / g. Inductively coupled plasma atomic emission spectrometry (ICP) was used to determine the relative Ni content to Al2O3 mass; the catalyst was named 8Ni@Al2O3. XRD patterns of the sample were compared with... Figure 1 Similar; the NH3-TPD of the sample is similar to Figure 2 Similarly, the total acidity calculated from this is 67 μmol·g. -1 The XPS values ​​of the sample are... Figure 3 Similarly, a binding energy of 852.6 eV corresponds to the metallic element Ni (2p0). 3 / 2The peak), with a binding energy of 855.4 eV, corresponds to divalent nickel (2). + The molar ratio of metallic Ni to oxidized NiO is calculated using the ratio of the two peak areas (Ni / NiO ratio) and is 1.21.

[0059] Example 3

[0060] Nickel acetate was used as the nickel source, aluminum nitrate as the aluminum source, N,N'-dimethyl-N,N'-dinitrosoterephthalamide (NTA) as the blowing agent, a mixture of citric acid and ethylene glycol as the co-blowing agent, and ethanol as the organic solvent. The mass ratio of nickel metal precursor (based on the mass of Ni), aluminum metal precursor (based on the mass of Al2O3), water, blowing agent, co-blowing agent, and organic solvent was 0.12:1:15:0.8:6:6. The mass ratio of citric acid to ethylene glycol in the co-blowing agent was 1:1.

[0061] The specific synthesis steps are as follows: 0.36g of nickel nitrate and 4.18g of aluminum nitrate were weighed and dissolved in 15g of water. 0.8g of foaming agent NTA, 3g of citric acid, 3g of glycerol and 6g of ethanol were added and stirred evenly. The mixture was heated and stirred in a 70℃ water bath for 6 hours until it became gel-foamed. It was then transferred to a 110℃ oven for drying for 12 hours, calcined at 550℃ for 6 hours, and reduced at 850℃ for 3 hours under a hydrogen atmosphere to obtain the Ni@Al2O3 catalyst.

[0062] The specific surface area of ​​the sample was calculated to be 47 m² using the BET and t-plot methods. 2 / g, pore volume is 0.09cm 3 / g. Inductively coupled plasma atomic emission spectrometry (ICP) was used to determine the relative Ni content to Al2O3 mass, which was 12wt%. This catalyst was named 12Ni@Al2O3. The XRD pattern of the sample and... Figure 1 Similar; the NH3-TPD of the sample is similar to Figure 2 Similarly, the total acidity calculated from this is 77 μmol·g. -1 The XPS values ​​of the sample are... Figure 3 Similarly, a binding energy of 852.6 eV corresponds to the metallic element Ni (2p0). 3 / 2 The peak), with a binding energy of 855.4 eV, corresponds to divalent nickel (2). + The molar ratio of metallic Ni to oxidized NiO is calculated using the ratio of the two peak areas (Ni / NiO ratio) and is 1.25.

[0063] Example 4

[0064] Nickel nitrate was used as the nickel source, aluminum acetylacetonate as the aluminum source, N,N'-dimethyl-N,N'-dinitrosoterephthalamide (NTA) as the blowing agent, a mixture of citric acid and ethylene glycol as the co-blowing agent, and ethanol as the organic solvent. The mass ratio of nickel metal precursor (based on the mass of Ni), aluminum metal precursor (based on the mass of Al2O3), water, blowing agent, co-blowing agent, and organic solvent was 0.15:1:10:0.5:6:10. The mass ratio of citric acid to ethylene glycol in the co-blowing agent was 0.5:1.

[0065] The specific synthesis steps are as follows: 0.47g of nickel nitrate and 6.36g of aluminum acetylacetonate were weighed and dissolved in 10g of water. 0.5g of foaming agent NTA, 2g of citric acid, 4g of glycerol and 10g of ethanol were added and stirred evenly. The mixture was heated and stirred in an 80℃ water bath for 6 hours until it became gel-foamed. It was then transferred to a 130℃ oven for drying for 12 hours, calcined at 550℃ for 6 hours, and reduced at 900℃ for 4 hours under a hydrogen atmosphere to obtain the Ni@Al2O3 catalyst.

