Columnar SBA-15 molecular sieve, Ni / SBA-15 catalyst as well as preparation method and application of Ni / SBA-15 catalyst

Abstract

The invention relates to the technical field of hydrogenation catalysis, in particular to a columnar SBA-15 molecular sieve and a preparation method and application thereof.The columnar SBA-15 molecular sieve is prepared according to the following method that P123, concentrated hydrochloric acid and water with the required amount are mixed and stirred till P123 is completely dissolved, and then a first mixed solution is obtained; adding a required amount of silicon source tetraethoxysilane into the first mixed solution, and stirring to obtain a second mixed solution; performing hydrothermal crystallization treatment on the second mixed solution to obtain a molecular sieve containing a template agent; and roasting the molecular sieve containing the template agent at high temperature to obtain the columnar SBA-15 molecular sieve. The Ni / SBA-15 catalyst prepared on the basis of the columnar SBA-15 molecular sieve is large in specific surface area, concentrated in pore size distribution, excellent in comprehensive catalytic performance, low in cost and environmentally friendly.

Description

Technical Field

[0001] The present invention relates to the technical field of hydrocatalytic technology, and provides a columnar SBA-15 molecular sieve, a Ni / SBA-15 catalyst, and their preparation methods and applications. Background Art

[0002] China is rich in C4 resources, but the chemical utilization rate is low. In addition, a small amount of alkynes in C4 hydrocarbons will lead to unsafe venting. During the chemical utilization process, diolefins and alkynes are prone to polymerization, causing catalyst poisoning, and the use of a large amount of butene and butane will dilute them and reduce their value. The catalytic hydrogenation technology can be used to hydrogenate the alkyne-containing materials into high-value chemical raw materials. The hydrogenation of diolefins and alkynes is mainly for the production of butene and butane by hydrogenation. The utilization value of butene is relatively high, and it is more meaningful to study the selective hydrogenation of C4 hydrocarbons to butene. The key to the selective hydrogenation process of C4 highly unsaturated hydrocarbons is to control the partial hydrogenation of reactants, inhibit the side reactions of over-hydrogenation and carbon deposition, otherwise it will lead to poor process selectivity and reduced yield of target products. To obtain the target products 1-butene or 2-butene, different selective hydrogenation catalysts should be used. Olefins are extremely easy to hydrogenate into alkanes, so the development of efficient catalysts has become the core of the selective hydrogenation technology. Supported catalysts are the main catalyst types for the selective hydrogenation of C4 alkynes, and their carriers are mainly Al 2 O 3 、SiO 2 、TiO 2 and molecular sieves, etc., which can effectively improve the selective hydrogenation activity, selectivity and stability, but still cannot meet the requirements of enterprise products. In recent years, due to its special hexagonal pore structure, SBA-15 molecular sieve has a large specific surface area and pore volume, and good stability, and has been widely used in the catalytic field. Its unique two-dimensional pores play a key role in the adsorption process of reaction molecules. The particle morphology and pore structure of SBA-15 molecular sieve have a great influence on the catalytic performance of the catalyst. By controlling the synthesis conditions, the two-dimensional length, morphology and particle size of the hexagonal structure SBA-15 molecular sieve can be controlled, thereby promoting the catalytic effect in the selective hydrogenation reaction of C4 hydrocarbons. Therefore, it is of great significance to obtain a columnar SBA-15 molecular sieve material with simple preparation conditions and controllable morphology and size and apply it to the selective hydrogenation catalyst of C4 hydrocarbons. Summary of the Invention

[0003] The present invention provides a columnar SBA-15 molecular sieve and a Ni / SBA-15 catalyst, which overcome the deficiencies of the above-mentioned prior art, and can effectively solve the problems of complex preparation process, single morphology and uncontrollable particle size of the existing columnar SBA-15 molecular sieve during preparation, resulting in low selectivity.

[0004] One of the technical solutions of the present invention is achieved by the following measures: A columnar SBA-15 molecular sieve is prepared by the following method:

[0005] In the first step, the required amount of P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide), concentrated hydrochloric acid and water are mixed and stirred until P123 is completely dissolved to obtain a first mixed solution;

[0006] In the second step, the required amount of silicon source tetraethyl orthosilicate is added to the first mixed solution, and after stirring, a second mixed solution is obtained;

[0007] In the third step, the second mixed solution is subjected to hydrothermal crystallization treatment to obtain a molecular sieve containing a template agent;

[0008] In the fourth step, the molecular sieve containing the template agent is calcined at a high temperature to obtain a columnar SBA-15 molecular sieve.

