Nickel-cobalt bimetallic nanoparticle material for synthesizing tetrahydrofurfuryl alcohol through full hydrogenation as well as preparation method and application of nickel-cobalt bimetallic nanoparticle material

Abstract

The invention discloses a nickel-cobalt bimetallic nanoparticle material for synthesizing tetrahydrofurfuryl alcohol through full hydrogenation as well as a preparation method and application of the nickel-cobalt bimetallic nanoparticle material. The method comprises the following steps: dissolving nickel acetate tetrahydrate and cobalt acetate tetrahydrate in absolute ethyl alcohol, carrying out ultrasonic treatment, adding an ethanol solution in which polyvinylpyrrolidone is dissolved, carrying out ultrasonic treatment, putting into a preheated oil bath pan, standing, refluxing, centrifuging, and taking precipitate, so as to obtain NiCo-precursor; the preparation method comprises the following steps: adding NiCo-precursor and dopamine hydrochloride into an ethanol solution of tris (hydroxymethyl) aminomethane, putting into an oil bath pan, uniformly stirring, centrifuging, washing and drying to obtain NiCo (at) PDA; and calcining in an inert atmosphere to obtain the catalyst. The nickel-cobalt bimetallic nanoparticle material is simple in preparation process, mild in reaction condition, high in catalyst activity, easy to separate and good in cycling stability, and is expected to show good application potential in industrial application.

Description

Technical Field

[0001] The present invention relates to the technical field of non-noble metal catalysts, and particularly relates to a preparation method of a nickel-cobalt bimetallic nanoparticle material for the total hydrogenation synthesis of tetrahydrofurfuryl alcohol. Background Art

[0002] Biomass is a renewable organic carbon resource, and people have shown great interest in catalytically converting biomass and its derivatives into value-added chemicals and biofuels, which helps to alleviate energy and environmental crises and promote sustainable development. Furfural, as a biomass derivative, is mainly obtained by the hydrolysis and dehydration of xylose under acidic conditions. The catalytic hydrogenation of furfural can produce various high-value-added compounds. Tetrahydrofurfuryl alcohol is an important downstream product of furfural, and its main applications are the synthesis of special chemicals such as dihydropyran, and it can also be used as a biofuel, fuel additive, diesel additive, and environmental solvent.

[0003] The selective hydrogenation of furfural to tetrahydrofurfuryl alcohol using a catalyst is a relatively common method. The 0.97% PdPt / TiO2 catalyst synthesized by Albilali (Albilali R, Douthwaite M, He Q, et al. The selective hydrogenation of furfural over supported palladium nanoparticle catalysts prepared by sol-immobilisation: effect of catalyst support and reaction conditions[J]. Catalysis Science & Technology, 2018, 8:252-267.) and others achieved a tetrahydrofurfuryl alcohol yield of 95% under the conditions of 30 °C, 0.3 MPa H2, and 4 h. The reaction conditions are mild and the product yield is high. However, the high prices and natural scarcity of the noble metals Pd and Pt are not conducive to large-scale applications. Chinese invention patent CN117603165A uses a Cu-Pd / HY supported catalyst to prepare tetrahydrofurfuryl alcohol, with good catalytic activity and selectivity. However, the purchase cost of the noble metal Pd is relatively expensive, which is not conducive to commercial applications. The process of catalytic hydrogenation of furfural to tetrahydrofurfuryl alcohol using the NiCoAl / C catalyst in Chinese invention patent CN117563600B is relatively complex, and the catalyst has problems such as difficult separation and low recycling rate. Li (Li S, Wang Y, Gao L J, et al. Short channeled Ni-Co / SBA-15 catalysts for highly selective hydrogenation of biomass-derived furfural to tetrahydrofurfuryl alcohol[J]. Microporous and Mesoporous Materials, 2018, 262:154-165.) and others used a Ni-Co / SBA-15 (molar ratio of Ni to Co is 0.67) catalyst to completely hydrogenate furfural to tetrahydrofurfuryl alcohol. The reaction temperature was 90 °C, the H2 pressure was 5 MPa, and the reaction time was 2 h. The furfural conversion rate was 100%, and the yield of tetrahydrofurfuryl alcohol was 92.1%. This process has problems such as high hydrogen pressure, harsh conditions, and complex catalyst preparation, which are not conducive to the efficient development of industrial production.

[0004] The noble metal catalysts used in the reported tetrahydrofurfuryl alcohol production process have the disadvantages of high cost and low reserves, which limit their large-scale application. The non-noble metal catalysts used have problems such as low recycling efficiency, complex production methods, and greater environmental impact. It is highly desirable to develop a non-noble metal-based catalyst that is easily obtainable, inexpensive, and highly catalytically active for the selective hydrogenation of furfural to tetrahydrofurfuryl alcohol, which is of great significance for significantly improving current energy technologies. Summary of the Invention

[0005] The object of the present invention is to provide a preparation method of a nickel-cobalt bimetallic nanoparticle material for the total hydrogenation synthesis of tetrahydrofurfuryl alcohol. In the nickel-cobalt bimetallic nanoparticle material prepared by the present invention, the synergistic effect of Ni and Co exhibits strong hydrogenation ability, with good activity and high selectivity. The present invention provides a non-noble metal-based catalyst that is easily obtainable, inexpensive, and highly catalytically active for the total hydrogenation of furfural to tetrahydrofurfuryl alcohol. The reaction temperature is 80-120 °C, the reaction time is 6-30 h, the hydrogen pressure is 0.2-3.0 MPa, the highest conversion rate of furfural reaches 99%, and the yield of tetrahydrofurfuryl alcohol reaches 99%. The reaction process involved in the present invention has the advantages of being recyclable, simple to operate, and mild reaction conditions, while also having high catalytic activity and high selectivity, and a high yield of the target product.