[0066] The specific surface area of ​​the sample was calculated to be 38 m² using the BET and t-plot methods. 2 / g, pore volume 0.07cm 3 / g. Inductively coupled plasma atomic emission spectrometry (ICP) was used to determine the relative Ni content to Al2O3 mass; the catalyst was named 15Ni@Al2O3. XRD analysis of the sample and... Figure 1 Similar; the NH3-TPD of the sample is similar to Figure 2 Similarly, the total acidity calculated from this is 85 μmol·g. -1 The XPS values ​​of the sample are... Figure 3 Similarly, a binding energy of 852.6 eV corresponds to the metallic element Ni (2p0). 3 / 2 The peak), with a binding energy of 855.4 eV, corresponds to divalent nickel (2). + The molar ratio of metallic Ni to oxidized NiO is calculated using the ratio of the two peak areas (Ni / NiO ratio) and is 1.32.

[0067] Examples 5-8

[0068] Tetrahydrofuran (THF) was used as the reaction solvent, with a THF / HMF mass ratio of 50 and an HMF / catalyst mass ratio of 1. The hydrogen pressure was 2.0 MPa, the reaction temperature was 150 °C, and the reaction time was 16 h. 0.2 g of the catalyst from Examples 1-4 above, along with 0.2 g of HMF and 10 g of THF, were added to a high-pressure reactor equipped with a stirrer, and the reactor was charged with 2.0 MPa of hydrogen. The temperature was raised to the preset temperature using a programmed heating mantle, and then stirred magnetically. The reaction was carried out at 150 °C for 16 h. The HMF conversion and THFDM selectivity of the reaction liquid were calculated by gas phase analysis, as shown in Table 1.

[0069] Table 1 Catalytic evaluation results of catalysts in Examples 1-4

[0070] 5 Example 1 <![CDATA[10Ni@Al2O3]]> >99 91.7 6 Example 2 <![CDATA[8Ni@Al2O3]]> >99 91.1 7 Example 3 <![CDATA[12Ni@Al2O3]]> >99 90.5 8 Example 4 <![CDATA[15Ni@Al2O3]]> >99 89.9

[0071] Example 9

[0072] Tetrahydrofuran (THF) was used as the reaction solvent, with a THF / HMF mass ratio of 80 and an HMF / catalyst mass ratio of 2.0. The hydrogen pressure was 1.5 MPa, the reaction temperature was 140 °C, and the reaction time was 20 h. 0.2 g of the catalyst from Example 1, 0.40 g of HMF, and 32.0 g of THF were added to a high-pressure reactor equipped with a stirrer, and 1.5 MPa of hydrogen gas was introduced. The temperature was raised to the preset temperature using a programmed heating mantle, and then stirred magnetically. The reaction was carried out at 140 °C for 20 h. Gas phase analysis of the reaction liquid showed complete HMF conversion (conversion rate > 99%) and a THFDM selectivity of 91.3%.

[0073] Example 10

[0074] Tetrahydrofuran (THF) was used as the reaction solvent, with a THF / HMF mass ratio of 80 and an HMF / catalyst mass ratio of 1.2. The hydrogen pressure was 1.8 MPa, the reaction temperature was 150 °C, and the reaction time was 15 h. 0.2 g of the catalyst from Example 1, 0.24 g of HMF, and 19.2 g of THF were added to a high-pressure reactor equipped with a stirrer, and 1.8 MPa of hydrogen gas was introduced. The temperature was raised to the preset temperature using a programmed heating mantle, and then stirred magnetically. The reaction was carried out at 150 °C for 15 h. Gas phase analysis of the reaction liquid showed complete HMF conversion and a THFDM selectivity of 92.2%.

[0075] Example 11

[0076] Tetrahydrofuran (THF) was used as the reaction solvent, with a THF / HMF mass ratio of 60 and an HMF / catalyst mass ratio of 1.5. The hydrogen pressure was 2.0 MPa, the reaction temperature was 130 °C, and the reaction time was 20 h. 0.2 g of the catalyst from Example 2, 0.30 g of HMF, and 18.0 g of THF were added to a high-pressure reactor equipped with a stirrer, and 2.0 MPa of hydrogen gas was introduced. The temperature was raised to the preset temperature using a programmed heating mantle, and then stirred magnetically. The reaction was carried out at 130 °C for 20 h. Gas phase analysis of the reaction liquid showed complete HMF conversion and a THFDM selectivity of 90.5%.

[0077] Example 12

[0078] Tetrahydrofuran (THF) was used as the reaction solvent, with a THF / HMF mass ratio of 70 and an HMF / catalyst mass ratio of 1.5. The hydrogen pressure was 2.0 MPa, the reaction temperature was 140 °C, and the reaction time was 16 h. 0.2 g of the catalyst from Example 2, 0.30 g of HMF, and 21.0 g of THF were added to a high-pressure reactor equipped with a stirrer, and 2.0 MPa of hydrogen gas was introduced. The temperature was raised to the preset temperature using a programmed heating mantle, and then stirred magnetically. The reaction was carried out at 140 °C for 16 h. Gas phase analysis of the reaction liquid showed complete HMF conversion and a THFDM selectivity of 91.8%.