[0009] The following is a further optimization or / and improvement of one of the above-mentioned technical solutions of the invention:

[0010] In the above-mentioned first step, the stirring temperature is 25°C to 45°C.

[0011] In the above-mentioned first step, the molar ratio of tetraethyl orthosilicate, P123, concentrated hydrochloric acid and water is 1:(0.015 to 0.019):(5.8 to 6.2):(135 to 140).

[0012] In the above-mentioned second step, the stirring temperature is 25°C to 45°C, the stirring speed is 500 r / min to 1000 r / min, and the stirring time is 20 h to 25 h.

[0013] In the above-mentioned third step, the temperature of hydrothermal crystallization is 110°C to 125°C, and the time is 20 h to 25 h.

[0014] In the above-mentioned fourth step, the operation of calcining at a high temperature is as follows: The molecular sieve containing the template agent is placed in a muffle furnace and heated to 500°C to 600°C at a heating rate of 2°C / min, and then calcined at a constant temperature for 5.5 h to 6.5 h.

[0015] The above-mentioned columnar SBA-15 molecular sieve has a length of 300 nm to 1100 nm, a diameter of 75 nm to 450 nm, a pore diameter of 7 nm to 10 nm, a pore volume of 1.0 cm 3 / g to 1.7 cm 3 / g, a specific surface area of 400 m 2 / g to 600 m 2 / g, and an aspect ratio of 1.5 to 5.

[0016] In the first step above, the stirring temperature is 38°C to 42°C; in the second step, the stirring temperature is 38°C to 42°C and the stirring speed is 550 r / min to 650 r / min.

[0017] The length of the above-mentioned columnar SBA-15 molecular sieve is 350 nm to 450 nm, the diameter is 80 nm to 120 nm, and the aspect ratio is 3 to 5.

[0018] The second technical solution of the present invention is achieved by the following measures: A preparation method of a columnar SBA-15 molecular sieve is carried out according to the following steps:

[0019] In the first step, the required amount of P123, concentrated hydrochloric acid and water are mixed and stirred until P123 is completely dissolved to obtain a first mixed solution;

[0020] In the second step, the required amount of silicon source tetraethyl orthosilicate is added to the first mixed solution, and after stirring, a second mixed solution is obtained;

[0021] In the third step, the second mixed solution is subjected to hydrothermal crystallization treatment to obtain a molecular sieve containing a template agent;

[0022] In the fourth step, the molecular sieve containing the template agent is calcined at a high temperature to obtain a columnar SBA-15 molecular sieve.

[0023] The third technical solution of the present invention is achieved by the following measures: A preparation method of a Ni / SBA-15 catalyst is carried out according to the following steps:

[0024] In step one, the required amount of nickel salt is dissolved in water to obtain a nickel salt solution;

[0025] In step two, the nickel salt solution is added to the required amount of columnar SBA-15 molecular sieve, and after mixing evenly, a reaction mixture is obtained;

[0026] In step three, the reaction mixture is successively subjected to ultrasonic treatment, standing, drying, calcination, and reduction treatments to obtain a Ni / SBA-15 catalyst.

[0027] The following is a further optimization and / or improvement of the third technical solution of the above invention:

[0028] The above nickel salt is Ni(NO 3 ) 2 ·6H 2 O; the mass ratio of the nickel salt to the columnar SBA-15 molecular sieve is 0.060:1.0 to 0.090:1.0.

[0029] The above-mentioned reaction mixture is successively subjected to ultrasonic treatment, standing, drying, calcination, and reduction treatments to obtain a Ni / SBA-15 catalyst, including:

[0030] After ultrasonic treatment of the reaction mixture for 20 min to 45 min, it was allowed to stand at room temperature for 10 h to 14 h, dried at 75 °C to 85 °C, and then placed in a muffle furnace. The muffle furnace was heated to 540 °C to 560 °C at a heating rate of 2 °C / min, and then calcined at a constant temperature for 5.5 h to 6.5 h to obtain solid particles; the solid particles were reduced in a hydrogen atmosphere to obtain the Ni / SBA-15 catalyst.