[0006] The object of the present invention can be achieved through the following technical solutions:

[0007] A preparation method of a nickel-cobalt bimetallic nanoparticle material for the total hydrogenation synthesis of tetrahydrofurfuryl alcohol. The preparation of the catalyst specifically includes the following steps:

[0008] (1) Nickel acetate tetrahydrate and cobalt acetate tetrahydrate are added to absolute ethanol and dissolved uniformly by ultrasonic treatment to obtain a metal salt mixed solution; polyvinylpyrrolidone is added to absolute ethanol and dissolved uniformly by ultrasonic treatment to obtain a transparent colorless solution;

[0009] (2) The metal salt mixed solution described in step (1) is mixed uniformly with the transparent colorless solution, placed in a preheated oil bath, allowed to stand and reflux, centrifuged to collect the precipitate, washed and dried to obtain a precursor of the nickel-cobalt bimetallic nanoparticle material, namely NiCo-precursor;

[0010] (3) The NiCo-precursor prepared in step (2) and dopamine hydrochloride are added to an ethanol solution of tris(hydroxymethyl)aminomethane, placed in a preheated oil bath, stirred evenly, centrifuged, washed and dried to obtain a core-shell composite material, namely NiCo@PDA.

[0011] (4) The NiCo@PDA material prepared in step (3) is heated for calcination treatment under an inert atmosphere to obtain a nickel-cobalt bimetallic nanoparticle material, namely NiCo NPs / NC.

[0012] Further, in step (1), the ultrasonic dissolution and homogenization are carried out at room temperature.

[0013] Further, in step (1), the molar ratio of nickel acetate tetrahydrate to cobalt acetate tetrahydrate is 1:2 to 3:1; in the metal salt mixed solution, the concentration of nickel acetate tetrahydrate is 0.01 to 0.05 mol / L, and the concentration of cobalt acetate tetrahydrate is 0.01 to 0.05 mol / L; the solubility of the transparent colorless solution is 0.0005 to 0.0010 mol / L.

[0014] Further, in step (2), the volume ratio of the metal salt mixed solution to the transparent colorless solution is 1:2 to 2:1; the static reflux time is 10 to 20 h; the static reflux temperature is 60 to 100 °C.

[0015] Further, in steps (2) and (3), the centrifuge speed required for centrifuging the solution is 4000 to 6000 rpm, and the time is 2 min; the washing is carried out with absolute ethanol.

[0016] Further, in steps (2) and (3), the drying is carried out in a drying oven, the drying temperature is 50 to 80 °C, and the drying time is 12 to 24 h.

[0017] Further, in step (3), the mass ratio of NiCo-precursor to dopamine hydrochloride is 1:(0.5 to 3.0); the concentration of tris(hydroxymethyl)aminomethane ethanol solution is 0.005 to 0.020 mol / L.

[0018] Further, in step (3), the stirring time is 1 to 5 h; the stirring temperature is 50 to 80 °C.

[0019] Further, in step (4), the inert atmosphere is nitrogen; the temperature of the calcination treatment is 300 to 800 °C, the time of the calcination treatment is 0.5 to 2 h, and the heating rate is 0.5 to 3 °C / min.

[0020] The nickel-cobalt bimetallic nanoparticle material described in the present invention is applied to the full hydrogenation synthesis of tetrahydrofurfuryl alcohol, including the following steps:

[0021] (1) Add furfural, nickel-cobalt bimetallic nanoparticle material and deionized water into the reaction kettle in sequence, introduce hydrogen with a pressure of 0.2 - 3.0 MPa, and place the reaction kettle on the heating furnace; the mass ratio of furfural to the nickel-cobalt bimetallic nanoparticle material catalyst is 1:(0.3 - 1.5), and the mass ratio of furfural to deionized water is 1:(50 - 100);

[0022] (2) Set the stirring speed at 600 - 1000 rpm, the reaction temperature at 80 - 120 °C, and the constant-temperature reaction time at 6 - 30 h;

[0023] (3) After the reaction is completed, wait for the reaction kettle to cool to room temperature, and separate the nickel-cobalt bimetallic nanoparticle material from the reaction solution by centrifugation to obtain the product tetrahydrofurfuryl alcohol.

[0024] In the present invention, the highest conversion rate of furfural is 88.4 - 99%, and the yield of tetrahydrofurfuryl alcohol is 89.2 - 99%.

[0025] Compared with the prior art, the technical effects of the present invention are as follows:

[0026] The nickel-cobalt bimetallic nanoparticle material involved in the present invention has the advantages of high catalytic activity, high selectivity and high stability. The reaction conditions for the hydrogenation of furfural to prepare tetrahydrofurfuryl alcohol are mild, the operation is simple, and the yield is high; the reaction temperature is 80 - 120 °C, the reaction time is 6 - 30 h, the hydrogen pressure is 0.2 - 3.0 MPa, the highest conversion rate of furfural is up to 99%, and the yield of tetrahydrofurfuryl alcohol reaches 99%. Secondly, the preparation method of the nickel-cobalt bimetallic nanoparticle material catalyst provided by the present invention is simple, can be recycled, and has good stability. The nickel-cobalt bimetallic nanoparticle material catalyst can be separated from the reaction system by centrifugation, and can be put into the reaction again after being washed with water and dried. The catalyst can still maintain good reaction activity after being recycled many times, and can effectively solve the problems existing in the separation, recovery and reuse of the current catalyst. Description of the Drawings

[0027] Figure 1 is the reaction formula for the hydrogenation of furfural to synthesize tetrahydrofurfuryl alcohol by the nickel-cobalt bimetallic nanoparticle material;

[0028] Figure 2 is the powder X-ray diffraction pattern of the nickel-cobalt bimetallic nanoparticle material;

