Preparation method and application of nano nickel-based alloy catalyst

Abstract

The invention discloses a preparation method and application of a catalyst for preparing hydrocarbon liquid fuel through grease hydrodeoxygenation, oxyphilic metal elements of tungsten, molybdenum, zirconium and zinc are introduced, oxyphilic metal salt and nickel salt are fully mixed with a carrier according to different proportions and then subjected to ultrasonic treatment, a solvent is subjected to vacuum rotary evaporation under the room temperature condition, and the catalyst is obtained. The supported nano nickel-based alloy catalyst is prepared by roasting at the temperature of 250-400 DEG C and reducing at the temperature of 650-690 DEG C, activation and breakage of C-O bonds of ester compounds under mild conditions are greatly enhanced, and hydrodeoxygenation conversion of the ester compounds under mild conditions is realized by utilizing a nickel metal center with high hydrogen dissociation activity. In addition, the hydrogenolysis side reaction of the nickel metal center to the liquid hydrocarbon product is inhibited, the excellent catalytic performance is shown, the reaction activity is high, the yield of the hydrocarbon target product is high, and the catalyst stability is good.

Description

Technical field:

[0001] The invention relates to the technical field of catalysts for preparing hydrocarbon liquid fuel by hydrodeoxygenation of oils and fats, and in particular to a preparation method and application of a nano nickel-based alloy catalyst. Background technology:

[0002] The use of renewable resources to prepare green liquid fuels is the core way to achieve carbon neutrality in the transportation sector. Including non-edible oils such as jatropha oil, algae oil and waste oil, it is a bio-derived raw material with wide availability, high abundance and low cost. In addition to containing about 10% oxygen, the molecular structure of this type of raw material is very similar to liquid fuels such as diesel. Therefore, it can be upgraded through a simple hydrodeoxygenation (HDO) method to obtain diesel-like hydrocarbons, becoming a very promising green liquid fuel.

[0003] So far, a lot of research has been conducted on the hydrodeoxygenation of oils and fats. However, most studies have pointed out that the reaction temperature of hydrodeoxygenation under solvent-free conditions is relatively harsh, such as a high temperature of more than 380°C. For example, Zhang (Fuel, 2020, 269, 117465) used Ni / HMCM-41 assisted by phosphotungstic acid as a catalyst at a high reaction temperature of 390°C, and the deoxygenation rate of methyl palmitate reached 86%. Therefore, it is very important to develop a high-performance catalyst to achieve further catalytic conversion of long-chain esters. Summary of the invention:

[0004] The purpose of the present invention is to provide a preparation method and application of a catalyst for preparing hydrocarbon liquid fuel by hydrodeoxygenation of oils and fats, which solves the problem that the temperature of the catalyst prepared by the prior art is too high and the deoxygenation rate of methyl palmitate is not high when the catalyst is used for preparing hydrocarbon liquid fuel by hydrodeoxygenation of oils and fats.

[0005] The present invention is achieved through the following technical solutions:

[0006] A method for preparing a nano nickel-based alloy catalyst for preparing hydrocarbon liquid fuel by hydrodeoxygenation of oils and fats, wherein the nano nickel-based alloy catalyst is a supported nano nickel-based alloy, and the active component is one of nickel-tungsten alloy, nickel-molybdenum alloy, nickel-zirconium alloy, and nickel-zinc alloy. The method comprises the following steps:

[0007] 1) dissolving a soluble nickel salt and another soluble metal salt in a solvent to obtain a metal salt solution, adding a carrier to the metal salt solution and ultrasonicating for 5-60 minutes, preferably 20-40 minutes, to prepare a catalyst precursor solution, and then performing vacuum rotary evaporation at room temperature of 5°C-30°C until the solvent is completely volatilized; the solvent is a mixture of methanol, ethanol and deionized water, and the other metal salt is one of tungsten, molybdenum, zirconium and zinc salts;

[0008] 2) calcining the remaining solid after the solution evaporates at 250° C. to 400° C. for 2 h to 8 h to obtain a catalyst precursor;

[0009] 3) The nano nickel-based alloy catalyst precursor is subjected to hydrogen reduction at a temperature of 650° C. to 690° C., preferably 680° C. to 690° C., for a reduction time of 2 h to 8 h, to obtain the supported nano nickel-based alloy catalyst.

[0010] Preferably, the soluble nickel salt is selected from nickel nitrate, nickel acetate and the like.

