A nickel-based catalyst, its preparation method and use

Abstract

The application discloses a nickel-based catalyst and a preparation method and application thereof. The method comprises the following steps: (1) selecting or self-preparing an alumina carrier; (2) preparing a nickel-containing active metal solution containing sodium gluconate and hexadecyl trimethyl ammonium chloride double surfactants; and (3) impregnating the alumina carrier in the step (1) in the nickel-containing active metal solution containing sodium gluconate and hexadecyl trimethyl ammonium chloride double surfactants prepared in the step (2), and then drying and calcining to obtain the nickel-based catalyst. The nickel-based catalyst prepared by the method has the alumina as the carrier, and the active metal nickel is highly dispersed on the alumina, and the nickel-based catalyst can be used in hydrogenation, dehydrogenation, oxidative dehalogenation, desulfurization, denitrification and other reactions.

Description

Technical Field

[0001] This invention relates to a nickel-based catalyst, its preparation method, and its application; more specifically, it relates to a nickel-based catalyst supported on alumina, its preparation method, and its application. Technical Background

[0002] Nickel-based catalysts possess high hydrogenation activity. Due to their excellent catalytic activity, simple preparation methods, low cost, superior performance, and ease of recycling, they are widely used in the hydrogenation of various unsaturated hydrocarbons. They are also excellent catalysts in certain conversion processes such as dehydrogenation, oxidative dehalogenation, and desulfurization, finding widespread applications in the petroleum, chemical, pharmaceutical, oil, fragrance, hydrogen peroxide, and synthetic fiber industries. However, nickel-based catalysts prepared by traditional impregnation methods often exhibit inconsistent nickel particle sizes and uneven dispersion, with most particles exceeding 10 nanometers in diameter. Furthermore, after high-temperature reactions, metallic Ni tends to agglomerate, and carbon deposits easily form on the catalyst surface during the reaction, leading to catalyst deactivation.

[0003] Patent CN109261153A discloses a supported nickel-based catalyst, its preparation method, and its application. The active components include nickel, zinc, and magnesium. The composite support is composed of silica and titanium dioxide. The mass percentage of nickel is 30-80%, the mass percentage of zinc is 0.1-15%, the mass percentage of magnesium is 0.1-15 wt%, the mass percentage of silica is 10-50%, and the mass percentage of titanium dioxide is 1-30%. The prepared Ni-Zn-Mg / SiO2-TiO2 supported nickel-based catalyst shows significant effects in the hydrorefining of white oil. However, the high nickel content results in poor dispersibility.

[0004] Patent CN201110199290.3 discloses a nickel-based catalyst, its preparation method, and its uses. The nickel-based catalyst has the following general structural formula: xNi·yCeAlO3·(100-xy)Al2O3, where 1≤x≤20 and 1≤y≤30. The catalyst is prepared by first impregnating dry γ-Al2O3 in a cerium salt aqueous solution at room temperature using an equal-volume impregnation method, followed by drying and calcination in air to obtain a modified support; then, the modified support is impregnated in a nickel salt aqueous solution at room temperature using an equal-volume impregnation method, followed by drying and calcination in air to obtain a catalyst precursor; finally, the catalyst precursor is reduced in hydrogen at 850–1050 °C. The nickel-based catalyst prepared by this method exhibits poor metal dispersion, and the reduced nickel element tends to aggregate.

[0005] Patent CN101927166A describes a co-precipitation method for preparing a highly active supported nickel catalyst for the hydrogenation of phthalic acid diesters to cyclohexanedicarboxylic acid. This catalyst can catalyze the hydrogenation of phthalic acid diesters to o-cyclohexanedicarboxylic acid diesters at relatively low temperatures and hydrogen pressures, achieving a conversion rate and selectivity of over 95%. However, the dispersion of the active nickel metal needs further improvement, and the catalyst preparation process is not easily scaled up for industrial applications.

[0006] CN201210122289.5 discloses a catalyst for the hydrogenation conversion of phthalate plasticizers into cyclohexanedicarboxylate plasticizers, its preparation method and application, using transition metal nickel as the active metal and phosphorus as an auxiliary agent, achieving high conversion rate and low by-product content, but the dispersion of nickel metal needs further improvement.