[0029] Figure 3 is the scanning electron microscope image of the nickel-cobalt bimetallic nanoparticle material, where (a) is the a-nickel-cobalt bimetallic nanoparticle material, (b) is the b-nickel-cobalt bimetallic nanoparticle material, (c) is the c-nickel-cobalt bimetallic nanoparticle material, and (d) is the d-nickel-cobalt bimetallic nanoparticle material;

[0030] Figure 4 It is a transmission electron microscope image of a nickel-cobalt bimetallic nanoparticle material, where (a) is the a-nickel-cobalt bimetallic nanoparticle material, (b) is the b-nickel-cobalt bimetallic nanoparticle material, (c) is the c-nickel-cobalt bimetallic nanoparticle material, and (d) is the d-nickel-cobalt bimetallic nanoparticle material;

[0031] Figure 5 It is the performance test result diagram of Example 5;

[0032] Figure 6 It is the gas chromatogram of Example 5;

[0033] Figure 7 It is the gas chromatography-mass spectrometry diagram of Example 5. Detailed implementation mode

[0034] The present invention will be further described below through examples, but the patent rights are not limited to these examples.

[0035] Example 1

[0036] In a 250 mL round-bottom flask, 1.3 mmol of nickel acetate tetrahydrate and 1.3 mmol of cobalt acetate tetrahydrate were added to 50 mL of absolute ethanol, and ultrasonically dissolved evenly to obtain a metal salt mixed solution; 0.0375 mmol of polyvinylpyrrolidone was added to 50 mL of absolute ethanol, and ultrasonically dissolved evenly to obtain a transparent colorless solution; the transparent colorless solution was added to the metal salt mixed solution, mixed evenly, placed in an oil bath preheated to 90 °C, allowed to stand and reflux for 16 h, centrifuged to collect the precipitate, washed and dried at 60 °C for 24 h to obtain a precursor of the nickel-cobalt bimetallic nanoparticle material, namely NiCo-precursor. 40 mg of NiCo-precursor and 100 mg of dopamine hydrochloride were added to an ethanol solution of 0.010 mol / L tris(hydroxymethyl)aminomethane, placed in an oil bath preheated to 60 °C, stirred for 2 h, centrifuged, washed and dried at 60 °C for 24 h to obtain a core-shell composite material, namely NiCo@PDA. The NiCo@PDA material was heated to 450 °C at a rate of 1 °C / min in a nitrogen atmosphere and calcined for 1.5 h to obtain the a-nickel-cobalt bimetallic nanoparticle material (a-NiCo NPs / NC).

[0037] Figure 2 It is the powder X-ray diffraction pattern of the a-nickel-cobalt bimetallic nanoparticle material obtained in this example. In the figure, the a-nickel-cobalt bimetallic nanoparticle material shows three characteristic diffraction peaks at 44.2°, 51.6°, and 75.9°, corresponding to the characteristic peaks of the Ni-Co alloy.

[0038] Figure 3Figure a is the scanning electron microscope image of the a-nickel cobalt bimetallic nanoparticle material obtained in this example. It can be seen from the figure that the material has the morphological characteristics of a prism, with a size of about 700-800 nm.

[0039] Figure 4 Figure a is the transmission electron microscope image of the a-nickel cobalt bimetallic nanoparticle material obtained in this example. It can be seen from the figure that the material is a hollow carbon shell containing nanoparticles, the thickness of the shell is about 20 nm, and the size is about 700-800 nm.

[0040] Example 2

[0041] In a 250 mL round-bottom flask, 1.0 mmol of nickel acetate tetrahydrate and 2.0 mmol of cobalt acetate tetrahydrate were added to 50 mL of absolute ethanol, and ultrasonic dissolution was carried out to obtain a uniform metal salt mixed solution; 0.025 mmol of polyvinylpyrrolidone was added to 50 mL of absolute ethanol, and ultrasonic dissolution was carried out to obtain a transparent colorless solution; the transparent colorless solution was added to the metal salt mixed solution, mixed evenly, placed in an oil bath preheated to 90 °C, allowed to stand and reflux for 16 h, centrifuged to collect the precipitate, washed and dried at 60 °C for 24 h to obtain the precursor of the nickel cobalt bimetallic nanoparticle material, namely NiCo-precursor. 40 mg of NiCo-precursor and 100 mg of dopamine hydrochloride were added to an ethanol solution of 0.010 mol / L tris(hydroxymethyl)aminomethane, placed in an oil bath preheated to 60 °C, stirred for 2 h, centrifuged, washed and dried at 60 °C for 24 h to obtain the core-shell composite material, namely NiCo@PDA. The NiCo@PDA material was heated to 350 °C at a rate of 1 °C / min under a nitrogen atmosphere and calcined for 2 h to obtain the b-nickel cobalt bimetallic nanoparticle material (b-NiCo NPs / NC).

[0042] Figure 2 Figure b is the powder X-ray diffraction pattern of the b-nickel cobalt bimetallic nanoparticle material obtained in this example. In the figure, the b-nickel cobalt bimetallic nanoparticle material shows three characteristic diffraction peaks at 44.2°, 51.6°, and 75.9°, corresponding to the characteristic peaks of the Ni-Co alloy.

[0043] Figure 3 Figure b is the scanning electron microscope image of the b-nickel cobalt bimetallic nanoparticle material obtained in this example. It can be seen from the figure that the material has the morphological characteristics of a prism, with a size of about 700-800 nm.

[0044] Figure 4Figure b is the transmission electron microscope image of the b-nickel cobalt bimetallic nanoparticle material obtained in this example. It can be seen from the figure that the material is a hollow carbon shell containing nanoparticles. The thickness of the shell is about 20 nm, and the size is about 700 - 800 nm.

