Bio-based 1, 4-butanediol and preparation method thereof

Abstract

The invention relates to bio-based 1, 4-butanediol and a preparation method thereof, and belongs to the technical field of chemical raw material synthesis. The preparation method of the bio-based 1, 4-butanediol comprises the following steps: preparing a bio-based 1, 4-succinic acid solution; continuously feeding the obtained bio-based 1, 4-succinic acid solution and hydrogen into a fixed bed containing a first-stage nickel-copper catalyst, and carrying out hydrogenation reaction to obtain a first-stage product; continuously feeding the obtained first-stage product and hydrogen into a fixed bed containing a second-stage nickel-copper catalyst, and carrying out hydrogenation reaction to obtain a second-stage product; and feeding the obtained second-stage product into a separation tower for separation and purification to obtain the bio-based 1, 4-butanediol. According to the method, the polymer-grade bio-based 1, 4-butanediol is prepared through continuous liquid phase hydrogenation of the bio-based 1, 4-succinic acid, the purity of the obtained polymer-grade bio-based 1, 4-butanediol is larger than or equal to 99.90%, and the product does not contain methyl-1, 4-butanediol and does not contain 2-(4-hydroxybutoxy)-tetrahydrofuran.

Description

Technical Field

[0001] The invention relates to the technical field of chemical raw material synthesis, in particular to bio-based 1,4-butanediol and a preparation method thereof. Background Art

[0002] 1,4-Butanediol, referred to as BDO, is the basic raw material for the production of polyesters such as polybutylene terephthalate (PBT), polybutylene terephthalate-adipate (PBAT), polybutylene succinate (PBS), and is an important organic and fine chemical raw material. At the same time, 1,4-butanediol is the main raw material for the production of tetrahydrofuran. Polytetramethylene glycol ether (PTMEG) obtained by the polymerization of tetrahydrofuran is the basic raw material for the production of high-elastic spandex (Lycra fiber), which is used to produce high-elastic knitwear such as high-end sportswear and swimwear.

[0003] There are many process routes for producing 1,4-butanediol, up to more than 17, but the industrial preparation of 1,4-butanediol mainly includes the Reppe method (acetylene aldehyde method) using formaldehyde and acetylene (carbide gas) as raw materials and the hydrogenation method using maleic anhydride, succinic acid and its derivatives as raw materials. Although the production cost of the acetylene aldehyde method is relatively low, carbide is a high-energy consumption raw material. The hydrogenation method can produce different products according to different process conditions; but the main disadvantages are that there are many hydrogenation by-products, the separation cost is high, and the hydrogenation acidic reaction system, generally the acid-resistant system will lead to poisoning of the active center and cannot be produced for a long period of time. If 1,4-butanediol can be produced by directional and highly selective hydrogenation by adjusting the catalytic active center, it will have great industrial potential.

[0004] Patent CN111018669A discloses a continuous preparation method of 1,4-butanediol, which must undergo two esterification reactions, resulting in the existing monoesterification-diesterification preparation process, which is relatively complex, requires many supporting production devices, requires large equipment investment, has a long production cycle, and has high production energy consumption. In addition, due to the special preparation process of bio-based succinic acid, the trace impurity components it contains will affect the catalytic activity of the catalyst, resulting in unsatisfactory performance indicators of the final product 1,4-butanediol.

[0005] Therefore, there is an urgent need to provide a method for producing bio-based 1,4-butanediol with low production cost and high purity. Summary of the invention

[0006] To solve the above technical problems, the present invention provides a bio-based 1,4-butanediol and a preparation method thereof. The nickel-copper catalyst in the present invention is composed of an ordered composite porous carbon / molybdenum disulfide material carrier, a nickel and copper precursor compound active component, and a hydrophobic compound component. Among them, the nickel loading in the first-stage hydrogenation catalyst is 30wt% to 60wt%, the copper loading is 1wt% to 5wt%, and the hydrophobic compound is 0.01wt% to 0.2wt%; the nickel loading in the second-stage hydrogenation catalyst is 5wt% to 10wt%, the copper loading is 30wt% to 60wt%, and the hydrophobic compound is 0.01wt% to 0.2wt%. The present invention continuously liquid-phase hydrogenates bio-based 1,4-butanediol to prepare polymer-grade bio-based 1,4-butanediol, and the purity of the obtained polymer-grade bio-based 1,4-butanediol is ≥99.90%, and the product does not contain methyl-1,4-butanediol.