[0011] Preferably, the other metal salt is selected from one of ammonium metatungstate, ammonium molybdate, zirconium nitrate, zinc nitrate and the like.

[0012] Preferably, in step 1), the total amount of the nickel salt and another soluble metal salt added is calculated based on the total amount of nickel-based alloy elements obtained, and the total loading amount is 10 wt%.

[0013] Preferably, in step 1), the amount of nickel salt added is calculated based on the obtained nickel element, and the nickel loading is 1wt% to 9wt%, preferably 4wt% to 8wt%, more preferably 4wt% to 6wt%, and most preferably 6wt%.

[0014] The carrier is any commercially available carrier material, such as silicon dioxide, aluminum oxide, hydrotalcite, etc.

[0015] The present invention also protects the application of the supported nano nickel-based alloy catalyst obtained by the above preparation method for preparing hydrocarbon liquid fuel by hydrodeoxygenation of oils and fats.

[0016] The reaction conditions are as follows: the reaction temperature is between 260°C and 340°C, the hydrogen pressure is between 1.0MPa and 5.0MPa, and the mass ratio of oil to catalyst is between 15-50.

[0017] Preferably, the reaction temperature is between 270°C and 300°C, the hydrogen pressure is between 2.0MPa and 4.0MPa, and the mass ratio of oil to catalyst is between 20-40.

[0018] The beneficial effects of the present invention are as follows: the present invention introduces oxophilic metal elements such as tungsten, molybdenum, zirconium and zinc, fully mixes soluble oxophilic metal salts and nickel salts with carriers in different proportions, performs ultrasonic treatment, and then vacuum rotary evaporates the solvent at room temperature. The supported nano nickel-based alloy catalyst is prepared through calcination at 250°C to 400°C and reduction at 650°C to 690°C, which greatly enhances the activation and breaking of CO bonds of ester compounds under mild conditions. The nickel metal center with high hydrogen dissociation activity is then used to realize the hydrogenation and deoxygenation conversion of ester compounds under relatively mild conditions, and the hydrogenolysis side reaction of the nickel metal center to liquid hydrocarbon products is suppressed, showing excellent catalytic performance, high reaction activity, high yield of hydrocarbon target products, good catalyst stability and the like. In the absence of solvent and at a reaction temperature of 280°C, the oil and fat hydrogenation and deoxygenation conversion rate is 100%, and the deoxygenation rate is increased by more than 5 times. Description of the drawings:

[0019] Figure 1 This is the XRD diagram of the nano nickel-based alloy catalyst prepared in Example 1 of the present invention.

[0020] Figure 2 The STEM electron microscope and EDX element surface scanning distribution diagrams of the nano nickel-based alloy catalyst prepared in Example 1 of the present invention, wherein A is the STEM diagram, and B, C, and D are the combined diagram of nickel and tungsten elements in the EDX element surface scanning distribution diagram results and the surface scanning element distribution diagrams of nickel and tungsten respectively. Specific implementation method:

[0021] The following is a further description of the present invention, rather than a limitation of the present invention.

[0022] Embodiment 1:

[0023] First, 1.48g of nickel nitrate hexahydrate and 0.266g of ammonium metatungstate were dissolved in a mixture of 40mL of methanol, ethanol and deionized water in a round-bottom flask. Then 5g of silica powder was added to the solution, followed by 30 minutes of ultrasonic treatment. The flask was then connected to a vacuum rotary evaporator and evaporated at room temperature at a rotation speed of 20rpm until all the solvent evaporated. The solid was then ground and calcined at 400℃ at a heating rate of 2℃ / min for 5h, and then reduced with hydrogen at 680℃ for 3h to obtain a nano nickel-tungsten alloy catalyst (recorded as 6wt%Ni-4wt%W).

[0024] The oil hydrodeoxygenation reaction was carried out in a high-pressure mechanical stirring reactor with a volume of 100 mL. Before the reaction, 6 g rapeseed oil and 0.2 g catalyst (6 wt% Ni-4 wt% W) were added to the reactor, and then hydrogen was charged and discharged three times to exhaust the air in the reactor, and finally 3 MPa of hydrogen was charged. The reactor was placed in a heating jacket for heating, and the mechanical stirring speed was 550 rpm. After reacting at 280 ° C for 5 hours, the reaction was stopped, the reactor was taken out and placed in ice water for cooling, and the obtained liquid was centrifuged to separate the catalyst to obtain hydrocarbon products. The product composition was analyzed by gas chromatography, and the performance evaluation results are shown in Table 1.