[0045] Example 3

[0046] In a 250 mL round-bottom flask, 1.5 mmol of nickel acetate tetrahydrate and 1.0 mmol of cobalt acetate tetrahydrate were added to 50 mL of absolute ethanol and dissolved uniformly by ultrasonic treatment to obtain a metal salt mixed solution; 0.05 mmol of polyvinylpyrrolidone was added to 50 mL of absolute ethanol and dissolved uniformly by ultrasonic treatment to obtain a transparent colorless solution; the transparent colorless solution was added to the metal salt mixed solution, mixed uniformly, placed in an oil bath preheated to 90 °C, allowed to stand and reflux for 16 h, centrifuged to collect the precipitate, washed and dried at 60 °C for 24 h to obtain the precursor of the nickel cobalt bimetallic nanoparticle material, namely NiCo-precursor. 40 mg of NiCo-precursor and 100 mg of dopamine hydrochloride were added to an ethanol solution of 0.010 mol / L tris(hydroxymethyl)aminomethane, placed in an oil bath preheated to 60 °C, stirred for 2 h, centrifuged, washed and dried at 60 °C for 24 h to obtain the core-shell composite material, namely NiCo@PDA. The NiCo@PDA material was heated to 500 °C at a rate of 2 °C / min in a nitrogen atmosphere and calcined for 1.0 h to obtain the c-nickel cobalt bimetallic nanoparticle material (c-NiCo NPs / NC).

[0047] Figure 2 Figure c is the powder X-ray diffraction pattern of the c-nickel cobalt bimetallic nanoparticle material obtained in this example. In the figure, the c-nickel cobalt bimetallic nanoparticle material shows three characteristic diffraction peaks at 44.2°, 51.6°, and 75.9°, corresponding to the characteristic peaks of the Ni-Co alloy.

[0048] Figure 3 Figure c is the scanning electron microscope image of the c-nickel cobalt bimetallic nanoparticle material obtained in this example. It can be seen from the figure that the material has the morphological characteristics of a prism, and the size is about 700 - 800 nm.

[0049] Figure 4 Figure c is the transmission electron microscope image of the c-nickel cobalt bimetallic nanoparticle material obtained in this example. It can be seen from the figure that the material is a hollow carbon shell containing nanoparticles. The thickness of the shell is about 20 nm, and the size is about 700 - 800 nm.

[0050] Example 4

[0051] In a 250 mL round-bottom flask, 2.0 mmol of nickel acetate tetrahydrate and 1.0 mmol of cobalt acetate tetrahydrate were added to 50 mL of absolute ethanol, and ultrasonic dissolution was carried out to obtain a uniform metal salt mixed solution; 0.04 mmol of polyvinylpyrrolidone was added to 50 mL of absolute ethanol, and ultrasonic dissolution was carried out to obtain a transparent colorless solution; the transparent colorless solution was added to the metal salt mixed solution, mixed evenly, placed in an oil bath preheated to 90 °C, and left to reflux for 16 h. The precipitate was obtained by centrifugation, washed and dried at 60 °C for 24 h to obtain a precursor of the nickel-cobalt bimetallic nanoparticle material, namely NiCo-precursor. 40 mg of NiCo-precursor and 100 mg of dopamine hydrochloride were added to an ethanol solution of 0.010 mol / L tris(hydroxymethyl)aminomethane, placed in an oil bath preheated to 60 °C, stirred for 2 h, centrifuged, washed and dried at 60 °C for 24 h to obtain a core-shell composite material, namely NiCo@PDA. The NiCo@PDA material was heated to 600 °C at a rate of 3 °C / min in a nitrogen atmosphere and calcined for 0.5 h to obtain the d-nickel-cobalt bimetallic nanoparticle material (d-NiCo NPs / NC).

[0052] Figure 2 is the powder X-ray diffraction pattern of the d-nickel-cobalt bimetallic nanoparticle material obtained in this example. In the figure, the d-nickel-cobalt bimetallic nanoparticle material exhibits three characteristic diffraction peaks at 44.2°, 51.6°, and 75.9°, corresponding to the characteristic peaks of the Ni-Co alloy.

[0053] Figure 3 d in is the scanning electron microscope image of the d-nickel-cobalt bimetallic nanoparticle material obtained in this example. It can be seen from the figure that the material has the morphological characteristics of a prism, and the size is about 700-800 nm.

[0054] Figure 4 d in is the transmission electron microscope image of the d-nickel-cobalt bimetallic nanoparticle material obtained in this example. It can be seen from the figure that the material is a hollow carbon shell containing nanoparticles, the thickness of the shell is about 20 nm, and the size is about 700-800 nm.

[0055] Example 5

[0056] Performance test of the nickel-cobalt bimetallic nanoparticle material for the catalytic full hydrogenation of furfural to tetrahydrofurfuryl alcohol.

[0057] In the reaction kettle, 0.1 g of furfural and 0.05 g of the a-nickel-cobalt bimetallic nanoparticle material were added in sequence, stirred and heated to the reaction temperature of 100 °C, and reacted at a constant temperature for 24 h. After the reaction, the a-nickel-cobalt bimetallic nanoparticle material was separated by centrifugation, and the reaction solution was analyzed by gas chromatography. The conversion rate of furfural was 99%, and the yield of tetrahydrofurfuryl alcohol was 99.5%.

[0058] Figure 5 It is the performance test result diagram of this embodiment. Under the given reaction conditions, the conversion rate of the substrate furfural slowly increases with the prolongation of the reaction time. After the reaction proceeds for 24 hours, furfural is basically completely converted. During the reaction process, as time continues to increase, the yield of the target product tetrahydrofurfuryl alcohol also gradually increases. After the reaction proceeds for 18 hours, the yield of tetrahydrofurfuryl alcohol exceeds 90%; when the reaction reaches 24 hours, the yield is as high as 99%.