[0007] The present invention is achieved through the following technical solutions:

[0008] The first object of the present invention is to provide a bio-based 1,4-butanediol, wherein the purity of the bio-based 1,4-butanediol is ≥99.90%, the bio-based 1,4-butanediol does not contain methyl-1,4-butanediol, does not contain 2-(4-hydroxybutoxy)-tetrahydrofuran, and the rest are impurities; the main impurities are tetrahydrofuran, the content of which is ≤0.05%, and n-butanol, the content of which is ≤0.05%.

[0009] The second object of the present invention is to provide a method for producing bio-based 1,4-butanediol, comprising the following steps:

[0010] (1) preparing a bio-based 1,4-succinic acid solution;

[0011] (2) continuously introducing the bio-based 1,4-succinic acid solution obtained in step (1) and hydrogen into a fixed bed containing a first-stage nickel-copper catalyst for hydrogenation reaction to obtain a first-stage product;

[0012] (3) continuously introducing the first-stage product obtained in step (2) and hydrogen into a fixed bed containing a second-stage nickel-copper catalyst for hydrogenation reaction to obtain a second-stage product;

[0013] (4) passing the second-stage product obtained in step (3) into a separation tower for separation and purification to obtain bio-based 1,4-butanediol;

[0014] In step (2), the nickel loading in the one-stage nickel-copper catalyst is 30wt% to 60wt%, the copper loading is 1wt% to 5wt%, and the content of the hydrophobic compound is 0.01wt% to 0.2wt%;

[0015] In step (3), the nickel loading in the second-stage nickel-copper catalyst is 5wt% to 10wt%, the copper loading is 30wt% to 60wt%, and the content of the hydrophobic compound is 0.01wt% to 0.2wt%

[0016] In one embodiment of the present invention, in step (1), the mass percentage of bio-based 1,4-succinic acid in the bio-based 1,4-succinic acid solution is 5 wt % to 30 wt %.

[0017] In one embodiment of the present invention, in step (1), the solvent of the bio-based 1,4-butanedioic acid solution is selected from one or more of tetrahydrofuran, γ-butyrolactone, diethyl ether, ethyl acetate, ethyl formate and methyl acetate; preferably tetrahydrofuran and γ-butyrolactone.

[0018] In one embodiment of the present invention, in step (2) and step (3), the flow rate of the bio-based 1,4-succinic acid solution is 0 to 5 mL / min;

[0019] and / or, the flow rate of the first stage product is 0 to 5 mL / min;

[0020] And / or, the flow rate of the hydrogen is 0 to 100 mL / min.

[0021] In one embodiment of the present invention, in step (2), the one-stage nickel-copper catalyst is obtained by the following preparation method:

[0022] S1, stirring and mixing asphalt and molybdenum disulfide; heat-treating the obtained mixture under oxygen conditions to obtain a porous carbon / molybdenum disulfide material carrier;

[0023] S2, dissolving a nickel precursor compound, a copper precursor compound, a hydrophobic compound and an acid solution in water to obtain a mixed solution; the mass ratio of the nickel precursor compound, the copper precursor compound and the hydrophobic compound is 80-99:0.1-20:0.01-1;

[0024] S3, impregnating the porous carbon / molybdenum disulfide material carrier obtained in step S1 into the mixed solution obtained in step S2 to obtain a catalyst intermediate;

[0025] S4, aging, drying and reducing the catalyst intermediate obtained in step S3 to obtain the one-stage nickel-copper catalyst.