[0031] The fourth technical solution of the present invention is achieved by the following measures: a Ni / SBA-15 catalyst prepared by a method for preparing a Ni / SBA-15 catalyst.

[0032] The fifth technical solution of the present invention is achieved by the following measures: an application of a Ni / SBA-15 catalyst in the selective hydrogenation of acetylenic C4 to butene.

[0033] The following is a further optimization and / or improvement of the above-mentioned fifth technical solution of the invention:

[0034] The reaction conditions for the selective hydrogenation of acetylenic C4 to butene are as follows:

[0035] The reaction temperature is 38 °C to 42 °C, the reaction pressure is 0.8 MPa to 1.2 MPa, the volume space velocity is 14 h -1 to 22 h -1 , and the hydrogen / hydrocarbon ratio is 140 to 180 (v / v).

[0036] The raw material composition for the selective hydrogenation of acetylenic C4 to butene includes, by mole percentage: the total amount of dienes and alkynes is 2% to 20%, butene is 60% to 70%, and butane is 22% to 31%.

[0037] The present invention provides a columnar SBA-15 molecular sieve, and a Ni / SBA-15 catalyst prepared based on the columnar SBA-15 molecular sieve, which has a large specific surface area and a concentrated pore size distribution. The Ni / SBA-15 catalyst of the present invention has excellent comprehensive catalytic performance in the selective hydrogenation reaction of acetylenic C4 hydrocarbons, and has the characteristics of low cost and environmental friendliness. Description of the Drawings

[0038] Attached Figure 1 is the SEM image of SBA-15 molecular sieves with different morphologies in Example 22 of the present invention.

[0039] Attached Figure 2 is the N 2 -adsorption and desorption isotherms (a, b) and pore size distribution curves (c, d) of Ni / SBA-15 catalysts with different morphologies in Example 22 of the present invention.

[0040] Attached Figure 3SEM images of SBA-15 molecular sieves with different sizes in Example 22 of the present invention.

[0041] Attachment Figure 4 N 2 -adsorption and desorption isotherms (a, b) and pore size distribution curves (c, d) of Ni / SBA-15 catalysts with different sizes in Example 22 of the present invention.

[0042] Attachment Figure 5 Catalyst performance evaluation diagrams of different sizes in Example 22 of the present invention. Detailed implementation manners

[0043] The present invention is not limited by the following embodiments, and specific implementation manners can be determined according to the technical solutions of the present invention and actual situations. All chemical reagents and chemical supplies mentioned in the present invention are well-known and commonly used chemical reagents and chemical supplies in the prior art unless otherwise specified; the percentages in the present invention are mass percentages unless otherwise specified; normal temperature and room temperature in the present invention generally refer to the temperature from 15°C to 25°C, and are generally defined as 25°C.

[0044] The present invention will be further described below in conjunction with embodiments:

[0045] Example 1: The preparation method of the columnar SBA-15 molecular sieve includes the following steps:

[0046] First step, mix the required amounts of P123, concentrated hydrochloric acid and water, and stir until P123 is completely dissolved to obtain a first mixed solution;

[0047] Second step, add the required amount of the silicon source tetraethyl orthosilicate to the first mixed solution, and stir to obtain a second mixed solution;

[0048] Third step, perform hydrothermal crystallization treatment on the second mixed solution to obtain a molecular sieve containing a template agent;

[0049] Fourth step, after calcining the molecular sieve containing the template agent at a high temperature, a columnar SBA-15 molecular sieve is obtained.

[0050] Example 2: As an optimization of the above embodiment, in the first step, the stirring temperature is 25°C to 45°C.

[0051] Example 3: As an optimization of the above embodiment, in the first step, the molar ratio of tetraethyl orthosilicate, P123, concentrated hydrochloric acid and water is 1:(0.015 to 0.019):(5.8 to 6.2):(135 to 140).

[0052] Example 4: As an optimization of the above examples, in the second step, the stirring temperature is 25°C to 45°C, the stirring speed is 500 r / min to 1000 r / min, and the stirring time is 20 h to 25 h.

[0053] Example 5: As an optimization of the above examples, in the third step, the temperature of hydrothermal crystallization is 110°C to 125°C, and the time is 20 h to 25 h. Specifically, the product after hydrothermal crystallization is washed successively with ethanol and water, and then placed in an oven at 80°C for drying for 6 h to obtain a molecular sieve containing a template agent.