[0079] Example 13

[0080] n-Butanol was used as the reaction solvent, with a n-butanol to HMF mass ratio of 120 and an HMF to catalyst mass ratio of 0.8. The hydrogen pressure was 3.0 MPa, the reaction temperature was 160 °C, and the reaction time was 12 h. 0.2 g of the catalyst from Example 2, 0.16 g of HMF, and 19.2 g of n-butanol were added to a high-pressure reactor equipped with a stirrer, and 3.0 MPa of hydrogen gas was introduced. The temperature was raised to the preset temperature using a programmed heating mantle, and then stirred magnetically. The reaction was carried out at 160 °C for 12 h. Gas phase analysis of the reaction liquid showed complete HMF conversion and a THFDM selectivity of 90.4%.

[0081] Example 14

[0082] n-Butanol was used as the reaction solvent, with a n-butanol to HMF mass ratio of 80 and an HMF to catalyst mass ratio of 0.8. The hydrogen pressure was 2.0 MPa, the reaction temperature was 160 °C, and the reaction time was 10 h. 0.2 g of the catalyst from Example 3, 0.16 g of HMF, and 12.8 g of n-butanol were added to a high-pressure reactor equipped with a stirrer, and 2.0 MPa of hydrogen gas was introduced. The temperature was raised to the preset temperature using a programmed heating mantle, and then stirred magnetically. The reaction was carried out at 160 °C for 10 h. Gas phase analysis of the reaction liquid showed complete HMF conversion and a THFDM selectivity of 89.8%.

[0083] Example 15

[0084] n-Butanol was used as the reaction solvent, with a n-butanol to HMF mass ratio of 100 and an HMF to catalyst mass ratio of 2.0. The hydrogen pressure was 2.0 MPa, the reaction temperature was 150 °C, and the reaction time was 15 h. 0.2 g of the catalyst from Example 3, 0.40 g of HMF, and 40.0 g of n-butanol were added to a high-pressure reactor equipped with a stirrer, and 2.0 MPa of hydrogen gas was introduced. The temperature was raised to the preset temperature using a programmed heating mantle, and then stirred magnetically. The reaction was carried out at 150 °C for 15 h. Gas phase analysis of the reaction liquid showed complete HMF conversion and a THFDM selectivity of 90.2%.

[0085] Example 16

[0086] n-Butanol was used as the reaction solvent, with a n-butanol to HMF mass ratio of 100 and an HMF to catalyst mass ratio of 1.0. The hydrogen pressure was 1.5 MPa, the reaction temperature was 130 °C, and the reaction time was 20 h. 0.2 g of the catalyst from Example 3, 0.20 g of HMF, and 20.0 g of n-butanol were added to a high-pressure reactor equipped with a stirrer, and 1.5 MPa of hydrogen gas was introduced. The temperature was raised to the preset temperature using a programmed heating mantle, and then stirred magnetically. The reaction was carried out at 130 °C for 20 h. Gas phase analysis of the reaction liquid showed complete HMF conversion and a THFDM selectivity of 90.6%.

[0087] To more intuitively describe the reaction conditions and results of Examples 9-16 above, the parameters and results are listed in Table 2.

[0088] Table 2 Catalytic performance results of Examples 9-16

[0089]

[0090]

[0091] Example 17

[0092] Tetrahydrofuran (THFDM) was used as the reaction solvent, with a THF / HMF mass ratio of 80 and an HMF / catalyst mass ratio of 2.0. The hydrogen pressure was 1.5 MPa, the reaction temperature was 140 °C, and the reaction time was 20 h. 0.2 g of the catalyst from Example 1, 0.40 g of HMF, and 32.0 g of THFDM were added to a high-pressure reactor with a stirrer, and 1.5 MPa of hydrogen gas was introduced. The temperature was raised to the preset temperature using a programmed heating mantle, and then stirred magnetically. The reaction was carried out at 140 °C for 20 h. The HMF conversion and THFDM selectivity were calculated by gas phase analysis of the reaction liquid. The used catalyst was washed, dried, and then used in the next reaction cycle, for a total of 4 cycles. The results are as follows. Figure 4 As shown in the figure. The results show that after four reactions, the HMF conversion was complete, and the THFDM selectivity remained at 89.2%, indicating that the catalyst of the present invention has good cycle stability.