[0026] In one embodiment of the present invention, in step (3), the second-stage nickel-copper catalyst is obtained by the following preparation method:

[0027] S11, stirring and mixing asphalt and molybdenum disulfide; heat-treating the obtained mixture under oxygen conditions to obtain a porous carbon / molybdenum disulfide material carrier;

[0028] S12, dissolving a nickel precursor compound, a copper precursor compound, a hydrophobic compound and an acid solution in water to obtain a mixed solution; the mass ratio of the nickel precursor compound, the copper precursor compound and the hydrophobic compound is 1-50:50-99:0.01-1;

[0029] S13, impregnating the porous carbon / molybdenum disulfide material carrier obtained in step S11 into the mixed solution obtained in step S12 to obtain a catalyst intermediate;

[0030] S14, aging, drying and reducing the catalyst intermediate obtained in step S13 to obtain the two-stage nickel-copper catalyst.

[0031] In one embodiment of the present invention, the mass average molecular weight of the asphalt is 600 to 2000, and the molecular weight distribution is 1.2 to 1.4;

[0032] And / or, the molybdenum disulfide is a nanosheet structure with 5 to 20 layers.

[0033] In one embodiment of the present invention, the mass ratio of the asphalt to molybdenum disulfide is 1:5 to 5:1;

[0034] And / or, the heat treatment conditions are: heat treatment at 200°C to 400°C for 3h to 8h.

[0035] In one embodiment of the present invention, the porous carbon / molybdenum disulfide material carrier has a pore volume of 0.2 mL / g to 0.7 mL / g, a particle size of 3 mm to 5 mm, and a bulk density of 750 kg / m 3 ~1100kg / m 3 .

[0036] In one embodiment of the present invention, the nickel precursor compound is selected from one or more of nickel chloride, nickel nitrate, nickel sulfate, basic nickel carbonate, nickel acetylacetonate, nickel oxalate, nickel acetate, nickel citrate, nickel hypophosphite, nickel phosphate and nickel formate;

[0037] and / or, the copper precursor compound is selected from one or more of copper chloride, copper nitrate and copper sulfate;

[0038] And / or, the structural formula of the hydrophobic compound is Where n≥6.

[0039] In one embodiment of the present invention, the acid solution is a dilute nitric acid solution with a concentration of 1 mol / L to 6 mol / L.

[0040] In one embodiment of the present invention, in step S4, the reduction conditions are: reduction at 160°C to 200°C for 6h to 10h under hydrogen and normal pressure. ，This makes the nickel-copper catalyst have hydrogenation activity.

[0041] In one embodiment of the present invention, in step S14, the reduction conditions are: reduction at 160°C to 200°C for 6h to 10h under hydrogen and normal pressure. ， This makes the nickel-copper catalyst have hydrogenation activity.

[0042] In one embodiment of the present invention, in step (2), the pressure of the hydrogenation reaction is 1 MPa to 10 MPa; preferably 2 MPa to 5 MPa;

[0043] And / or, the temperature of the hydrogenation reaction is 25°C to 100°C; preferably 80°C to 100°C;

[0044] And / or, the system reaction space velocity of the hydrogenation reaction is 0.6 hr -1 ~6.0hr -1 .

[0045] In one embodiment of the present invention, in step (3), the pressure of the hydrogenation reaction is 3MPa to 10MPa; preferably 5MPa to 8MPa;

[0046] And / or, the temperature of the hydrogenation reaction is 100°C to 200°C; preferably 120°C to 150°C;

[0047] And / or, the system reaction space velocity of the hydrogenation reaction is 0.6 hr -1 ~6.0hr -1 .

[0048] The particle strength of the first-stage nickel-copper catalyst and the second-stage nickel-copper catalyst prepared by the present invention is ≥400N / cm. In addition, the cluster sizes of the first-stage nickel-copper catalyst and the second-stage nickel-copper catalyst are: length 80nm-150nm, width about 30nm-100nm, thickness about 10nm-30nm. And the purity of the prepared bio-based 1,4-butanediol is ≥99.90%, does not contain methyl-1,4-butanediol, does not contain 2-(4-hydroxybutoxy)-tetrahydrofuran; the main impurities are tetrahydrofuran, the content is ≤0.05%, and n-butanol, the content is ≤0.05%.