[0007] CN 110078617 A A method for preparing cyclohexanedicarboxylate by catalytic hydrogenation of phthalates. The catalyst used has nickel as the main active component, iron as an auxiliary agent, and alumina as a support. The reaction was carried out at a temperature of 110–160℃, a pressure of 3–7 MPa, and a space velocity of 0.2–0.4 h⁻¹. -1 Phthalate was hydrogenated under certain conditions to give cyclohexanedicarboxylate in a yield of 99.83%. However, the reaction space velocity was low, resulting in low production efficiency. In addition, the dispersion of gold and nickel in the catalyst needs to be further improved. Summary of the Invention

[0008] To address the shortcomings of existing technologies, this invention provides a nickel-based catalyst, its preparation method, and its applications. The nickel-based catalyst prepared by this method uses alumina as a support, with active nickel metal highly dispersed on the alumina. This nickel-based catalyst can be used for reactions such as hydrogenation, dehydrogenation, oxidative dehalogenation, desulfurization, and denitrification.

[0009] The first aspect of this invention is to provide a method for preparing a nickel-based catalyst, the method comprising the following steps: (1) Select or prepare an alumina carrier; (2) Prepare a nickel-containing active metal solution containing sodium gluconate and hexadecyltrimethylammonium chloride as dual surfactants; (3) The alumina support in step (1) is impregnated with a nickel-containing active metal solution containing sodium gluconate and hexadecyltrimethylammonium chloride dual surfactants prepared in step (2), and then dried and calcined to obtain a nickel-based catalyst.

[0010] In the above method, the alumina support in step (1) may contain appropriate amounts of SiO2, P2O5, and / or B2O3, generally ranging from 0.1 wt% to 5.0 wt% of the weight of the alumina support. The Al2O3 has a surface area greater than or equal to 300 m².2 / g, preferably 350~400m 2 / g; pore volume is greater than or equal to 1.2 mL / g, preferably 1.2~1.5 mL / g; pore size is 11~18 nm.

[0011] The process of making the alumina carrier in step (1) of the above method is as follows: Weigh an appropriate amount of alumina dry adhesive powder, add an adhesive, and obtain the alumina carrier by extrusion molding, drying, and calcination. The amount of adhesive added is 2.0%~15.0% of the weight of the alumina dry adhesive powder. The extrusion is in the shape of a clover leaf. Drying conditions: 100~150℃ for 2~8 hours, preferably 110~130℃ for 4~6 hours. Calcination conditions: 600~800℃ for 3~8 hours, preferably 4~6 hours.

[0012] The above method pretreats the alumina support in step (1) with diluted phosphoric acid. The specific treatment process is as follows: The alumina support is vacuumed at a vacuum level of 0.2-0.8 MPa for 10-30 minutes. A phosphoric acid solution is introduced into the vacuumed alumina support, with a volume ratio of alumina support to phosphoric acid solution of 1:1-1.5 and a mass percentage concentration of 5%-10%. The alumina support with introduced phosphoric acid is pressurized at a pressure of 0.5-0.8 MPa for 0.5-3 hours, preferably 1.0-2.0 hours. The treatment temperature is 15-50°C, and the atmosphere is inert. The treated alumina support is washed with deionized water, with the amount of washing water being 2-15 times the amount of support, preferably 5-10 times. After washing, the alumina support is dried and calcined. The drying temperature is 100-120°C, the heating rate is 15-20°C / h, and the drying time is 2-8 hours, preferably 4-6 hours. The roasting temperature is 500~600℃, and the roasting time is 3~8 hours, preferably 4~6 hours.

[0013] In the above method, the pH value of the nickel-containing active metal solution in step (2) is 5.0 to 9.0, and the concentration of sodium gluconate surfactant in the obtained impregnation solution is 0.5 to 5.0 g / 100 ml, preferably 1.0 to 3.0 g / 100 ml, and the concentration of hexadecyltrimethylammonium chloride surfactant is 0.5 to 10.0 g / 100 ml, preferably 3.0 to 5.0 g / 100 ml.