[0054] Example 6: As an optimization of the above examples, in the fourth step, the operation of calcination at high temperature is as follows: The molecular sieve containing a template agent is placed in a muffle furnace and heated to 500°C to 600°C at a heating rate of 2°C / min, and then calcined at a constant temperature for 5.5 h to 6.5 h.

[0055] Example 7: As an optimization of the above examples, the length of the columnar SBA-15 molecular sieve is 300 nm to 1100 nm, the diameter is 75 nm to 450 nm, the pore diameter is 7 nm to 10 nm, the pore volume is 1.0 cm 3 / g to 1.7 cm 3 / g, the specific surface area is 400 m 2 / g to 600 m 2 / g, and the aspect ratio is 1.5 to 5.

[0056] Example 8: As an optimization of the above examples, in the first step, the stirring temperature is 38°C to 42°C; in the second step, the stirring temperature is 38°C to 42°C, and the stirring speed is 550 r / min to 650 r / min.

[0057] Example 9: As an optimization of the above examples, the length of the columnar SBA-15 molecular sieve is 350 nm to 450 nm, the diameter is 80 nm to 120 nm, and the aspect ratio is 3 to 5. Under the optimized conditions, when the stirring temperature in the first and second steps is 38°C to 42°C and the stirring speed in the second step is 550 r / min to 650 r / min, the prepared columnar SBA-15 molecular sieve has a better morphology, with a length of 350 nm to 450 nm, a diameter of 80 nm to 120 nm, and an aspect ratio of 3 to 5.

[0058] Example 10: The preparation method of the Ni / SBA-15 catalyst is carried out according to the following steps:

[0059] Step 1, dissolve the required amount of nickel salt in water to obtain a nickel salt solution;

[0060] Step 2, add the nickel salt solution to the required amount of columnar SBA-15 molecular sieve, and after mixing evenly, obtain a reaction mixture;

[0061] Step 3: After subjecting the reaction mixture to ultrasonic treatment, static settling, drying, calcination, and reduction treatment in sequence, a Ni / SBA-15 catalyst is obtained.

[0062] The Ni / SBA-15 catalyst of the present invention is prepared by the equal-volume impregnation method.

[0063] Example 11: As an optimization of the above example, the nickel salt is Ni(NO 3 ) 2 ·6H 2 O; the mass ratio of the nickel salt to the columnar SBA-15 molecular sieve is 0.060:1.0 to 0.090:1.0.

[0064] Example 12: As an optimization of the above example, after subjecting the reaction mixture to ultrasonic treatment, static settling, drying, calcination, and reduction treatment in sequence, a Ni / SBA-15 catalyst is obtained, including:

[0065] After ultrasonic treating the reaction mixture for 20 min to 45 min, statically settling it at room temperature for 10 h to 14 h, drying it at 75°C to 85°C, then placing it in a muffle furnace, and raising the temperature of the muffle furnace to 540°C to 560°C at a heating rate of 2°C / min, and then maintaining the temperature for calcination for 5.5 h to 6.5 h to obtain solid particles; the solid particles are reduced in a hydrogen atmosphere to obtain a Ni / SBA-15 catalyst.

[0066] Example 13: Application of the Ni / SBA-15 catalyst in the selective hydrogenation of acetylenic C4 to butene.

[0067] Example 14: As an optimization of the above example, the reaction conditions for the selective hydrogenation of acetylenic C4 to butene are:

[0068] The reaction temperature is 38°C to 42°C, the reaction pressure is 0.8 MPa to 1.2 MPa, the volume space velocity is 14 h -1 to 22 h -1 , and the hydrogen / hydrocarbon ratio is 140 to 180 (v / v).

[0069] Example 15: As an optimization of the above example, the raw material composition for the selective hydrogenation of acetylenic C4 to butene includes, by mole percentage: the total amount of dienes and alkynes is 2% to 20%, butene is 60% to 70%, and butane is 22% to 31%.