[0049] The technical solution of the present invention adopts a high-strength molybdenum disulfide / porous carbon carrier, which can avoid the problem of non-precious metal nickel and copper catalytic centers being lost into the product under pressurized hydrogenation conditions, thereby causing the catalyst activity to gradually decrease, thereby ensuring long-term production; in addition, the hydrophobic compound can make the hydrogenation product quickly desorb from the catalyst surface, and then by adjusting the reaction pressure and temperature, the degree of hydrogenation of the two C=O bonds of succinic acid can be controlled to obtain the target product.

[0050] The porous carbon / molybdenum disulfide carrier of the present invention, due to the layered structural characteristics of molybdenum disulfide, when the carrier is subjected to high temperature treatment, the asphalt will extend along the layered voids, and then undergo dehydration, de-organic matter and other processes at a certain temperature to form a layered carbon structure, which is firmly combined with molybdenum disulfide and produces a large number of pore structures, which is conducive to the dispersion of active metal components. At the same time, this composite carrier structure naturally has a very high mechanical strength, and it is easy to achieve a particle strength of ≥400N / cm, while the particle strength of traditional alumina is difficult to achieve this. The mechanical strength of alumina particles of commercial catalyst carriers can generally reach 100N / cm.

[0051] The above technical solution has the following advantages compared with the prior art:

[0052] (1) The catalyst used in the present invention has an ultra-high strength of ≥400 N / cm, and the metal is not easily lost during the reaction, which plays a key role in the synthesis of high-purity bio-based 1,4-butanediol.

[0053] (2) The catalyst used in the present invention uses porous carbon / molybdenum disulfide as a carrier. The catalyst carrier itself has a certain hydrogenation activity, which can promote the improvement of reaction activity, thereby reducing the reaction temperature, improving the reaction selectivity, and further improving the purity of the product.

[0054] (3) The present invention uses bio-based 1,4-butanediol as a reaction raw material, and the catalyst used uses a hydrophobic compound as an additive, which can make the product bio-based 1,4-butanediol desorb from the catalyst surface as quickly as possible. On the one hand, it can accelerate the reaction speed, and on the other hand, it can avoid further reaction of the product on the catalyst surface, thereby achieving the ultimate goal of achieving product purity of polymerization grade. DETAILED DESCRIPTION

[0055] The present invention is further described below in conjunction with specific embodiments so that those skilled in the art can better understand the present invention and implement it, but the embodiments are not intended to limit the present invention.

[0056] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods, and the materials, reagents, etc. used are all available from commercial sources unless otherwise specified.

[0057] The purity and impurity content of the product were tested by gas chromatography, with a gas chromatography column HP-5 (30m×320μm×0.25μm) and a FID detector. The column temperature conditions were initial temperature 60℃, first-order termination temperature 90℃, heating rate 15℃ / min, and holding for 2min, second-order termination temperature: 230℃, heating rate 10℃ / min, injection port temperature 260℃, split ratio 100:1, injection volume: 0.2μL, hydrogen flow rate: 30mL / min, nitrogen flow rate: 25mL / min. Using acetone as solvent, the standard curves of 1,4-butanediol, tetrahydrofuran, methyl-1,4-butanediol, 2-(4-hydroxybutoxy)-tetrahydrofuran, γ-butyrolactone, n-butanol and 1,4-butanediol were established.

[0058] The strength test of hydrogenation catalyst was carried out in accordance with HG / T 2782 standard.

[0059] Example 1

[0060] This embodiment provides a method for preparing bio-based 1,4-butanediol, and the specific steps are as follows:

[0061] (1) Preparation of carrier: Asphalt and molybdenum disulfide were stirred and mixed in a mass ratio of 1:1, and heat treated at 300°C for 4 h under oxygen conditions to prepare a porous carbon / molybdenum disulfide carrier with a pore volume of 0.5 mL / g and a particle size of 5 mm;

[0062] (2) Preparation of a one-stage nickel-copper catalyst: Weigh 50.00 g of basic nickel carbonate (molecular weight: 376.17), 159.5 mL (5 mol / L) of dilute nitric acid solution, 4.58 g of copper nitrate, 0.30 g of sodium dodecyl sulfate, and 500.00 g of deionized water, and stir at 45°C until all solids are dissolved to obtain a nickel-copper solution; impregnate the obtained porous carbon / molybdenum disulfide support into the nickel-copper solution; age the obtained mixture at 60°C for 14 h under stirring, and then dry it at 120°C for 12 h, load it into a tube, and reduce it under hydrogen at 200°C for 6 h to obtain a one-stage nickel-copper catalyst.