[0093] Example 18

[0094] Nickel nitrate was used as the nickel source, aluminum nitrate as the aluminum source, N,N'-dinitrospentamethylenetetramine (DPT) as the blowing agent, a mixture of oxalic acid and 1,3-propanediol as the co-blowing agent, and ethanol as the organic solvent. The mass ratio of nickel metal precursor (based on Ni mass), aluminum metal precursor (based on Al2O3 mass), water, blowing agent, co-blowing agent, and organic solvent was 0.03:1:40:0.3:2:12. The mass ratio of oxalic acid to 1,3-propanediol in the co-blowing agent was 3:1.

[0095] The specific synthesis steps are as follows: 0.09g of nickel nitrate and 4.18g of aluminum nitrate were weighed and dissolved in 40g of water. Then, 0.3g of foaming agent DPT, 1.5g of oxalic acid, 0.5g of 1,3-propanediol and 12g of ethanol were added and stirred evenly. The mixture was heated and stirred in an oil bath at 140℃ for 4 hours until it reached a gel foam state. The mixture was then transferred to an oven at 100℃ and dried for 12 hours. After that, it was calcined at 550℃ for 6 hours and reduced at 450℃ for 5 hours under a hydrogen atmosphere to obtain the Ni@Al2O3 catalyst.

[0096] The specific surface area of ​​the sample was calculated to be 33 m² using the BET and t-plot methods. 2 / g, pore volume 0.05cm 3 / g. Inductively coupled plasma atomic emission spectrometry (ICP) was used to determine the relative Ni content to Al2O3 mass; the catalyst was named 3Ni@Al2O3. XRD patterns of the sample were compared with... Figure 1 Similar; the NH3-TPD of the sample is similar to Figure 2 Similarly, the total acidity calculated from this is 57 μmol·g. -1 The XPS values ​​of the sample are... Figure 3Similarly, a binding energy of 852.6 eV corresponds to the metallic element Ni (2p0). 3 / 2 The peak), with a binding energy of 855.4 eV, corresponds to divalent nickel (2). + The molar ratio of metallic Ni to oxidized NiO is calculated using the ratio of the two peak areas (Ni / NiO ratio) and is 1.05.

[0097] Tetrahydrofuran (THF) was used as the reaction solvent, with a THF / HMF mass ratio of 80 and an HMF / catalyst mass ratio of 2.0. The hydrogen pressure was 1.5 MPa, the reaction temperature was 140 °C, and the reaction time was 20 h. 0.2 g of the catalyst, 0.40 g of HMF, and 32.0 g of THF were added to a stirred high-pressure reactor, and 1.5 MPa of hydrogen gas was introduced. The temperature was raised to the preset temperature using a programmed heating mantle, and the reactor was magnetically stirred and then stirred. The reaction was carried out at 140 °C for 20 h. Gas phase analysis of the reaction liquid showed that HMF was completely converted, and the THFDM selectivity was 86.7%. The used catalyst was washed, dried, and then used in the next reaction, for a total of four cycles. The results showed that after four reactions, HMF was completely converted, and the THFDM selectivity remained at 84.2%.

[0098] Example 19

[0099] Nickel nitrate was used as the nickel source, aluminum nitrate as the aluminum source, diazoaminobenzene (DAB) as the blowing agent, a mixture of acetic acid and 1,4-butanediol as the co-blowing agent, and ethanol as the organic solvent. The mass ratio of nickel metal precursor (based on the mass of Ni), aluminum metal precursor (based on the mass of Al2O3), water, blowing agent, co-blowing agent, and organic solvent was 0.18:1:50:1.2:1:15. The mass ratio of acetic acid to 1,4-butanediol in the co-blowing agent was 4:1.

[0100] The specific synthesis steps are as follows: 0.56g of nickel nitrate and 4.18g of aluminum nitrate were weighed and dissolved in 50g of water. Then, 1.2g of foaming agent DAB, 0.8g of acetic acid, 0.2g of 1,4-butanediol and 15g of ethanol were added and stirred evenly. The mixture was heated and stirred in an oil bath at 160℃ for 4 hours until it reached a gel foam state. The mixture was then transferred to an oven at 100℃ and dried for 12 hours. After that, it was calcined at 550℃ for 6 hours and reduced at 950℃ for 5 hours under a hydrogen atmosphere to obtain the Ni@Al2O3 catalyst.