[0059] Figure 6 and Figure 7 It is the gas chromatography - mass spectrometry diagram of this embodiment. It can be seen from the figure that only the target product tetrahydrofurfuryl alcohol is detected in the reaction solution, and almost no substrate furfural is detected, which indicates that under the given reaction conditions, the substrate furfural is almost completely converted. In addition, no possible by - products are detected in the reaction solution, which indicates that this reaction system has extremely high selectivity for tetrahydrofurfuryl alcohol. From the ion fragmentation diagram, the structural fragment situation of the prepared tetrahydrofurfuryl alcohol can be revealed in detail, and these structural fragments are completely consistent with the standard gas chromatography - mass spectrometry diagram of tetrahydrofurfuryl alcohol.

[0060] Example 6

[0061] Performance test of nickel - cobalt bimetallic nanoparticle material for catalytic full - hydrogenation of furfural to synthesize tetrahydrofurfuryl alcohol.

[0062] In the reaction kettle, 0.1 g of furfural and 0.10 g of α - nickel - cobalt bimetallic nanoparticle material were added in sequence, stirred, heated and raised the temperature to the reaction temperature of 110 °C, and kept the temperature constant for reaction for 20 h. After the reaction ended, the α - nickel - cobalt bimetallic nanoparticle material was separated by centrifugation, and the reaction solution was analyzed by gas chromatography. The conversion rate of furfural was 98.2%, and the yield of tetrahydrofurfuryl alcohol was 99.1%.

[0063] Example 7

[0064] Performance test of nickel - cobalt bimetallic nanoparticle material for catalytic full - hydrogenation of furfural to synthesize tetrahydrofurfuryl alcohol.

[0065] In the reaction kettle, 0.1 g of furfural and 0.05 g of α - nickel - cobalt bimetallic nanoparticle material were added in sequence, stirred, heated and raised the temperature to the reaction temperature of 100 °C, and kept the temperature constant for reaction for 12 h. After the reaction ended, the α - nickel - cobalt bimetallic nanoparticle material was separated by centrifugation, and the reaction solution was analyzed by gas chromatography. The conversion rate of furfural was 93.5%, and the yield of tetrahydrofurfuryl alcohol was 76.8%.

[0066] Example 8

[0067] Performance test of nickel - cobalt bimetallic nanoparticle material for catalytic full - hydrogenation of furfural to synthesize tetrahydrofurfuryl alcohol.

[0068] In a reaction kettle, 0.1 g of furfural and 0.03 g of α-nickel cobalt bimetallic nanoparticle material were added in sequence. The mixture was stirred and heated to the reaction temperature of 120 °C and reacted at a constant temperature for 24 h. After the reaction, the α-nickel cobalt bimetallic nanoparticle material was separated by centrifugation, and the reaction solution was analyzed by gas chromatography. The conversion rate of furfural was 99%, and the yield of tetrahydrofurfural was 93.3%.

[0069] Example 9

[0070] Performance test of nickel cobalt bimetallic nanoparticle material in the catalytic full hydrogenation of furfural to synthesize tetrahydrofurfuryl alcohol.

[0071] In a reaction kettle, 0.1 g of furfural and 0.08 g of α-nickel cobalt bimetallic nanoparticle material were added in sequence. The mixture was stirred and heated to the reaction temperature of 80 °C and reacted at a constant temperature for 18 h. After the reaction, the α-nickel cobalt bimetallic nanoparticle material was separated by centrifugation, and the reaction solution was analyzed by gas chromatography. The conversion rate of furfural was 91.2%, and the yield of tetrahydrofurfural was 82.5%.

[0072] Example 10

[0073] Performance test of nickel cobalt bimetallic nanoparticle material in the catalytic full hydrogenation of furfural to synthesize tetrahydrofurfuryl alcohol.

[0074] In a reaction kettle, 0.1 g of furfural and 0.04 g of α-nickel cobalt bimetallic nanoparticle material were added in sequence. The mixture was stirred and heated to the reaction temperature of 90 °C and reacted at a constant temperature for 30 h. After the reaction, the α-nickel cobalt bimetallic nanoparticle material was separated by centrifugation, and the reaction solution was analyzed by gas chromatography. The conversion rate of furfural was 99%, and the yield of tetrahydrofurfural was 96.9%.

[0075] Example 11

[0076] Performance test of nickel cobalt bimetallic nanoparticle material in the catalytic full hydrogenation of furfural to synthesize tetrahydrofurfuryl alcohol.

[0077] In a reaction kettle, 0.1 g of furfural and 0.03 g of α-nickel cobalt bimetallic nanoparticle material were added in sequence. The mixture was stirred and heated to the reaction temperature of 110 °C and reacted at a constant temperature for 18 h. After the reaction, the α-nickel cobalt bimetallic nanoparticle material was separated by centrifugation, and the reaction solution was analyzed by gas chromatography. The conversion rate of furfural was 97.6%, and the yield of tetrahydrofurfural was 89.3%.

[0078] Example 12

[0079] Performance test of nickel cobalt bimetallic nanoparticle material in the catalytic full hydrogenation of furfural to synthesize tetrahydrofurfuryl alcohol.

[0080] In a reaction kettle, 0.1 g of furfural and 0.05 g of α-nickel cobalt bimetallic nanoparticle material were successively added, stirred and heated to a reaction temperature of 80 °C, and reacted at a constant temperature for 24 h. After the reaction, the α-nickel cobalt bimetallic nanoparticle material was separated by centrifugation, and the reaction solution was analyzed by gas chromatography. The conversion rate of furfural was 96.6%, and the yield of tetrahydrofurfural was 88.7%.

[0081] Example 13

[0082] Performance test of nickel cobalt bimetallic nanoparticle material in the catalytic full hydrogenation of furfural to synthesize tetrahydrofurfuryl alcohol.

[0083] In a reaction kettle, 0.1 g of furfural and 0.04 g of β-nickel cobalt bimetallic nanoparticle material were successively added, stirred and heated to a reaction temperature of 80 °C, and reacted at a constant temperature for 30 h. After the reaction, the β-nickel cobalt bimetallic nanoparticle material was separated by centrifugation, and the reaction solution was analyzed by gas chromatography. The conversion rate of furfural was 92.2%, and the yield of tetrahydrofurfural was 82.4%.