[0014] In the above method, the nickel in step (2) is derived from at least one of nickel hydroxide, nickel sulfate, nickel nitrate, nickel chloride, and nickel oxide. The solution may contain additives, namely copper and titanium. The copper source is at least one of copper sulfate, copper nitrate, copper chloride, and copper oxide. The titanium source is at least one selected from titanium tetrachloride, titanium tetrafluoride, titanium nitrate, titanium sulfate, and titanium acetate. In the above method, in step (2), the nickel-containing active metal solution has a titanium source with a mass fraction of 1.0% to 7.5% (calculated as titanium oxide), preferably 1.5% to 5.0%; a nickel source with a mass fraction of 20.5% to 43.5% (calculated as nickel oxide), preferably 25.0% to 35.0%; and a copper source with a mass fraction of 1.0% to 6.0% (calculated as copper oxide), preferably 1.5% to 4.5%.

[0015] In the above method, the impregnation in step (3) can be either equal-volume impregnation or over-volume impregnation. In the over-volume impregnation method, the volume ratio of the impregnation liquid to the catalyst support is preferably 1.2 to 1.5. The impregnation conditions are: temperature 20 to 80°C, time 1.0 to 2.0 h. Impregnation can be performed once or multiple times. The drying is carried out at 80 to 130°C for 2 to 4 hours, and the calcination is carried out at 200 to 450°C for 3 to 5 hours.

[0016] A nickel-based catalyst prepared by the above method, wherein the dispersion of the active metal Ni is: I Ni / I Al The value is 0.160~0.250, preferably 0.180~0.220, wherein, I Ni / I Al This represents the ratio of nickel atoms to aluminum atoms on the catalyst surface.

[0017] The catalysts described above, based on their mass, include: NiO, with a nickel content of 15.0%–40.0%, preferably 20.0%–30.0%; TiO2, with a titanium content of 0.5%–5.0%, preferably 1.0%–3.0%; and CuO, with a copper content of 0.5%–5.0%, preferably 1.0%–2.5%. In the above-mentioned catalyst, the specific surface area of ​​the catalyst is 160~180m². 2 / g; pore volume is 0.45~0.60mL / g, and average pore size is 11~13nm. Metal grain size is 2-10nm, preferably 4-6nm; The pore size distribution in the catalyst channels is as follows: pores <3nm account for ≤0.6% of the total pore volume, preferably 0.40-0.55%, and pores 3~15nm account for ≥94.0% of the total pore volume, preferably 94-96%.

[0018] Compared with the prior art, the nickel-based catalyst, its preparation method, and its application of the present invention have the following advantages: 1. In this invention, the preparation method uses macroporous Al2O3 as a catalyst support, which is impregnated in an impregnation solution, dried, and calcined to obtain the catalyst; the impregnation solution includes sodium gluconate and hexadecyltrimethylammonium chloride, nickel source, titanium source, and copper source. The synergistic effect of sodium gluconate and hexadecyltrimethylammonium chloride improves the dispersion of the active metal and controls the grain size of the active metal, thereby improving the stability of the catalyst.

[0019] 2. In this invention, the catalyst support is pretreated with phosphoric acid under vacuum pressure, which blocks the pores in the catalyst channels, making the pore distribution of the catalyst particularly concentrated, improving the selectivity of the catalyst, and suppressing the occurrence of side reactions.

[0020] 3. In this invention, the catalyst uses nickel as the active metal component and titanium and copper as promoters. The addition of copper can provide electrons for the reduction of nickel and promote the reduction of nickel components. The addition of titanium reduces the activation energy of the reaction and improves the activity and selectivity of the catalyst. Detailed Implementation

[0021] The technical solution of the present invention is further described below through embodiments and comparative examples, but the scope of protection of the present invention is not limited by the embodiments.

[0022] In this invention, the specific surface area, pore volume, and pore size of the catalyst were analyzed and tested using an ASAP2420 physical adsorption instrument.

[0023] In this invention, the content of each component in the catalyst is determined by using a Rigaku Electric Co., Ltd. 3013 X-ray fluorescence spectrometer to determine the content of each component in the catalyst by X-ray fluorescence method.

[0024] In this invention, the size of the catalyst metal grains was determined by observing the structural features of the sample using a JEM-2100F field emission transmission electron microscope manufactured by JEOL Corporation of Japan.