[0101] The specific surface area of ​​the sample was calculated to be 40 m² using the BET and t-plot methods. 2 / g, pore volume is 0.06cm 3 / g. Inductively coupled plasma atomic emission spectrometry (ICP) was used to determine the relative Ni content to Al2O3 mass, which was calculated to be 16wt%. This catalyst was named 16Ni@Al2O3. The XRD pattern of the sample and... Figure 1 Similar; the NH3-TPD of the sample is similar to Figure 2 Similarly, the total acidity calculated from this is 79 μmol·g. -1 The XPS values ​​of the sample are... Figure 3 Similarly, a binding energy of 852.6 eV corresponds to the metallic element Ni (2p0). 3 / 2 The peak), with a binding energy of 855.4 eV, corresponds to divalent nickel (2). + The molar ratio of metallic Ni to oxidized NiO is calculated using the ratio of the two peak areas (Ni / NiO ratio) and is 1.52.

[0102] Tetrahydrofuran (THF) was used as the reaction solvent, with a THF / HMF mass ratio of 80 and an HMF / catalyst mass ratio of 2.0. The hydrogen pressure was 1.5 MPa, the reaction temperature was 140 °C, and the reaction time was 20 h. 0.2 g of the catalyst, 0.40 g of HMF, and 32.0 g of THF were added to a stirred high-pressure reactor, and 1.5 MPa of hydrogen gas was introduced. The temperature was raised to the preset temperature using a programmed heating mantle, and the reactor was magnetically stirred and then stirred. The reaction was carried out at 140 °C for 20 h. Gas phase analysis of the reaction liquid showed that HMF was completely converted, and the THFDM selectivity was 87.5%. The used catalyst was washed, dried, and then used in the next reaction, for a total of four cycles. The results showed that after four reactions, HMF was completely converted, and the THFDM selectivity remained at 85.1%.

[0103] Comparative Example 1

[0104] The Ni / Al2O3 catalyst was prepared by impregnation method. The specific synthesis steps were as follows: 0.31g of nickel nitrate was dissolved in 10g of water, and 0.5g of foaming agent NTA, 2g of citric acid, 2g of glycerol and 10g of ethanol were added and stirred evenly. 1g of Al2O3 support was added to the above solution and stirred thoroughly until the solid reached the initial wet state. It was heated and stirred in an 80℃ water bath for 8 hours until it became gel-foamed. It was then transferred to a 120℃ oven for drying for 12 hours, calcined at 550℃ for 6 hours, and reduced at 800℃ for 4 hours under a hydrogen atmosphere to obtain the Ni / Al2O3 catalyst.

[0105] The specific surface area of ​​the sample was calculated to be 28 m² using the BET and t-plot methods. 2 / g, pore volume 0.15cm 3 / g. The relative Ni content, calculated relative to the mass of Al₂O₃, was 10 wt% using inductively coupled plasma atomic emission spectrometry (ICP). The total acidity, calculated from the NH₃-TPD of the sample, was 185 μmol·g. -1XPS calculations of the sample yielded the molar ratio of metallic Ni to oxidized NiO, which was calculated to be 0.81 using the ratio of the two peak areas (Ni / NiO ratio).

[0106] Tetrahydrofuran (THF) was used as the reaction solvent, with a THF / HMF mass ratio of 80 and an HMF / catalyst mass ratio of 2.0. The hydrogen pressure was 1.5 MPa, the reaction temperature was 140 °C, and the reaction time was 20 h. 0.2 g of the catalyst, 0.40 g of HMF, and 32.0 g of THF were added to a stirred high-pressure reactor, and 1.5 MPa of hydrogen gas was introduced. The temperature was raised to the preset temperature using a programmed heating mantle, and the reactor was then stirred magnetically. After reacting at 140 °C for 20 h, gas-phase analysis of the reaction liquid showed complete HMF conversion and a THFDM selectivity of 73.7%.

[0107] Comparative Example 2

[0108] The Ni@Al2O3 catalyst was prepared by a co-precipitation method. The specific synthesis steps were as follows: 0.31 g of nickel nitrate and 4.18 g of aluminum nitrate were dissolved in 10 g of water. Then, 0.5 g of NTA (a foaming agent), 2 g of citric acid, 2 g of glycerol, and 10 g of ethanol were added and stirred until homogeneous. The mixture was heated and stirred in a 40°C water bath. 28 wt% concentrated ammonia was slowly added dropwise while vigorous stirring to maintain the pH of the reaction system at 9. After filtration and washing, the filtrate had a pH of 7. The filtrate was then dried in a 120°C oven for 12 hours, calcined at 550°C for 6 hours, and reduced at 800°C for 4 hours under a hydrogen atmosphere to obtain the Ni@Al2O3 catalyst.