[0063] Preparation of a two-stage nickel-copper catalyst: weigh 9.16 g of basic nickel carbonate (molecular weight 376.17), 29.2 mL (5 mol / L) of dilute nitric acid solution, 50.00 g of copper nitrate, 0.30 g of sodium dodecyl sulfate, and 500.00 g of deionized water, stir at 45°C until all solids are dissolved to obtain a nickel-copper solution; immerse the obtained porous carbon / molybdenum disulfide support in the nickel-copper solution; under stirring, age the mixture at 60°C for 14 h, dry it at 120°C for 12 h, load it into a tube, and reduce it under hydrogen at 200°C for 6 h to obtain a two-stage nickel-copper catalyst.

[0064] (3) preparing a 5 wt % bio-based 1,4-butanedioic acid γ-butyrolactone solution; mixing the bio-based 1,4-butanedioic acid γ-butyrolactone solution at a flow rate of 0.5 mL / min with hydrogen at a flow rate of 200 mL / min, and then continuously entering a 50 mL hydrogenation tubular reactor containing a first-stage nickel-copper catalyst, with a reaction temperature of 96° C. and a reaction pressure of 2.8 MPa(A) to obtain a γ-butyrolactone solution;

[0065] A γ-butyrolactone solution with a flow rate of 0.5 mL / min was mixed with hydrogen with a flow rate of 200 mL / min and continuously entered a 50 mL hydrogenation tubular reactor containing a two-stage nickel-copper catalyst at a reaction temperature of 130°C and a reaction pressure of 5.2 MPa (A). It then continuously entered a distillation separation tower to separate and obtain bio-based 1,4-butanediol.

[0066] Example 2

[0067] This embodiment provides a method for preparing bio-based 1,4-butanediol, which is similar to that of Embodiment 1, except that:

[0068] In step (2), the basic nickel carbonate in the two-stage nickel-copper catalyst preparation process is replaced with nickel nitrate;

[0069] The obtained two-stage nickel-copper catalyst is subjected to catalytic hydrogenation to prepare bio-based 1,4-butanediol.

[0070] Example 3

[0071] This embodiment provides a method for preparing bio-based 1,4-butanediol, which is similar to that of Embodiment 1, except that:

[0072] In step (2), the copper nitrate in the two-stage nickel-copper catalyst preparation process is replaced with copper chloride;

[0073] The obtained two-stage nickel-copper catalyst is subjected to catalytic hydrogenation to prepare bio-based 1,4-butanediol.

[0074] Example 4

[0075] This embodiment provides a method for preparing bio-based 1,4-butanediol, which is similar to that of Embodiment 1, except that:

[0076] During the catalytic hydrogenation process, a 10 wt% γ-butyrolactone solution of bio-based 1,4-butanedioic acid is prepared and catalytically hydrogenated to obtain bio-based 1,4-butanediol.

[0077] Example 5

[0078] This embodiment provides a method for preparing bio-based 1,4-butanediol, which is similar to that of Embodiment 1, except that:

[0079] During the catalytic hydrogenation process, a 5 wt% tetrahydrofuran solution of bio-based 1,4-butanediol was prepared and catalytically hydrogenated to obtain bio-based 1,4-butanediol.

[0080] Comparative Example 1

[0081] This comparative example provides a method for preparing bio-based 1,4-butanediol, which is similar to Example 1, except that:

[0082] No copper nitrate is added during the preparation of the first-stage nickel-copper catalyst and the second-stage nickel-copper catalyst.