[0025] In this invention, the dispersion of the active metal was obtained by analyzing the active metal components on the catalyst surface using X-ray photoelectron spectroscopy, specifically a MULTILAB 2000 X-ray photoelectron spectroscopy system (USA). A higher dispersion value indicates a more uniform dispersion of the active metal. Ni / I Al These represent the ratio of nickel atoms to aluminum atoms on the catalyst surface, respectively. Specific test conditions are as follows: AlKa photoelectron source, Eb = 1486.6 eV; reference C 1s, 284.8 eV. Peak shift caused by charging was corrected.

[0026] Example 1 (1) Weigh 300g of silicon-containing alumina dry glue, add 12g of guar gum powder, 10g of carbon black and 12g of dilute nitric acid, knead at room temperature for 30 minutes to form a plastic body, extrude it into clover strips on an extruder, dry the wet strips at 110℃ for 4 hours in a drying oven, and keep them at 650℃ for 4 hours in a calcining furnace to obtain alumina carrier; (2) Weigh 100 g of carrier and place it in a vacuum device. Then, evacuate the device to a vacuum level of 0.5 MPa for 10 min. Next, add 120 mL of phosphoric acid solution (5% by mass) to the evacuated carrier. Then, transfer the carrier to an autoclave, purge with nitrogen, and pressurize it at a pressure of 0.5 MPa for 2 h at a temperature of 25°C. Then, wash the treated carrier with deionized water (8 times the amount of carrier). Then, dry the carrier at 120°C with a heating rate of 15 g / h for 6 h. Finally, calcine the carrier at 550°C for 5 h.

[0027] (3) After dissolving a solution containing nickel nitrate, copper nitrate, and titanium trichloride in water, sodium gluconate and hexadecyltrimethylammonium chloride are added and stirred to dissolve, resulting in an impregnation solution. The mass fraction of nickel oxide is 34.0%, the mass fraction of copper oxide is 1.8%, the mass fraction of titanium oxide is 3.1%, the mass fraction of sodium gluconate is 2.5 g / 100ml, and the mass fraction of hexadecyltrimethylammonium chloride is 4.0 g / 100ml.

[0028] Weigh 100g of the catalyst support prepared in step (2), impregnate it with 150mL of impregnation solution at 60℃ for 2 hours, dry it at 120℃ for 5 hours, and then calcine it at 400℃ for 4 hours. Catalyst A is obtained. Its properties are shown in Table 1.

[0029] Example 2 (1) Weigh 300g of silicon-containing alumina dry glue, add 12g of guar gum powder, 10g of carbon black and 12g of dilute nitric acid, knead at room temperature for 30 minutes to form a plastic body, extrude it into clover strips on an extruder, dry the wet strips at 110℃ for 4 hours in a drying oven, and keep them at 650℃ for 4 hours in a calcining furnace to obtain alumina carrier; (2) Weigh 100 g of carrier and place it in a vacuum device. Then, evacuate the device to a vacuum level of 0.5 MPa for 10 min. Next, add 120 mL of phosphoric acid solution (5% by mass) to the evacuated carrier. Then, transfer the carrier to an autoclave, purge with nitrogen, and pressurize it at a pressure of 0.5 MPa for 2 h at a temperature of 25°C. Then, wash the treated carrier with deionized water (8 times the amount of carrier). Then, dry the carrier at 120°C with a heating rate of 15 g / h for 6 h. Finally, calcine the carrier at 550°C for 5 h.

[0030] (3) After dissolving a solution containing nickel nitrate, copper nitrate, and titanium trichloride in water, sodium gluconate and hexadecyltrimethylammonium chloride are added and stirred to dissolve, resulting in an impregnation solution. The mass fraction of nickel oxide is 25.5%, the mass fraction of copper oxide is 2.8%, the mass fraction of titanium oxide is 3.1%, the mass fraction of sodium gluconate is 2.5 g / 100 ml, and the mass fraction of hexadecyltrimethylammonium chloride is 4.0 g / 100 ml.

[0031] Weigh 100g of the catalyst support prepared in step (2), impregnate it with 150mL of impregnation solution at 60℃ for 2 hours, dry it at 120℃ for 5 hours, and then calcine it at 400℃ for 4 hours. Catalyst B is obtained. Its properties are shown in Table 1.