[0025] Figure 1 : is the XRD pattern of the nano nickel-based alloy catalyst prepared in this embodiment. Figure 1 It can be seen that the prepared catalyst does not have the characteristic diffraction peak of metal nickel, but the diffraction peak of nickel-tungsten alloy (Ni 17 W3), indicating that the main crystal phase of the synthesized catalyst is a nickel-tungsten alloy phase.

[0026] Figure 2 : is the STEM and EDX elemental distribution diagram of the nano nickel-based alloy catalyst prepared in this embodiment. Figure 2 It can be seen that the prepared catalyst is a nano nickel-tungsten alloy catalyst.

[0027] Example 2

[0028] First, 1.973g of nickel nitrate hexahydrate and 0.133g of ammonium metatungstate were dissolved in a mixture of 40mL of methanol, ethanol and deionized water in a round-bottom flask. Then 5g of silica powder was added to the solution, followed by 30 minutes of ultrasonic treatment. The flask was then connected to a vacuum rotary evaporator and evaporated at room temperature at a rotation speed of 20rpm until all the solvent evaporated. The solid was then ground and calcined at 400℃ at a heating rate of 2℃ / min for 5h, and then reduced with hydrogen at 660℃ for 3h to obtain a nano nickel-tungsten alloy catalyst (8wt% Ni-2wt% W).

[0029] The oil hydrodeoxygenation reaction was carried out in a high-pressure mechanical stirring reactor with a volume of 100 mL. Before the reaction, 6 g rapeseed oil and 0.2 g catalyst (8 wt% Ni-2 wt% W) were added to the reactor, and then hydrogen was charged and discharged three times to exhaust the air in the reactor, and finally 3 MPa of hydrogen was charged. The reactor was placed in a heating jacket for heating, and the mechanical stirring speed was 550 rpm. After reacting at 280 ° C for 5 hours, the reaction was stopped, the reactor was taken out and placed in ice water for cooling, and the obtained liquid was centrifuged to separate the catalyst to obtain hydrocarbon products. The product composition was analyzed by gas chromatography, and the performance evaluation results are shown in Table 1.

[0030] Example 3

[0031] First, 0.986g of nickel nitrate hexahydrate and 0.400g of ammonium metatungstate were dissolved in a mixture of 40mL of methanol, ethanol and deionized water in a round-bottom flask. Then 5g of silica powder was added to the solution, followed by 30 minutes of ultrasonic treatment. The flask was then connected to a vacuum rotary evaporator and evaporated at room temperature at a rotation speed of 20rpm until all the solvent evaporated. The solid was then ground and calcined at 400℃ at a heating rate of 2℃ / min for 5h, and then reduced with hydrogen at 690℃ for 3h to obtain a nano nickel-tungsten alloy catalyst (4wt% Ni-6wt% W).

[0032] The oil hydrodeoxygenation reaction was carried out in a high-pressure mechanical stirring reactor with a volume of 100 mL. Before the reaction, 6 g rapeseed oil and 0.2 g catalyst (4 wt% Ni-6 wt% W) were added to the reactor, and then hydrogen was charged and discharged three times to exhaust the air in the reactor, and finally 3 MPa of hydrogen was charged. The reactor was placed in a heating jacket for heating, and the mechanical stirring speed was 550 rpm. After reacting at 280 ° C for 5 hours, the reaction was stopped, the reactor was taken out and placed in ice water for cooling, and the obtained liquid was centrifuged to separate the catalyst to obtain hydrocarbon products. The product composition was analyzed by gas chromatography, and the performance evaluation results are shown in Table 1.

[0033] Example 4

[0034] First, 1.48g of nickel nitrate hexahydrate and 0.408g of ammonium molybdate were dissolved in a mixture of 40mL of methanol, ethanol and deionized water in a round-bottom flask. Then 5g of silica powder was added to the solution, followed by 30 minutes of ultrasonic treatment. The flask was then connected to a vacuum rotary evaporator and evaporated at room temperature at a rotation speed of 20rpm until all the solvent evaporated. The solid was then ground and calcined at 400°C at a heating rate of 2°C / min for 5h, and then reduced with hydrogen at 680°C for 4h to obtain a nano nickel-molybdenum alloy catalyst (6wt% Ni-4wt% Mo).