[0084] Example 14

[0085] Performance test of nickel cobalt bimetallic nanoparticle material in the catalytic full hydrogenation of furfural to synthesize tetrahydrofurfuryl alcohol.

[0086] In a reaction kettle, 0.1 g of furfural and 0.04 g of β-nickel cobalt bimetallic nanoparticle material were successively added, stirred and heated to a reaction temperature of 110 °C, and reacted at a constant temperature for 20 h. After the reaction, the β-nickel cobalt bimetallic nanoparticle material was separated by centrifugation, and the reaction solution was analyzed by gas chromatography. The conversion rate of furfural was 97.8%, and the yield of tetrahydrofurfural was 95.1%.

[0087] Example 15

[0088] Performance test of nickel cobalt bimetallic nanoparticle material in the catalytic full hydrogenation of furfural to synthesize tetrahydrofurfuryl alcohol.

[0089] In a reaction kettle, 0.1 g of furfural and 0.03 g of β-nickel cobalt bimetallic nanoparticle material were successively added, stirred and heated to a reaction temperature of 90 °C, and reacted at a constant temperature for 24 h. After the reaction, the β-nickel cobalt bimetallic nanoparticle material was separated by centrifugation, and the reaction solution was analyzed by gas chromatography. The conversion rate of furfural was 96.4%, and the yield of tetrahydrofurfural was 91.2%.

[0090] Example 16

[0091] Performance test of nickel cobalt bimetallic nanoparticle material in the catalytic full hydrogenation of furfural to synthesize tetrahydrofurfuryl alcohol.

[0092] In a reaction kettle, 0.1 g of furfural and 0.08 g of b-nickel-cobalt bimetallic nanoparticle material were successively added, stirred and heated to the reaction temperature of 120 °C, and reacted at a constant temperature for 18 h. After the reaction, the b-nickel-cobalt bimetallic nanoparticle material was separated by centrifugation, and the reaction solution was analyzed by gas chromatography. The conversion rate of furfural was 99%, and the yield of tetrahydrofurfural was 90.5%.

[0093] Example 17

[0094] Performance test of nickel-cobalt bimetallic nanoparticle material in the catalytic full hydrogenation of furfural to synthesize tetrahydrofurfuryl alcohol.

[0095] In a reaction kettle, 0.1 g of furfural and 0.05 g of b-nickel-cobalt bimetallic nanoparticle material were successively added, stirred and heated to the reaction temperature of 100 °C, and reacted at a constant temperature for 30 h. After the reaction, the b-nickel-cobalt bimetallic nanoparticle material was separated by centrifugation, and the reaction solution was analyzed by gas chromatography. The conversion rate of furfural was 94.4%, and the yield of tetrahydrofurfural was 93.6%.

[0096] Example 18

[0097] Performance test of nickel-cobalt bimetallic nanoparticle material in the catalytic full hydrogenation of furfural to synthesize tetrahydrofurfuryl alcohol.

[0098] In a reaction kettle, 0.1 g of furfural and 0.10 g of b-nickel-cobalt bimetallic nanoparticle material were successively added, stirred and heated to the reaction temperature of 100 °C, and reacted at a constant temperature for 12 h. After the reaction, the b-nickel-cobalt bimetallic nanoparticle material was separated by centrifugation, and the reaction solution was analyzed by gas chromatography. The conversion rate of furfural was 90.7%, and the yield of tetrahydrofurfural was 75.5%.

[0099] Example 19

[0100] Performance test of nickel-cobalt bimetallic nanoparticle material in the catalytic full hydrogenation of furfural to synthesize tetrahydrofurfuryl alcohol.

[0101] In a reaction kettle, 0.1 g of furfural and 0.08 g of b-nickel-cobalt bimetallic nanoparticle material were successively added, stirred and heated to the reaction temperature of 80 °C, and reacted at a constant temperature for 24 h. After the reaction, the b-nickel-cobalt bimetallic nanoparticle material was separated by centrifugation, and the reaction solution was analyzed by gas chromatography. The conversion rate of furfural was 92.4%, and the yield of tetrahydrofurfural was 81.6%.

[0102] Example 20

[0103] Performance test of nickel-cobalt bimetallic nanoparticle material in the catalytic full hydrogenation of furfural to synthesize tetrahydrofurfuryl alcohol.

[0104] In a reaction kettle, 0.1 g of furfural and 0.08 g of c-nickel cobalt bimetallic nanoparticle material were added in sequence. After stirring and heating to the reaction temperature of 120 °C, the reaction was carried out at a constant temperature for 12 h. After the reaction, the c-nickel cobalt bimetallic nanoparticle material was separated by centrifugation, and the reaction solution was analyzed by gas chromatography. The conversion rate of furfural was 91.4%, and the yield of tetrahydrofurfural was 80.8%.

[0105] Example 21

[0106] Performance test of nickel cobalt bimetallic nanoparticle material in the catalytic full hydrogenation of furfural to synthesize tetrahydrofurfuryl alcohol.

[0107] In a reaction kettle, 0.1 g of furfural and 0.04 g of c-nickel cobalt bimetallic nanoparticle material were added in sequence. After stirring and heating to the reaction temperature of 90 °C, the reaction was carried out at a constant temperature for 18 h. After the reaction, the c-nickel cobalt bimetallic nanoparticle material was separated by centrifugation, and the reaction solution was analyzed by gas chromatography. The conversion rate of furfural was 92.6%, and the yield of tetrahydrofurfural was 81.7%.

[0108] Example 22

[0109] Performance test of nickel cobalt bimetallic nanoparticle material in the catalytic full hydrogenation of furfural to synthesize tetrahydrofurfuryl alcohol.