[0032] Example 3 (1) Weigh 300g of silicon-containing alumina dry glue, add 12g of guar gum powder, 10g of carbon black and 12g of dilute nitric acid, knead at room temperature for 30 minutes to form a plastic body, extrude it into clover strips on an extruder, dry the wet strips at 110℃ for 4 hours in a drying oven, and keep them at 650℃ for 4 hours in a calcining furnace to obtain alumina carrier; (2) Weigh 100 g of carrier and place it in a vacuum device. Then, evacuate the device to a vacuum level of 0.5 MPa for 10 min. Next, add 120 mL of phosphoric acid solution (5% by mass) to the evacuated carrier. Then, transfer the carrier to an autoclave, purge with nitrogen, and pressurize it at a pressure of 0.5 MPa for 2 h at a temperature of 25°C. Then, wash the treated carrier with deionized water (8 times the amount of carrier). Then, dry the carrier at 120°C with a heating rate of 15 g / h for 6 h. Finally, calcine the carrier at 550°C for 5 h.

[0033] (3) After dissolving a solution containing nickel nitrate, copper nitrate, and titanium trichloride in water, sodium gluconate and hexadecyltrimethylammonium chloride are added and stirred to dissolve, resulting in an impregnation solution. The mass fraction of nickel oxide is 29.2%, the mass fraction of copper oxide is 2.4%, the mass fraction of titanium oxide is 2.7%, the mass fraction of sodium gluconate is 2.4 g / 100ml, and the mass fraction of hexadecyltrimethylammonium chloride is 3.9 g / 100ml.

[0034] Weigh 100g of the catalyst support prepared in step (2), impregnate it with 150mL of impregnation solution at 60℃ for 2 hours, dry it at 120℃ for 5 hours, and then calcine it at 410℃ for 4 hours. Catalyst C is obtained. Its properties are shown in Table 1.

[0035] Example 4 (1) Weigh 300g of silicon-containing alumina dry glue, add 12g of guar gum powder, 10g of carbon black and 12g of dilute nitric acid, knead at room temperature for 30 minutes to form a plastic body, extrude it into clover strips on an extruder, dry the wet strips at 110℃ for 4 hours in a drying oven, and keep them at 650℃ for 4 hours in a calcining furnace to obtain alumina carrier; (2) Weigh 100 g of carrier and place it in a vacuum device. Then, evacuate the vacuum to 0.5 MPa for 10 min. Next, add 120 mL of phosphoric acid solution (5% by mass) to the evacuated carrier. Then, transfer the carrier to an autoclave, purge with nitrogen, and pressurize it at 0.5 MPa for 2 h at a temperature of 25°C. Then, wash the treated carrier with deionized water (8 times the amount of carrier). Then, dry the carrier at 120°C at a heating rate of 15 g / h for 6 h. Finally, calcine the carrier at 560°C for 5 h.

[0036] (3) After dissolving a solution containing nickel nitrate, copper nitrate, and titanium trichloride in water, sodium gluconate and hexadecyltrimethylammonium chloride are added and stirred to dissolve, resulting in an impregnation solution. The mass fraction of nickel oxide is 28.5%, the mass fraction of copper oxide is 2.9%, the mass fraction of titanium oxide is 1.7%, the mass fraction of sodium gluconate is 2.5 g / 100ml, and the mass fraction of hexadecyltrimethylammonium chloride is 4.0 g / 100ml.

[0037] Weigh 100g of the catalyst support prepared in step (2), impregnate it with 150mL of impregnation solution at 60℃ for 2 hours, dry it at 120℃ for 5 hours, and then calcine it at 400℃ for 4 hours. Catalyst D is obtained. Its properties are shown in Table 1.

[0038] Comparative Example 1 Other conditions are the same as in Example 4, except that sodium gluconate is not added in step (3), and the catalyst product number is E.

[0039] Comparative Example 2 Other conditions are the same as in Example 4, except that hexadecyltrimethylammonium chloride is not added in step (3), and the catalyst product number is F.

[0040] Comparative Example 3 Other conditions are the same as in Example 4, except that sodium gluconate and hexadecyltrimethylammonium chloride are not added in step (3), and the catalyst product number is G.