[0083] The obtained two-stage nickel-copper catalyst is subjected to catalytic hydrogenation to prepare bio-based 1,4-butanediol.

[0084] Comparative Example 2

[0085] This comparative example provides a method for preparing bio-based 1,4-butanediol, which is similar to Example 1, except that:

[0086] Sodium dodecyl sulfate is not added during the preparation of the first-stage nickel-copper catalyst and the second-stage nickel-copper catalyst.

[0087] The obtained two-stage nickel-copper catalyst is subjected to catalytic hydrogenation to prepare bio-based 1,4-butanediol.

[0088] Comparative Example 3

[0089] This comparative example provides a method for preparing bio-based 1,4-butanediol, which is similar to Example 1, except that:

[0090] No copper nitrate and sodium dodecyl sulfate are added during the preparation of the first-stage nickel-copper catalyst and the second-stage nickel-copper catalyst.

[0091] The obtained two-stage nickel-copper catalyst is subjected to catalytic hydrogenation to prepare bio-based 1,4-butanediol.

[0092] Comparative Example 4

[0093] This comparative example provides a method for preparing bio-based 1,4-butanediol, which is similar to Example 1, except that:

[0094] No molybdenum disulfide is added during the preparation of the first-stage nickel-copper catalyst and the second-stage nickel-copper catalyst.

[0095] The obtained two-stage nickel-copper catalyst is subjected to catalytic hydrogenation to prepare bio-based 1,4-butanediol.

[0096] Test Case

[0097] The strength of the catalysts prepared in the examples and comparative examples was tested according to the HG / T 2782 standard. The test results are shown in Table 1 below:

[0098] Table 1

[0099] Catalyst strength (N / cm) Second stage catalyst strength (N / cm) Example 1 453.3 450.9 Example 2 451.8 453.2 Example 3 457.2 451.0 Example 4 453.3 450.9 Example 5 453.3 450.9 Comparative Example 1 453.8 450.6 Comparative Example 2 454.6 451.2 Comparative Example 3 451.5 450.4 Comparative Example 4 205.1 201.3

[0100] It can be seen from Table 1 that the strength of the supported catalyst prepared in the example exceeds 450 N / cm. By combining high-strength molybdenum disulfide with porous carbon, the strength of the supported catalyst can be greatly improved.

[0101] The product purity and impurity content were tested by gas chromatography. The conversion rate of the hydrogenation process after 1000h of continuous experiment is shown in Table 2 below:

[0102] Table 2

[0103]

[0104] It can be seen from Table 2 that the catalyst of the present invention still has high catalytic activity and selectivity after 1000 hours of continuous hydrogenation, which is manifested in that high-purity 1,4-butanediol can be prepared under certain pressure and temperature conditions.

[0105] Obviously, the above embodiments are merely examples for clear explanation and are not intended to limit the implementation methods. For those skilled 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 list all the implementation methods here. The obvious changes or modifications derived from these are still within the protection scope of the invention.

Claims

1. A bio-based 1,4-butanediol, characterized in that: The purity of the bio-based 1,4-butanediol is ≥99.90%, does not contain methyl-1,4-butanediol, does not contain 2-(4-hydroxybutoxy)-tetrahydrofuran, and the rest are impurities; the impurities include tetrahydrofuran and n-butanol; the content of the tetrahydrofuran is ≤0.05%, and the content of the n-butanol is ≤0.05%.

2. The method for preparing bio-based 1,4-butanediol according to claim 1, characterized in that: The following steps are involved: (1) preparing a bio-based 1,4-succinic acid solution; (2) continuously introducing the bio-based 1,4-succinic acid solution obtained in step (1) and hydrogen into a fixed bed containing a first-stage nickel-copper catalyst for hydrogenation reaction to obtain a first-stage product; (3) continuously introducing the first-stage product obtained in step (2) and hydrogen into a fixed bed containing a second-stage nickel-copper catalyst for hydrogenation reaction to obtain a second-stage product; (4) passing the second-stage product obtained in step (3) into a separation tower for separation and purification to obtain bio-based 1,4-butanediol; In step (2), the nickel loading in the one-stage nickel-copper catalyst is 30wt% to 60wt%, the copper loading is 1wt% to 5wt%, and the content of the hydrophobic compound is 0.01wt% to 0.2wt%; In step (3), the nickel loading in the second-stage nickel-copper catalyst is 5wt% to 10wt%, the copper loading is 30wt% to 60wt%, and the content of the hydrophobic compound is 0.01wt% to 0.2wt%.