[0070] Example 16: The preparation process of the Ni / SBA-15 catalyst is as follows:

[0071] ① Preparation of columnar SBA-15 molecular sieve:

[0072] Take 4.00 g of P123, 20.73 mL of concentrated hydrochloric acid, and 87.92 mL of deionized water and place them in a beaker. Stir continuously for 1 h under a water bath at 30 °C until the P123 is completely dissolved to obtain a first mixed solution;

[0073] Dropwise add 8.452 g of tetraethyl orthosilicate to the first mixed solution, heat it under a water bath at 30 °C and stir for 24 h at a stirring rate of 900 r / min to obtain a second mixed solution;

[0074] Transfer the second mixed solution into a polytetrafluoroethylene autoclave and place it in an oven for crystallization at a crystallization temperature of 120 °C and a crystallization time of 24 h to obtain a third mixed solution;

[0075] Wash the third mixed solution successively with ethanol and deionized water, and dry it at 80 °C for 6 h to obtain columnar SBA-15 molecular sieve containing a template agent;

[0076] Place the columnar SBA-15 molecular sieve containing a template agent in a muffle furnace and calcine it under a programmed temperature rise. The columnar SBA-15 molecular sieve is obtained, where the programmed temperature rise rate is 2 °C / min, the calcination temperature is 550 °C, and the constant temperature calcination time is 6 h.

[0077] The morphology of the columnar SBA-15 molecular sieve obtained in this example is as follows: the length is from 700 nm to 1100 nm, the diameter is from 350 nm to 450 nm, the pore diameter is 7.74 nm, the pore volume is 1.0 cm 3 / g, the specific surface area is 432.78 m 2 / g, and the aspect ratio is from 1.5 to 3.

[0078] ② Preparation of Ni / SBA-15 catalyst:

[0079] Prepare the Ni / SBA-15 catalyst by the equal-volume impregnation method;

[0080] Add 3.5 mL of deionized water to 0.080 g of Ni(NO 3 ) 2 ·6H 2 O to obtain a nickel salt solution;

[0081] Dropwise add the nickel salt solution to 1.0 g of columnar SBA-15 molecular sieve. After 30 min of ultrasonic treatment, 12 h of standing, and drying at 80 °C for 6 h in sequence, place the columnar SBA-15 molecular sieve containing the nickel salt in a muffle furnace and calcine it under a programmed temperature rise to obtain solid particles. The programmed temperature rise rate in the muffle furnace is 2 °C / min, the calcination temperature is 550 °C, and the calcination time is 6 h;

[0082] After pressing and sieving the solid particles, reduction is carried out under a hydrogen atmosphere to obtain the Ni / SBA-15 catalyst. Among them, when sieving, the mesh number of the sieve is 30 to 40 meshes, the reduction temperature is 450 °C, and the reduction time is 8 h.

[0083] Example 17: The preparation process of the Ni / SBA-15 catalyst is as follows:

[0084] ① Preparation of columnar SBA-15 molecular sieve:

[0085] Take 4.00 g of P123, 20.73 mL of concentrated hydrochloric acid, and 87.92 mL of deionized water and place them in a beaker. Stir continuously for 1 h under a water bath condition of 40 °C until P123 is completely dissolved to obtain a first mixed solution;

[0086] Dropwise add 8.452 g of tetraethyl orthosilicate to the first mixed solution, heat and stir in a water bath at 40 °C for 24 h, and the stirring rate is 900 r / min to obtain a second mixed solution;

[0087] Transfer the second mixed solution into a polytetrafluoroethylene kettle and place it in an oven for crystallization. The crystallization temperature is 120 °C and the crystallization time is 24 h to obtain a third mixed solution;

[0088] Wash the third mixed solution successively with ethanol and deionized water, and dry it at 80 °C for 6 h to obtain a columnar SBA-15 molecular sieve containing a template agent;

[0089] Place the columnar SBA-15 molecular sieve containing the template agent in a muffle furnace and calcine it under a programmed temperature rise. The columnar SBA-15 molecular sieve is obtained, where the programmed temperature rise rate is 2 °C / min, the calcination temperature is 550 °C, and the calcination time is 6 h.

[0090] The morphology of the columnar SBA-15 molecular sieve obtained in this example is: the length is 500 nm to 650 nm, the diameter is 100 nm to 150 nm, the pore diameter is 7.77 nm, the pore volume is 1.63 cm 3 / g, the specific surface area is 568.12 m 2 / g, and the aspect ratio is 3 to 5.