[0110] In a reaction kettle, 0.1 g of furfural and 0.03 g of c-nickel cobalt bimetallic nanoparticle material were added in sequence. After stirring and heating to the reaction temperature of 100 °C, the reaction was carried out at a constant temperature for 24 h. After the reaction, the c-nickel cobalt bimetallic nanoparticle material was separated by centrifugation, and the reaction solution was analyzed by gas chromatography. The conversion rate of furfural was 97.3%, and the yield of tetrahydrofurfural was 89.2%.

[0111] Example 23

[0112] Performance test of nickel cobalt bimetallic nanoparticle material in the catalytic full hydrogenation of furfural to synthesize tetrahydrofurfuryl alcohol.

[0113] In a reaction kettle, 0.1 g of furfural and 0.05 g of c-nickel cobalt bimetallic nanoparticle material were added in sequence. After stirring and heating to the reaction temperature of 90 °C, the reaction was carried out at a constant temperature for 12 h. After the reaction, the c-nickel cobalt bimetallic nanoparticle material was separated by centrifugation, and the reaction solution was analyzed by gas chromatography. The conversion rate of furfural was 88.4%, and the yield of tetrahydrofurfural was 75.8%.

[0114] Example 24

[0115] Performance test of nickel cobalt bimetallic nanoparticle material in the catalytic full hydrogenation of furfural to synthesize tetrahydrofurfuryl alcohol.

[0116] In a reaction kettle, 0.1 g of furfural and 0.03 g of c-nickel cobalt bimetallic nanoparticle material were added in sequence, stirred and heated to the reaction temperature of 80 °C, and reacted at a constant temperature for 30 h. After the reaction, the c-nickel cobalt bimetallic nanoparticle material was separated by centrifugation, and the reaction solution was analyzed by gas chromatography. The conversion rate of furfural was 89.9%, and the yield of tetrahydrofurfural was 82.3%.

[0117] Example 25

[0118] Performance test of nickel cobalt bimetallic nanoparticle material for catalytic full hydrogenation of furfural to tetrahydrofurfuryl alcohol.

[0119] In a reaction kettle, 0.1 g of furfural and 0.04 g of c-nickel cobalt bimetallic nanoparticle material were added in sequence, stirred and heated to the reaction temperature of 110 °C, and reacted at a constant temperature for 24 h. After the reaction, the c-nickel cobalt bimetallic nanoparticle material was separated by centrifugation, and the reaction solution was analyzed by gas chromatography. The conversion rate of furfural was 99%, and the yield of tetrahydrofurfural was 99.3%.

[0120] Example 26

[0121] Performance test of nickel cobalt bimetallic nanoparticle material for catalytic full hydrogenation of furfural to tetrahydrofurfuryl alcohol.

[0122] In a reaction kettle, 0.1 g of furfural and 0.05 g of d-nickel cobalt bimetallic nanoparticle material were added in sequence, stirred and heated to the reaction temperature of 100 °C, and reacted at a constant temperature for 18 h. After the reaction, the d-nickel cobalt bimetallic nanoparticle material was separated by centrifugation, and the reaction solution was analyzed by gas chromatography. The conversion rate of furfural was 99%, and the yield of tetrahydrofurfural was 96.7%.

[0123] Example 27

[0124] Performance test of nickel cobalt bimetallic nanoparticle material for catalytic full hydrogenation of furfural to tetrahydrofurfuryl alcohol.

[0125] In a reaction kettle, 0.1 g of furfural and 0.08 g of d-nickel cobalt bimetallic nanoparticle material were added in sequence, stirred and heated to the reaction temperature of 100 °C, and reacted at a constant temperature for 20 h. After the reaction, the d-nickel cobalt bimetallic nanoparticle material was separated by centrifugation, and the reaction solution was analyzed by gas chromatography. The conversion rate of furfural was 99%, and the yield of tetrahydrofurfural was 95.8%.

[0126] Example 28

[0127] Performance test of nickel cobalt bimetallic nanoparticle material for catalytic full hydrogenation of furfural to tetrahydrofurfuryl alcohol.

[0128] In the reactor, 0.1 g of furfural and 0.03 g of d-nickel-cobalt bimetallic nanoparticle material were added in sequence. The mixture was stirred and heated to the reaction temperature of 110 °C and reacted at a constant temperature for 30 h. After the reaction, the d-nickel-cobalt bimetallic nanoparticle material was separated by centrifugation, and the reaction solution was analyzed by gas chromatography. The conversion rate of furfural was 96.4%, and the yield of tetrahydrofurfural was 95.4%.

[0129] Example 29

[0130] Performance test of nickel-cobalt bimetallic nanoparticle material for catalytic full hydrogenation of furfural to tetrahydrofurfuryl alcohol.

[0131] In the reactor, 0.1 g of furfural and 0.10 g of d-nickel-cobalt bimetallic nanoparticle material were added in sequence. The mixture was stirred and heated to the reaction temperature of 120 °C and reacted at a constant temperature for 18 h. After the reaction, the d-nickel-cobalt bimetallic nanoparticle material was separated by centrifugation, and the reaction solution was analyzed by gas chromatography. The conversion rate of furfural was 99%, and the yield of tetrahydrofurfural was 98.8%.

[0132] Example 30

[0133] Performance test of nickel-cobalt bimetallic nanoparticle material for catalytic full hydrogenation of furfural to tetrahydrofurfuryl alcohol.

[0134] In the reactor, 0.1 g of furfural and 0.05 g of d-nickel-cobalt bimetallic nanoparticle material were added in sequence. The mixture was stirred and heated to the reaction temperature of 80 °C and reacted at a constant temperature for 24 h. After the reaction, the d-nickel-cobalt bimetallic nanoparticle material was separated by centrifugation, and the reaction solution was analyzed by gas chromatography. The conversion rate of furfural was 96.3%, and the yield of tetrahydrofurfural was 89.4%.