[0035] The oil hydrodeoxygenation reaction was carried out in a high-pressure mechanical stirring reactor with a volume of 100 mL. Before the reaction, 6 g of rapeseed oil and 0.2 g of catalyst (6 wt% Ni-4 wt% Mo) were added to the reactor, and then hydrogen was charged and discharged three times to exhaust the air in the reactor, and finally 3 MPa of hydrogen was charged. The reactor was placed in a heating jacket for heating, and the mechanical stirring speed was 550 rpm. After reacting at 280 ° C for 5 hours, the reaction was stopped, the reactor was taken out and placed in ice water for cooling, and the obtained liquid was centrifuged to separate the catalyst to obtain hydrocarbon products. The product composition was analyzed by gas chromatography, and the performance evaluation results are shown in Table 1.

[0036] Example 5

[0037] First, 1.48g of nickel nitrate hexahydrate and 0.943g of zirconium nitrate pentahydrate were dissolved in a mixture of 40mL of methanol, ethanol and deionized water in a round-bottom flask. Then 5g of silica powder was added to the solution, followed by 30 minutes of ultrasonic treatment. The flask was then connected to a vacuum rotary evaporator and evaporated at room temperature at a rotation speed of 20rpm until all the solvent evaporated. The solid was then ground and calcined at 400℃ at a heating rate of 2℃ / min for 5h, and then reduced with hydrogen at 680℃ for 4h to obtain a nano nickel-zirconium alloy catalyst (6wt% Ni-4wt% Zr).

[0038] The oil hydrodeoxygenation reaction was carried out in a high-pressure mechanical stirring reactor with a volume of 100 mL. Before the reaction, 6 g rapeseed oil and 0.2 g catalyst (6 wt% Ni-4 wt% Zr) were added to the reactor, and then hydrogen was charged and discharged three times to exhaust the air in the reactor, and finally 3 MPa of hydrogen was charged. The reactor was placed in a heating jacket for heating, and the mechanical stirring speed was 550 rpm. After reacting at 280 ° C for 5 hours, the reaction was stopped, the reactor was taken out and placed in ice water for cooling, and the obtained liquid was centrifuged to separate the catalyst to obtain hydrocarbon products. The product composition was analyzed by gas chromatography, and the performance evaluation results are shown in Table 1.

[0039] Example 6

[0040] First, 1.48g of nickel nitrate hexahydrate and 0.910g of zinc nitrate hexahydrate were dissolved in a mixture of 40mL of methanol, ethanol and deionized water in a round-bottom flask. Then 5g of silica powder was added to the solution, followed by 30 minutes of ultrasonic treatment. The flask was then connected to a vacuum rotary evaporator and evaporated at room temperature at a rotation speed of 20rpm until all the solvent evaporated. The solid was then ground and calcined at 400℃ at a heating rate of 2℃ / min for 5h, and then reduced with hydrogen at 680℃ for 5h to obtain a nano nickel-tungsten alloy catalyst (6wt% Ni-4wt% Zn).

[0041] The oil hydrodeoxygenation reaction was carried out in a 100 mL high-pressure mechanical stirring reactor. Before the reaction, 6 g rapeseed oil and 0.2 g catalyst were added to the reactor, and then hydrogen was charged and discharged three times to exhaust the air in the reactor, and finally 3 MPa of hydrogen was charged. The reactor was placed in a heating jacket for heating, and the mechanical stirring speed was 550 rpm. After reacting at 280 ° C for 5 hours, the reaction was stopped, the reactor was taken out and placed in ice water for cooling, and the obtained liquid was centrifuged to separate the catalyst to obtain hydrocarbon products. The product composition was analyzed by gas chromatography, and the performance evaluation results are shown in Table 1.

[0042] Example 7

[0043] First, 1.48g of nickel nitrate hexahydrate and 0.266g of ammonium metatungstate were dissolved in a mixture of 40mL of methanol, ethanol and deionized water in a round-bottom flask. Then 5g of alumina powder was added to the solution, followed by 30 minutes of ultrasonic treatment. The flask was then connected to a vacuum rotary evaporator and evaporated at room temperature at a rotation speed of 20rpm until all the solvent evaporated. The solid was then ground and calcined at 400℃ at a heating rate of 2℃ / min for 5h, and then reduced with hydrogen at 680℃ for 3h to obtain a nano nickel-tungsten alloy catalyst (6wt% Ni-4wt% W).