[0109] The specific surface area of ​​the sample was calculated to be 42 m² using the BET and t-plot methods. 2 / g, pore volume 0.05cm 3 / g. The relative Ni content, calculated relative to the mass of Al₂O₃, was 10 wt% using inductively coupled plasma atomic emission spectrometry (ICP). The total acid content, calculated from the NH₃-TPD of the sample, was 42 μmol·g. -1 XPS calculations of the sample yielded the molar ratio of metallic Ni to oxidized NiO, which was calculated to be 0.75 using the ratio of the two peak areas (Ni / NiO ratio).

[0110] Tetrahydrofuran (THF) was used as the reaction solvent, with a THF / HMF mass ratio of 80 and an HMF / catalyst mass ratio of 2.0. The hydrogen pressure was 1.5 MPa, the reaction temperature was 140 °C, and the reaction time was 20 h. 0.2 g of the catalyst, 0.40 g of HMF, and 32.0 g of THF were added to a stirred high-pressure reactor, and 1.5 MPa of hydrogen gas was introduced. The temperature was raised to the preset temperature using a programmed heating mantle, and the reactor was then stirred magnetically. After reacting at 140 °C for 20 h, gas-phase analysis of the reaction liquid showed complete HMF conversion and a THFDM selectivity of 67.8%.

[0111] Comparative Example 3

[0112] Nickel nitrate was used as the nickel source, aluminum nitrate as the aluminum source, a mixture of citric acid and glycerol as the foaming agent, and ethanol as the organic solvent. The mass ratio of nickel metal precursor (based on the mass of Ni), aluminum metal precursor (based on the mass of Al2O3), water, foaming agent, and organic solvent was 0.10:1:10:4:10. The mass ratio of citric acid to glycerol in the foaming agent was 1:1.

[0113] The specific synthesis steps are as follows: 0.31g of nickel nitrate and 4.18g of aluminum nitrate were weighed and dissolved in 10g of water. Then, 2g of citric acid, 2g of glycerol and 10g of ethanol were added and stirred evenly. The mixture was heated and stirred in an 80℃ water bath for 8 hours until it became gel-foamed. The mixture was then transferred to a 120℃ oven and dried for 12 hours. After that, it was calcined at 550℃ for 6 hours and reduced at 800℃ for 4 hours under a hydrogen atmosphere to obtain the Ni@Al2O3 catalyst.

[0114] The specific surface area of ​​the sample was calculated to be 25 m² using the BET and t-plot methods. 2 / g, pore volume 0.05cm 3 / g. The relative Ni content, calculated relative to the mass of Al₂O₃, was 10 wt% using inductively coupled plasma atomic emission spectrometry (ICP). The total acid content, calculated from the NH₃-TPD of the sample, was 87 μmol·g. -1 XPS calculations of the sample yielded the molar ratio of metallic Ni to oxidized NiO, which was calculated to be 0.89 using the ratio of the two peak areas (Ni / NiO ratio).

[0115] Tetrahydrofuran (THF) was used as the reaction solvent, with a THF / HMF mass ratio of 80 and an HMF / catalyst mass ratio of 2.0. The hydrogen pressure was 1.5 MPa, the reaction temperature was 140 °C, and the reaction time was 20 h. 0.2 g of the catalyst, 0.40 g of HMF, and 32.0 g of THF were added to a high-pressure reactor equipped with a stirrer, and 1.5 MPa of hydrogen gas was introduced. The temperature was raised to the preset temperature using a programmed heating mantle, and the reactor was then stirred magnetically. After reacting at 140 °C for 20 h, gas-phase analysis of the reaction liquid showed complete HMF conversion and a THFDM selectivity of 75.3%.

[0116] Comparative Example 4

[0117] Nickel nitrate was used as the nickel source, aluminum nitrate as the aluminum source, N,N'-dimethyl-N,N'-dinitrosoterephthalamide (NTA) as the blowing agent, a mixture of citric acid and glycerol as the co-blowing agent, and ethanol as the organic solvent. The mass ratio of nickel metal precursor (based on the mass of Ni), aluminum metal precursor (based on the mass of Al2O3), water, blowing agent, co-blowing agent, and organic solvent was 0.10:1:10:0.5:4:10. The mass ratio of citric acid to glycerol in the co-blowing agent was 1:1.