3. The preparation method according to claim 2, characterized in that: In step (1), the mass percentage of bio-based 1,4-succinic acid in the bio-based 1,4-succinic acid solution is 5wt% to 30wt%.

4. The preparation method according to claim 2, characterized in that: In step (1), the solvent of the bio-based 1,4-butanedioic acid solution is selected from one or more of tetrahydrofuran, γ-butyrolactone, ether, ethyl acetate, ethyl formate and methyl acetate.

5. The preparation method according to claim 2, characterized in that: In step (2) and step (3), the flow rate of the bio-based 1,4-succinic acid solution is 0 to 5 mL / min; and / or, the flow rate of the first stage product is 0 to 5 mL / min; And / or, the flow rate of the hydrogen is 0 to 100 mL / min.

6. The preparation method according to claim 2, characterized in that: In step (2), the one-stage nickel-copper catalyst is obtained by the following preparation method: S1, stirring and mixing asphalt and molybdenum disulfide; heat-treating the obtained mixture under oxygen conditions to obtain a porous carbon / molybdenum disulfide material carrier; S2, dissolving a nickel precursor compound, a copper precursor compound, a hydrophobic compound and an acid solution in water to obtain a mixed solution; the mass ratio of the nickel precursor compound, the copper precursor compound and the hydrophobic compound is 80-99:0.1-20:0.01-1; S3, impregnating the porous carbon / molybdenum disulfide material carrier obtained in step S1 into the mixed solution obtained in step S2 to obtain a catalyst intermediate; S4, aging, drying and reducing the catalyst intermediate obtained in step S3 to obtain the one-stage nickel-copper catalyst.

7. The preparation method according to claim 2, characterized in that: In step (3), the second-stage nickel-copper catalyst is obtained by the following preparation method: S11, stirring and mixing asphalt and molybdenum disulfide; heat-treating the obtained mixture under oxygen conditions to obtain a porous carbon / molybdenum disulfide material carrier; S12, dissolving a nickel precursor compound, a copper precursor compound, a hydrophobic compound and an acid solution in water to obtain a mixed solution; the mass ratio of the nickel precursor compound, the copper precursor compound and the hydrophobic compound is 1-50:50-99:0.01-1; S13, impregnating the porous carbon / molybdenum disulfide material carrier obtained in step S11 into the mixed solution obtained in step S12 to obtain a catalyst intermediate; S14, aging, drying and reducing the catalyst intermediate obtained in step S13 to obtain the two-stage nickel-copper catalyst.

8. The preparation method according to claim 6 or 7, characterized in that: The nickel precursor compound is selected from one or more of nickel chloride, nickel nitrate, nickel sulfate, basic nickel carbonate, nickel acetylacetonate, nickel oxalate, nickel acetate, nickel citrate, nickel hypophosphite, nickel phosphate and nickel formate; and / or, the copper precursor compound is selected from one or more of copper chloride, copper nitrate and copper sulfate; And / or, the structural formula of the hydrophobic compound is Among them, n≥6.

9. The preparation method according to claim 2, characterized in that: In step (2), the pressure of the hydrogenation reaction is 1 MPa to 10 MPa; And / or, the temperature of the hydrogenation reaction is 25°C to 100°C; And / or, the system reaction space velocity of the hydrogenation reaction is 0.6 hr -1 ~6.0hr -1 .

10. The preparation method according to claim 2, characterized in that: In step (3), the pressure of the hydrogenation reaction is 3MPa to 10MPa; And / or, the temperature of the hydrogenation reaction is 100°C to 200°C; And / or, the system reaction space velocity of the hydrogenation reaction is 0.6 hr -1 ~6.0hr -1 .

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