[0091] ② Preparation of Ni / SBA-15 catalyst:

[0092] The Ni / SBA-15 catalyst is prepared by the equal-volume impregnation method;

[0093] Add 3.5 mL of deionized water to 0.080 g of Ni(NO 3 ) 2 ·6H 2 O to obtain a nickel salt solution;

[0094] The nickel salt solution was added dropwise to 1.0 g of columnar SBA-15 molecular sieve. After 30 min of ultrasonic treatment, 12 h of static standing, and drying at 80 °C for 6 h in sequence, the columnar SBA-15 molecular sieve containing the nickel salt was placed in a muffle furnace and calcined under programmed temperature rise to obtain solid particles. The programmed temperature rise rate in the muffle furnace was 2 °C / min, the calcination temperature was 550 °C, and the calcination time was 6 h;

[0095] After the solid particles were pressed into tablets and sieved, they were reduced under a hydrogen atmosphere to obtain the Ni / SBA-15 catalyst. Among them, when sieving, the mesh number of the sieve was 30 to 40 meshes, the reduction temperature was 450 °C, and the reduction time was 8 h.

[0096] Example 18: The preparation process of the Ni / SBA-15 catalyst is as follows:

[0097] ① Preparation of columnar SBA-15 molecular sieve:

[0098] Take 4.20 g of P123, 21.40 mL of concentrated hydrochloric acid, and 85.42 mL of deionized water and place them in a beaker. Stir continuously for 1 h under the condition of a 40 °C water bath until P123 is completely dissolved to obtain the first mixed solution;

[0099] Add 9.00 g of tetraethyl orthosilicate dropwise to the first mixed solution, heat it in a 40 °C water bath and stir for 24 h, and the stirring rate is 600 r / min to obtain the second mixed solution;

[0100] Transfer the second mixed solution into a polytetrafluoroethylene kettle and place it in an oven for crystallization. The crystallization temperature is 120 °C and the crystallization time is 24 h to obtain the third mixed solution;

[0101] Wash the third mixed solution with ethanol and deionized water in sequence, and dry it at 80 °C for 6 h to obtain the columnar SBA-15 molecular sieve containing the template agent;

[0102] Place the columnar SBA-15 molecular sieve containing the template agent in a muffle furnace and calcine it under programmed temperature rise to obtain the columnar SBA-15 molecular sieve. Among them, the programmed temperature rise rate is 2 °C / min, the calcination temperature is 560 °C, and the constant temperature calcination time is 5.5 h.

[0103] The morphology of the columnar SBA-15 molecular sieve obtained in this example is: the length is 350 nm to 450 nm, the diameter is 80 nm to 120 nm, the pore diameter is 9.05 nm, the pore volume is 1.49 cm 3 / g, and the specific surface area is 475.11 m 2 / g, and the aspect ratio is 3 to 5.

[0104] ② Preparation of Ni / SBA-15 catalyst:

[0105] The Ni / SBA-15 catalyst was prepared by the equal-volume impregnation method;

[0106] 3.5 mL of deionized water was added to 0.080 g of Ni(NO 3 ) 2 ·6H 2 O to obtain a nickel salt solution;

[0107] The nickel salt solution was added dropwise to 1.0 g of columnar SBA-15 molecular sieve. After 30 min of ultrasonic treatment, 12 h of static settlement, and 6 h of drying at 80 °C in sequence, the columnar SBA-15 molecular sieve containing the nickel salt was placed in a muffle furnace and calcined under programmed temperature increase to obtain solid particles. The programmed temperature increase rate in the muffle furnace was 2 °C / min, the calcination temperature was 550 °C, and the calcination time was 6 h;

[0108] After the solid particles were pressed into tablets and sieved, they were reduced under a hydrogen atmosphere to obtain the Ni / SBA-15 catalyst. Among them, when sieving, the mesh number of the sieve was 30 to 40 meshes, the reduction temperature was 450 °C, and the reduction time was 8 h.

[0109] Example 19: The Ni / columnar SBA-15 molecular sieve catalyst obtained in Example 16 was used for the selective hydrogenation reaction of acetylenic C4.

[0110] Raw material composition: The content of diolefin + alkyne was 2.80 wt.%, the content of butene was 67.82 wt.%, the content of butane was 29.30 wt.%, and the rest were C1-C3 hydrocarbons.

[0111] Reaction conditions: The reaction temperature was 40 °C, the reaction pressure was 1.0 MPa, the volume space velocity was 18 h -1 , the hydrogen / hydrocarbon ratio was 160 (v / v), and the Ni loading was 1.5 wt.% (calculated as Ni).