[0041] Comparative Example 4 The catalyst was prepared according to the method of patent CN102658182A. Macroporous aluminum hydroxide dry powder, acetic acid, and guar gum powder were mixed in a mass ratio of 1:0.02:0.043, and then deionized water was added and kneaded. The mixture was then dropped into spherical particles with a particle size of Ф2.5. The particles were placed at room temperature for 5 hours to air dry, dried at 120℃ for 4 hours, and then calcined at 680-900℃ for 2-3 hours to obtain Ф2.5 alumina spherical support.

[0042] A solution was prepared by adding citric acid and phosphoric acid to 100 ml of water at a mass ratio of 1:0.00503. This solution was then used to impregnate the aforementioned Ф2.5 alumina (P: 300ml). 2 Spherical carriers (V: 0.78 ml / g) were dried at 125°C for 3 hours, and then calcined at 550°C for 4 hours to obtain P / Al2O3 support; then 130.3 g of Ni(NO3) was added per 100 ml of water. 2· Prepare an aqueous solution of Ni(NO3)2 using a 1:1 mass ratio of Ni(NO3)2 to 6H2O. 2· The above P / Al2O3 support was impregnated with 6H2O aqueous solution, air-dried naturally, dried at 120℃ for 3 hours, and then calcined at 500℃ for 6 hours to obtain catalyst sample H.

Claims

1. A method for preparing a nickel-based catalyst, characterized in that: The method includes the following: (1) Select or prepare an alumina carrier. Pretreat the alumina carrier with diluted phosphoric acid. The specific treatment process is as follows: Vacuum the alumina carrier with a vacuum degree of 0.2-0.8 MPa and a vacuum time of 10-30 min; introduce phosphoric acid solution into the vacuumed alumina carrier with a volume ratio of 1:1-1.5 between the alumina carrier and the phosphoric acid solution and a mass percentage concentration of 5%-10%; pressurize the alumina carrier with introduced phosphoric acid with a pressure of 0.5-0.8 MPa for 0.5-3 h, a treatment temperature of 15-50 °C, and an inert atmosphere; wash the treated alumina carrier with deionized water with a washing water volume of 2-15 times the carrier volume. (2) Prepare a nickel-containing active metal solution containing sodium gluconate and hexadecyltrimethylammonium chloride as dual surfactants; wherein the pH value of the nickel-containing active metal solution is 5.0~9.0, the concentration of sodium gluconate surfactant in the nickel-containing active metal solution is 0.5~5.0g / 100mL, and the concentration of hexadecyltrimethylammonium chloride surfactant is 0.5~10.0g / 100mL; the nickel-containing active metal solution contains additives, the additives being copper and titanium; in the nickel-containing active metal solution, the mass fraction of titanium source (calculated as titanium oxide) is 1.0%~7.5%, the mass fraction of nickel source (calculated as nickel oxide) is 20.5%~43.5%, and the mass fraction of copper source (calculated as copper oxide) is 1.0%~6.0%; (3) The alumina support after the pretreatment in step (1) is impregnated with a nickel-containing active metal solution containing sodium gluconate and hexadecyltrimethylammonium chloride dual surfactants prepared in step (2), and then dried and calcined to obtain a nickel-based catalyst. In the nickel-based catalyst, the dispersion of metallic Ni is: I Ni / I Al The value is between 0.160 and 0.250, where I Ni / I Al This represents the ratio of nickel atoms to aluminum atoms on the catalyst surface; the metal grain size is 2~6 nm. The nickel-based catalyst has the following pore size distribution: pores <3nm account for ≤0.6% of the total pore volume, and pores 3~15nm account for ≥94.0% of the total pore volume.

2. The method according to claim 1, characterized in that: The alumina carrier mentioned in step (1) contains SiO2, P2O5 and / or B2O3, with a content of 0.1wt% to 5.0wt% of the weight of the alumina carrier.

3. The method according to claim 1, characterized in that: The specific surface area of ​​the alumina carrier is greater than or equal to 300 m². 2 / g, pore volume is greater than or equal to 1.2mL / g, pore size is 11~18nm.

4. The method according to claim 3, characterized in that: The specific surface area of ​​the alumina carrier is 350–400 m². 2 / g; pore volume is 1.2~1.5mL / g.