[0118] The specific synthesis steps are as follows: 0.31g of nickel nitrate and 4.18g of aluminum nitrate were weighed and dissolved in 10g of water. Then, 0.5g of foaming agent NTA, 2g of citric acid, 2g of glycerol and 10g of ethanol were added and stirred evenly. The mixture was heated and stirred in an 80℃ water bath for 8 hours until it became gel-foamed. The mixture was then transferred to a 120℃ oven for drying for 12 hours, calcined at 550℃ for 6 hours, and reduced at 400℃ for 4 hours under a hydrogen atmosphere to obtain the Ni@Al2O3 catalyst.

[0119] The specific surface area of ​​the sample was calculated to be 40 m² using the BET and t-plot methods. 2 / g, pore volume 0.08cm 3 / g. The relative Ni content, calculated relative to the mass of Al₂O₃, was 10 wt% using inductively coupled plasma atomic emission spectrometry (ICP). The total acid content, calculated from the NH₃-TPD of the sample, was 96 μmol·g. -1 XPS calculations of the sample yielded the molar ratio of metallic Ni to oxidized NiO, which was calculated to be 0.67 using the ratio of the two peak areas (Ni / NiO ratio).

[0120] Tetrahydrofuran (THF) was used as the reaction solvent, with a THF / HMF mass ratio of 80 and an HMF / catalyst mass ratio of 2.0. The hydrogen pressure was 1.5 MPa, the reaction temperature was 140 °C, and the reaction time was 20 h. 0.2 g of the catalyst, 0.40 g of HMF, and 32.0 g of THF were added to a stirred high-pressure reactor, and 1.5 MPa of hydrogen gas was introduced. The temperature was raised to the preset temperature using a programmed heating mantle, and the reactor was then stirred magnetically. After reacting at 140 °C for 20 h, gas-phase analysis of the reaction liquid showed complete HMF conversion and a THFDM selectivity of 77.9%.

[0121] Comparative Example 5

[0122] Nickel nitrate was used as the nickel source, aluminum nitrate as the aluminum source, azodicarbonamide (AC) as the blowing agent, citric acid as the co-blowing agent, and ethanol as the organic solvent. The mass ratio of nickel metal precursor (calculated by the mass of Ni), aluminum metal precursor (calculated by the mass of Al2O3), water, blowing agent, co-blowing agent, and organic solvent was 0.08:1:20:0.7:5:8.

[0123] The specific synthesis steps are as follows: Weigh 0.25g of nickel nitrate and 4.18g of aluminum nitrate and dissolve them in 20g of water. Then add 0.7g of foaming agent AC, 5g of citric acid and 8g of ethanol and stir evenly. Heat and stir in a 200℃ water bath for 4 hours until gel foaming. Transfer to a 120℃ oven and dry for 12 hours. Then calcine at 550℃ for 6 hours. After reduction at 800℃ for 4 hours in a hydrogen atmosphere, the catalyst is obtained.

[0124] The specific surface area of ​​the sample was calculated to be 33 m² using the BET and t-plot methods. 2 / g, pore volume is 0.06cm 3 / g. Inductively coupled plasma atomic emission spectrometry (ICP) was used to determine the relative Ni content to Al₂O₃ mass, which was 8 wt%. The total acid content, calculated from the NH₃-TPD of the sample, was 97 μmol·g. -1 XPS calculations of the sample yielded the molar ratio of metallic Ni to oxidized NiO, which was calculated to be 0.86 using the ratio of the two peak areas (Ni / NiO ratio).

[0125] Tetrahydrofuran (THF) was used as the reaction solvent, with a THF / HMF mass ratio of 50 and an HMF / catalyst mass ratio of 1. The hydrogen pressure was 2.0 MPa, the reaction temperature was 150 °C, and the reaction time was 16 h. 0.2 g of the catalyst from the comparative example, along with 0.2 g of HMF and 10 g of THF, were added to a stirred high-pressure reactor, which was then purged with 2.0 MPa of hydrogen. The temperature was raised to the preset temperature using a programmed heating mantle, and the reactor was then stirred magnetically. After reacting at 150 °C for 16 h, gas-phase analysis of the reaction liquid showed complete HMF conversion and a THFDM selectivity of 80.6%.

[0126] The specific embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combining the various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for preparing 2,5-tetrahydrofurandiethanol from 5-hydroxymethylfurfural, characterized in that, 5-Hydroxymethylfurfural reacts with hydrogen as the hydrogen source in the presence of a catalyst to yield 2,5-tetrahydrofurandimethyl. The catalyst comprises an alumina support and an active component, nickel, wherein the molar ratio of Ni / NiO in the active component nickel is 1.00–1.80:1; and the total acidity of the catalyst is 50–200 µmol•g. -1 The catalyst has a specific surface area of ​​30~150 m². 2 / g; the pore volume of the catalyst is 0.02~0.12 cm³. 3 / g.