[0112] The target product was butene. The conversion rate of diolefin + alkyne in the raw material was 55.32%, and the selectivity to butene was 27.00%.

[0113] Example 20: The Ni / columnar SBA-15 molecular sieve catalyst obtained in Example 17 was used for the selective hydrogenation reaction of acetylenic C4.

[0114] Raw material composition: The content of diolefin + alkyne was 2.80 wt.%, the content of butene was 67.82 wt.%, the content of butane was 29.30 wt.%, and the rest were C1 to C3 hydrocarbons.

[0115] Reaction conditions: The reaction temperature was 40 °C, the reaction pressure was 1.0 MPa, the volume space velocity was 18 h -1 , the hydrogen / hydrocarbon ratio was 160 (v / v), and the Ni loading was 1.5 wt.% (calculated as Ni).

[0116] The target product is butene, the conversion rate of diolefin + alkyne in the raw material is 64.58%, and the selectivity for butene is 78.37%.

[0117] Example 21: The Ni / cylindrical SBA-15 molecular sieve catalyst obtained in Example 18 was used for the selective hydrogenation reaction of acetylene-rich C4.

[0118] Raw material composition: The content of diolefin + alkyne is 2.80 wt.%, the content of butene is 67.82 wt.%, the content of butane is 29.30 wt.%, and the rest are C1-C3 hydrocarbons.

[0119] The reaction conditions were: reaction temperature 40 °C, reaction pressure 1.0 MPa, space velocity 18 h -1 , hydrogen / hydrocarbon ratio 160 (v / v), and Ni loading of 1.5 wt.% (calculated as Ni).

[0120] The target product is butene, the conversion rate of diolefin + alkyne in the raw material is 77.62%, and the selectivity for butene is 62.11%.

[0121] Comparative Example 1: The difference from Example 17 is that in the preparation of SBA-15 molecular sieve, the first mixed solution was obtained as follows: 4.00 g of P123, 6.97 mL of concentrated hydrochloric acid, 131.02 mL of deionized water, 26.52 mL of absolute ethanol, and 0.708 g of cetyltrimethylammonium bromide were continuously stirred under a water bath condition at 40 °C until P123 was completely dissolved to obtain the first mixed solution. The rest of the steps were the same.

[0122] The SBA-15 molecular sieve obtained in this comparative example is a spherical SBA-15 molecular sieve with a diameter of 2.5 μm to 3.5 μm, a pore diameter of 1.98 nm, a pore volume of 0.68 cm 3 / g, and a specific surface area of 760.54 m 2 / g.

[0123] The nickel-based catalyst was further prepared from the spherical SBA-15 molecular sieve according to the steps of Example 17, denoted as Ni / SBA-15 molecular sieve (SS) catalyst.

[0124] Comparative Example 2: The difference from Example 17 is that the water bath temperature was 50 °C in the steps of obtaining the first mixed solution and the second mixed solution. The rest of the steps were the same.

[0125] The SBA-15 molecular sieve obtained in this comparative example is a strip-shaped SBA-15 molecular sieve with a length of 1100 nm to 1300 nm, a diameter of 80 nm to 120 nm, a pore diameter of 9.42 nm, and a pore volume of 1.40 cm 3 / g, with a specific surface area of 430.62 m 2 / g, and an aspect ratio of 10 to 17.

[0126] The nickel-based catalyst was further prepared from the strip-shaped SBA-15 molecular sieve according to the steps of Example 17, denoted as Ni / SBA-15 molecular sieve (SL) catalyst.

[0127] Comparative Example 3: The Ni / SBA-15 molecular sieve (SS) catalyst obtained in Comparative Example 1 was used for the selective hydrogenation of acetylenic C4. The raw material composition and reaction conditions were the same as those in Example 19.

[0128] In this comparative example, the product composition was butene and butane, the conversion of dienes + alkynes in the raw material was 67.83%, and the selectivity to butene was 0.

[0129] Comparative Example 4: The Ni / SBA-15 molecular sieve (SL) catalyst obtained in Comparative Example 2 was used for the selective hydrogenation of acetylenic C4.

[0130] The raw material composition and reaction conditions were the same as those in Example 19.

[0131] In this comparative example, the product composition was butene and butane, the conversion of dienes + alkynes in the raw material was 99.99%, and the selectivity to butene was 0.