5. The method according to claim 1, characterized in that: The process of making alumina carrier in step (1) is as follows: Weigh alumina dry adhesive powder, add adhesive, and obtain alumina carrier by extrusion molding, drying and calcination.

6. The method according to claim 5, characterized in that: The amount of adhesive added is 2.0% to 15.0% of the weight of alumina dry adhesive powder. It is extruded into a clover shape. Drying conditions: 100 to 150°C for 2 to 8 hours. Calcination conditions: 600 to 800°C for 3 to 8 hours.

7. The method according to claim 6, characterized in that: Drying conditions: 110-130℃, drying for 4-6 hours, calcination time for 4-6 hours.

8. The method according to claim 1, characterized in that: The alumina carrier with introduced phosphoric acid was subjected to pressure treatment for 1.0 to 2.0 hours; the treated alumina carrier was then washed with deionized water, with the amount of water being 5 to 10 times the amount of carrier.

9. The method according to claim 8, characterized in that: After washing, the product is dried and calcined. The drying temperature is 100-120℃, the heating rate is 15-20℃ / h, the drying time is 2-8h, and the calcination temperature is 500-600℃ for 3-8 hours.

10. The method according to claim 9, characterized in that: The drying time is 4 to 6 hours, and the calcination time is 4 to 6 hours.

11. The method according to claim 1, characterized in that: In step (2), the concentration of sodium gluconate surfactant in the obtained nickel-containing active metal solution is 1.0-3.0 g / 100 mL, and the concentration of hexadecyltrimethylammonium chloride surfactant is 3.0-5.0 g / 100 mL.

12. The method according to claim 1, characterized in that: The nickel mentioned in step (2) is derived from at least one of nickel hydroxide, nickel sulfate, nickel nitrate, nickel chloride, and nickel oxide.

13. The method according to claim 1, characterized in that: The copper source is at least one of copper sulfate, copper nitrate, copper chloride, and copper oxide; the titanium source is at least one of titanium tetrachloride, titanium tetrafluoride, titanium nitrate, titanium sulfate, and titanium acetate.

14. The method according to claim 1, characterized in that: In step (2), in the nickel-containing active metal solution, the mass fraction of titanium source (calculated as titanium oxide) is 1.5% to 5.0%, the mass fraction of nickel source (calculated as nickel oxide) is 25.0% to 35.0%, and the mass fraction of copper source (calculated as copper oxide) is 1.5% to 4.5%.

15. The method according to claim 1, characterized in that: In step (3), the impregnation is carried out by equal volume impregnation or over-volume impregnation. In the over-volume impregnation method, the volume ratio of the impregnation liquid to the catalyst support is 1.2 to 1.

5.

16. The method according to claim 15, characterized in that: The impregnation conditions are as follows: temperature 20-80℃, time 1.0-2.0h, impregnation once or multiple times, drying at 80-130℃ for 2-4 hours after impregnation, and calcination at 200-450℃ for 3-5 hours.

17. A nickel-based catalyst prepared by the method according to any one of claims 1-16, characterized in that: Based on the mass of the catalyst, the content includes: 15.0% to 40.0% nickel (based on NiO), 0.5% to 5.0% titanium (based on TiO2), and 0.5% to 5.0% copper (based on CuO).

18. The nickel-based catalyst according to claim 17, characterized in that: Based on the mass of the catalyst, the content includes: 20.0% to 30.0% nickel (based on NiO), 1.0% to 3.0% titanium (based on TiO2), and 1.0% to 2.5% copper (based on CuO).

19. The nickel-based catalyst according to claim 17, characterized in that: The dispersion of metallic Ni is: I Ni / I Al The range is 0.180 to 0.

220.

20. The nickel-based catalyst according to claim 17, characterized in that: The catalyst has a specific surface area of ​​160~180m². 2 / g; pore volume is 0.45~0.60mL / g, average pore size is 11~13nm, and metal grain size is 4~6nm.

21. The nickel-based catalyst according to claim 17, characterized in that: The pore size distribution in the catalyst channels is as follows: pores <3nm account for ≤0.6% of the total pore volume, and pores 3~15nm account for ≥94.0% of the total pore volume.

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