[0044] The oil hydrodeoxygenation reaction was carried out in a 100 mL high-pressure mechanical stirring reactor. Before the reaction, 6 g rapeseed oil and 0.2 g catalyst were added to the reactor, and then hydrogen was charged and discharged three times to exhaust the air in the reactor, and finally 3 MPa of hydrogen was charged. The reactor was placed in a heating jacket for heating, and the mechanical stirring speed was 550 rpm. After reacting at 280 ° C for 5 hours, the reaction was stopped, the reactor was taken out and placed in ice water for cooling, and the obtained liquid was centrifuged to separate the catalyst to obtain hydrocarbon products. The product composition was analyzed by gas chromatography, and the performance evaluation results are shown in Table 1.

[0045] Comparative Example 1

[0046] First, 2.466 g of nickel nitrate hexahydrate was dissolved in 40 mL of methanol, ethanol and deionized water in a round-bottom flask. Then 5 g of silica powder was added to the solution, followed by 30 minutes of ultrasonic treatment. The flask was then connected to a vacuum rotary evaporator and evaporated at room temperature at a rotation speed of 20 rpm until all the solvent evaporated. The solid was then ground and calcined at 400 ° C at a heating rate of 2 ° C / min for 5 h, and then reduced with hydrogen at a temperature of 650 ° C to obtain a nano nickel catalyst (10wt% Ni).

[0047] The oil hydrodeoxygenation reaction was carried out in a 100 mL high-pressure mechanical stirring reactor. Before the reaction, 6 g rapeseed oil and 0.2 g catalyst were added to the reactor, and then hydrogen was charged and discharged three times to exhaust the air in the reactor, and finally 3 MPa of hydrogen was charged. The reactor was placed in a heating jacket for heating, and the mechanical stirring speed was 550 rpm. After reacting at 280 ° C for 5 hours, the reaction was stopped, the reactor was taken out and placed in ice water for cooling, and the obtained liquid was centrifuged to separate the catalyst to obtain hydrocarbon products. The product composition was analyzed by gas chromatography, and the performance evaluation results are shown in Table 1.

[0048] Comparative Example 2

[0049] The catalyst was a 20% Pt / C commercial noble metal catalyst produced by Johnson Matthey.

[0050] The oil hydrodeoxygenation reaction was carried out in a 100 mL high pressure mechanical stirring reactor. Before the reaction, 6 g rapeseed oil and 0.2 g catalyst (20% Pt / C) were added to the reactor, and then hydrogen was charged and discharged three times to exhaust the air in the reactor, and finally 3 MPa of hydrogen was charged. The reactor was placed in a heating jacket for heating, and the mechanical stirring speed was 550 rpm. After reacting at 280 ° C for 5 hours, the reaction was stopped, the reactor was taken out and placed in ice water for cooling, and the obtained liquid was centrifuged to separate the catalyst to obtain hydrocarbon products. The product composition was analyzed by gas chromatography, and the performance evaluation results are shown in Table 1.

[0051] Comparative Example 3

[0052] Refer to Example 1, except that the catalyst calcination temperature is 550°C and the reduction temperature is 500°C. The corresponding hydrodeoxygenation performance evaluation results are shown in Table 1.

[0053] Comparative Example 4

[0054] Referring to Example 1, the difference is that the catalyst is a nickel-iron alloy. The corresponding hydrodeoxygenation performance evaluation results are shown in Table 1.

[0055] Comparative Example 5

[0056] Referring to Example 1, the difference is that the catalyst is a nickel-cerium alloy. The corresponding hydrodeoxygenation performance evaluation results are shown in Table 1.

[0057] Comparative Example 6

[0058] Referring to Example 1, the difference is that the catalyst is a nickel-aluminum alloy. The corresponding hydrodeoxygenation performance evaluation results are shown in Table 1.

[0059] Table 1 Reaction results of catalysts obtained from Examples 1 to 7 and Comparative Examples 1 to 6

[0060]

[0061] As can be seen from Table 1, the nano nickel-based alloy catalyst provided by the present invention is used in the reaction of preparing hydrocarbon liquid fuel by hydrodeoxygenation of oils and fats. When there is no solvent and the reaction temperature is 280°C, the oil conversion rate is 100%, the deoxidation rate reaches more than 95%, and the ratio of different nickel-based alloy elements has a small effect on the deoxidation rate. According to the total loading amount of the nickel-based alloy elements obtained as 10wt%, the nickel loading amount is preferably 4wt%-8wt%, more preferably 4wt%-6wt%, and most preferably 6wt%.