[0135] The above embodiments of the present invention are merely examples for clearly illustrating the present invention, rather than limitations on the implementation manners of the present invention. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to enumerate all the implementation manners here. Any modifications, equivalent replacements, and improvements made within the spirit and principle of the present invention shall be included within the protection scope of the claims of the present invention.

Claims

1. A preparation method of a nickel-cobalt bimetallic nanoparticle material for the total hydrogenation synthesis of tetrahydrofurfuryl alcohol, characterized in that, It includes the following steps: (1) Add nickel acetate tetrahydrate and cobalt acetate tetrahydrate into absolute ethanol, and ultrasonically dissolve them evenly to obtain a mixed metal salt solution; add polyvinylpyrrolidone into absolute ethanol, and ultrasonically dissolve it evenly to obtain a transparent colorless solution; (2) Mix the mixed metal salt solution obtained in step (1) with the transparent colorless solution evenly, put it into a preheated oil bath, stand and reflux, centrifuge to obtain the precipitate, wash and dry it to obtain the precursor NiCo-precursor of the nickel-cobalt bimetallic nanoparticle material; (3) Add the precursor NiCo-precursor of the nickel-cobalt bimetallic nanoparticle material obtained in step (2) and dopamine hydrochloride into an ethanol solution of tris(hydroxymethyl)aminomethane, put it into a preheated oil bath, stir evenly, centrifuge, wash and dry it to obtain the core-shell composite material NiCo@PDA; (4) Heat the core-shell composite material NiCo@PDA obtained in step (3) for calcination treatment under an inert atmosphere to obtain the nickel-cobalt bimetallic nanoparticle material NiCo NPs / NC.

2. The preparation method of the nickel-cobalt bimetallic nanoparticle material for the total hydrogenation synthesis of tetrahydrofurfuryl alcohol according to claim 1, characterized in that, In step (1), the ultrasonic dissolution is carried out at room temperature.

3. The preparation method of the nickel-cobalt bimetallic nanoparticle material for fully hydrogenating and synthesizing tetrahydrofurfuryl alcohol according to claim 1, characterized in that, In step (1), the molar ratio of nickel acetate tetrahydrate to cobalt acetate tetrahydrate is 1:2 to 3:1; in the mixed metal salt solution, the concentration of nickel acetate tetrahydrate is 0.01 to 0.05 mol / L, and the concentration of cobalt acetate tetrahydrate is 0.01 to 0.05 mol / L; the concentration of the transparent colorless solution is 0.0005 to 0.0010 mol / L.

4. The preparation method of the nickel-cobalt bimetallic nanoparticle material for fully hydrogenating and synthesizing tetrahydrofurfuryl alcohol according to claim 1, characterized in that, In step (2), the volume ratio of the mixed metal salt solution to the transparent colorless solution is 1:2 to 2:1; the standing reflux time is 10 to 20 h; the standing reflux temperature is 60 to 100 °C.

5. The preparation method of the nickel-cobalt bimetallic nanoparticle material for fully hydrogenating and synthesizing tetrahydrofurfuryl alcohol according to claim 1, characterized in that, In steps (2) and (3), the centrifugation speed is 4000 to 6000 rpm, and the time is 1 to 3 min; the washing is carried out with absolute ethanol; The drying is carried out in an oven, the drying temperature is 50 to 80 °C, and the drying time is 12 to 24 h.

6. The preparation method of the nickel-cobalt bimetallic nanoparticle material for the total hydrogenation synthesis of tetrahydrofurfuryl alcohol according to claim 1, characterized in that, In step (3), the mass ratio of the precursor NiCo-precursor of the nickel-cobalt bimetallic nanoparticle material to dopamine hydrochloride is 1:(0.5 to 3.0); the concentration of the tris(hydroxymethyl)aminomethane ethanol solution is 0.005 to 0.020 mol / L.

7. The preparation method of the nickel-cobalt bimetallic nanoparticle material for the total hydrogenation synthesis of tetrahydrofurfuryl alcohol according to claim 1, characterized in that, In step (3), the stirring time is 1 to 5 h; the stirring temperature is 50 to 80 °C.

8. The preparation method of the nickel-cobalt bimetallic nanoparticle material for fully hydrogenating and synthesizing tetrahydrofurfuryl alcohol according to claim 1, characterized in that, In step (4), the inert atmosphere is nitrogen; the temperature of the calcination treatment is 300 to 800 °C, the time of the calcination treatment is 0.5 to 2 h, and the heating rate is 0.5 to 3 °C / min.

9. The nickel-cobalt bimetallic nanoparticle material prepared by the method according to any one of claims 1 to 9.

10. The nickel-cobalt bimetallic nanoparticle material according to claim 9 is applied to the full hydrogenation synthesis of tetrahydrofurfuryl alcohol, characterized in that, It includes the following steps: (1) Furfural, nickel-cobalt bimetallic nanoparticle material and deionized water are successively added into the reaction kettle, hydrogen is introduced with a pressure of 0.2 - 3.0 MPa, and the reaction kettle is placed on the heating furnace; the mass ratio of furfural to the nickel-cobalt bimetallic nanoparticle material catalyst is 1:(0.3 - 1.5), and the mass ratio of furfural to deionized water is 1:(50 - 100); (2) Set the stirring speed at 600 - 1000 rpm, the reaction temperature at 80 - 120 °C, and the constant-temperature reaction time at 6 - 30 h; (3) After the reaction is completed, wait for the reaction kettle to cool to room temperature, and separate the nickel-cobalt bimetallic nanoparticle material from the reaction solution by centrifugation to obtain the product tetrahydrofurfuryl alcohol; The highest conversion rate of furfural is 88.4 - 99%, and the yield of tetrahydrofurfuryl alcohol is 89.2 - 99%.

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