2. The method according to claim 1, characterized in that, The molar ratio of Ni / NiO in the active component nickel is 1.10~1.40:

1.

3. The method according to claim 1, characterized in that, The catalyst, based on the mass of the alumina support, has a nickel content (calculated as Ni) of 2wt% to 30wt%.

4. The method according to claim 3, characterized in that, The catalyst, based on the mass of the alumina support, has a nickel content of 4wt% to 15wt% (calculated as Ni) as the active component.

5. The method according to claim 1, characterized in that, The total acidity of the catalyst is 60~150 µmol•g. -1 ; And / or, the specific surface area of ​​the catalyst is 35~100 m². 2 / g; And / or, the catalyst has a pore volume of 0.05~0.10 cm³. 3 / g.

6. The method according to claim 1, characterized in that, The method for preparing the catalyst includes the following steps: foaming a nickel metal precursor, an aluminum metal precursor, water, a foaming agent, a foaming aid, and an organic solvent; drying, calcining, and reducing the foamed material to obtain the catalyst.

7. The method according to claim 6, characterized in that, The mass ratio of nickel metal precursor (calculated by the mass of Ni), aluminum metal precursor (calculated by the mass of Al2O3), water, foaming agent, foaming agent and organic solvent is 0.02~0.20:1:3~50:0.2~2:0.2~20:1~20.

8. The method according to claim 7, characterized in that, The mass ratio of nickel metal precursor (calculated by the mass of Ni), aluminum metal precursor (calculated by the mass of Al2O3), water, foaming agent, foaming aid, and organic solvent is 0.04~0.17:1:5~30:0.5~1:3~10:2~10.

9. The method according to claim 6, characterized in that, The nickel metal precursor includes one or more of nickel nitrate, nickel acetate, nickel chloride, nickel acetylacetonate, and nickel sulfate; And / or, the aluminum metal precursor includes one or more of aluminum nitrate, aluminum chloride, aluminum sulfate, aluminum isopropoxide, and aluminum acetylacetonate; And / or, the organic solvent is one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, and isobutanol.

10. The method according to claim 9, characterized in that, The nickel metal precursor is at least one of nickel nitrate and nickel acetate; And / or, the aluminum metal precursor is at least one of aluminum nitrate and aluminum acetylacetonate; And / or, the organic solvent is at least one of methanol and ethanol.

11. The method according to claim 6, characterized in that, The foaming agent is at least one selected from N,N'-dimethyl-N,N'-dinitrosoterephthalamide, N,N'-dinitrosopentamethylenetetramine, diazoaminobenzene, azodicarbonamide, and azobisisobutyronitrile.

12. The method according to claim 11, characterized in that, The foaming agent is at least one of N,N'-dimethyl-N,N'-dinitrosoterephthalamide or azodicarbonamide.

13. The method according to claim 6, characterized in that, The foaming agent is a mixture of organic acid and polyol, with a mass ratio of organic acid to polyol of 0.2~5:

1.

14. The method according to claim 13, characterized in that, In the foaming agent, the mass ratio of organic acid to polyol is 0.5~2:

1.

15. The method according to claim 13, characterized in that, The organic acid is one or more of citric acid, lauric acid, salicylic acid, oxalic acid, and acetic acid; And / or, the polyol is one or more of glycerol, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, and diethylene glycol.

16. The method according to claim 15, characterized in that, The organic acid is citric acid; And / or, the polyol is at least one of glycerol and ethylene glycol.

17. The method according to claim 6, characterized in that, The foaming temperature is 20~160℃; the foaming time is 2~20 hours; And / or, the drying temperature is 50~200℃; the drying time is 2~30 hours; And / or, the calcination temperature is 300~650℃; the calcination time is 1~12 hours; and the calcination atmosphere is an oxygen-containing gas.

18. The method according to claim 17, characterized in that, The foaming temperature is 50~100℃; the foaming time is 6~12 hours; And / or, the drying temperature is 60~150℃; the drying time is 3~24 hours.

19. The method according to claim 6, characterized in that, The reduction temperature is 400~1000℃; the reduction time is 2~10 hours.

20. The method according to claim 19, characterized in that, The reduction temperature is 600~900℃; the reduction time is 3~6 hours.

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