[0062] The corresponding pure nickel catalyst (Comparative Example 1) has a grease conversion rate of only 33%, and a deoxygenation rate of only about 16%. The commercial Pt / C catalyst (Comparative Example 2) has only a conversion rate of 82.5% and a deoxygenation rate of nearly 33% under the same reaction conditions. When the calcination temperature of the nickel-tungsten alloy catalyst is increased and the reduction temperature is reduced (Comparative Example 3), the reaction performance is greatly reduced, with only a conversion rate of 28.3% and a deoxygenation rate of 12.9%. The performance of nickel iron (Comparative Example 4), nickel cerium (Comparative Example 5) and nickel aluminum (Comparative Example 6) prepared under the same conditions is not as good as the nano nickel-based alloy catalyst described in the present invention. It can be seen that the nano nickel-based alloy catalyst of the present invention exhibits excellent catalytic performance in the hydrodeoxygenation conversion of grease under mild conditions.

[0063] The applicant declares that the present invention illustrates the detailed method of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed method, that is, it does not mean that the present invention must rely on the above-mentioned detailed method to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A method for preparing a nano nickel-based alloy catalyst for preparing hydrocarbon liquid fuel by hydrodeoxygenation of oils and fats, characterized in that: The nano nickel-based alloy catalyst is a supported nano nickel-based alloy, and the active component is one of nickel-tungsten alloy, nickel-molybdenum alloy, nickel-zirconium alloy, and nickel-zinc alloy. The method comprises the following steps: 1) dissolving a soluble nickel salt and another soluble metal salt in a solvent to obtain a metal salt solution, adding a carrier to the metal salt solution and ultrasonicating for 5-60 minutes to prepare a catalyst precursor solution, and then performing vacuum rotary evaporation at room temperature of 5°C-30°C until the solvent is completely volatilized; the solvent is a mixture of methanol, ethanol and deionized water, and the other metal salt is one of tungsten, molybdenum, zirconium and zinc salts; 2) calcining the remaining solid after the solution evaporates at 250° C. to 400° C. for 2 h to 8 h to obtain a catalyst precursor; 3) The nano nickel-based alloy catalyst precursor is subjected to hydrogen reduction at a temperature of 650° C. to 690° C. for a reduction time of 2 h to 8 h to obtain the supported nano nickel-based alloy catalyst.

2. The preparation method according to claim 1, characterized in that: Step 1) the ultrasonic time is 20-40 minutes; Step 3) the hydrogen reduction temperature is 680°C to 690°C.

3. The preparation method according to claim 1, characterized in that: In step 1), the soluble nickel salt is selected from nickel nitrate and nickel acetate; the other metal salt is selected from ammonium metatungstate, ammonium molybdate, zirconium nitrate and zinc nitrate.

4. The preparation method according to claim 1, characterized in that: The carrier is one of silicon dioxide, aluminum oxide and hydrotalcite.

5. The preparation method according to claim 1, characterized in that: In step 1), the total amount of the nickel salt and another soluble metal salt added is calculated based on the total amount of nickel-based alloy elements obtained, and the total loading amount is 10wt%. The amount of the nickel salt added is calculated based on the nickel element obtained, and the nickel loading amount is 1wt% to 9wt%.

6. The preparation method according to claim 5, characterized in that: The nickel loading was 4wt%-8wt%.

7. The preparation method according to claim 5, characterized in that: The nickel loading was 4wt%-6wt%.

8. The use of the supported nano nickel-based alloy catalyst obtained by the preparation method according to claim 1, characterized in that: Used for the hydrodeoxygenation of oils and fats to produce hydrocarbon liquid fuels.

9. The use according to claim 8, characterized in that: The reaction conditions are as follows: the reaction temperature is between 260°C and 340°C, the hydrogen pressure is between 1.0MPa and 5.0MPa, and the mass ratio of oil to catalyst is between 15-50.

10. The use according to claim 8, characterized in that: The reaction temperature is between 270°C and 300°C, the hydrogen pressure is between 2.0MPa and 4.0MPa, and the mass ratio of oil to catalyst is between 20-40.

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