[0132] Example 22: Various influencing factors in the preparation of the Ni / SBA-15 catalyst and the performance of the Ni / SBA-15 molecular sieve catalyst were investigated.

[0133] (1) Screening of carrier materials

[0134] Supported catalysts are the main catalyst type for the selective hydrogenation of C4 alkynes. Their carriers are mainly Al 2 O 3 , SiO 2 , TiO 2 and molecular sieves, etc., which can effectively improve the selective hydrogenation activity, selectivity and stability. Currently, the Al 2 O 3 carrier is used in industry, but there are still problems of excessive acidity and hydrogenation, which cannot meet the requirements of enterprise products. The pure silicon-type carrier lacks acidic sites and is suitable for use as a hydrogenation catalyst carrier. In order to compare and study the effects of different Al 2 O 3 and SiO 2 type carriers on the selective hydrogenation performance of acetylenic C4, Al 2 O 3, Nickel-based catalysts were prepared using pseudoboehmite, silica gel, ZSM-5, SBA-15 molecular sieve, and KIT-6 as supports for hydrogenation reactions (under the reaction conditions of Example 18), and the catalysts were denoted as Ni / Al, Ni / PB, Ni / Si, Ni / Z, Ni / S, and Ni / KIT, respectively. Tables 1 and 2 show the product distribution after the hydrogenation reaction of Ni-based catalysts with different supports, the calculated conversion rate of dienes + alkynes, and the butene selectivity. It can be seen that the content of dienes + alkynes in the reaction products of Ni / Al, Ni / PB, and Ni / Z is high, but the conversion rate is low; the conversion rate of dienes + alkynes in the catalytic reaction products of Ni / KIT is very high, but the over-hydrogenation phenomenon is serious, and the selectivity for butene is poor; while the product distributions of Ni / Si and Ni / S are relatively ideal, but within the reaction time (8 hours), the content of "green oil" (low-molecular-weight olefin polymers generated during the reaction) in the side reaction products of the Ni / Si catalyst is the highest, and the stability is poor. The support type and morphology have a great influence on the selective hydrogenation performance of acetylenic-rich C4. Considering the activity, selectivity, and stability comprehensively, Ni / S (SBA-15 molecular sieve) is the most suitable selective hydrogenation catalyst for acetylenic-rich C4.

[0135] Table 1

[0136] Number Diolefin + alkyne content / % Butene content / % Butane content / % Ni / S 0.99％ 69.23％ 29.58％ Ni / Z 2.65％ 67.97％ 29.30％ Ni / KIT 0.01％ 51.93％ 47.99％ Ni / Si 1.62％ 69.00％ 29.30％ Ni / PB 2.68％ 67.94％ 29.30％ Ni / Al 2.68％ 67.94％ 29.30％

[0137] Table 2

[0138] Number Diolefin + alkyne conversion rate / % Butene selectivity / % Ni / S 64.58％ 78.37％ Ni / Z 5.40％ 100％ Ni / KIT 99.71％ 0 Ni / Si 42.09％ 100％ Ni / PB 4.35％ 100％ Ni / Al 4.17％ 100％

[0139] (2) Morphology control of SBA-15 molecular sieve

[0140] The support morphology does have a great influence on the selective hydrogenation performance. For the convenience of description, in the following research discussions, the columnar SBA-15 molecular sieve (short) prepared in Example 16 is denoted as SC, and the Ni / SBA-15 catalyst is denoted as Ni / SC; the columnar SBA-15 molecular sieve (long) prepared in Example 17 is denoted as SR, and the Ni / SBA-15 catalyst is denoted as Ni / SR; the spherical SBA-15 molecular sieve prepared in Comparative Example 1 is denoted as SS, and the Ni / SBA-15 molecular sieve (SS) catalyst is denoted as Ni / SS. The strip-shaped SBA-15 molecular sieve prepared in Comparative Example 2 is denoted as SL, and the Ni / SBA-15 catalyst is denoted as Ni / SL.

[0141] From the morphologies of the SBA-15 molecular sieves prepared in Examples 16, 17, and Comparative Examples 1 and 2 Figure 1), different synthesis temperatures and surfactants (Comparative Example 1) can be used to synthesize SBA-15 molecular sieves of different morphologies. This is because, during the preparation process, as the water bath temperature increases, the length of the SBA-15 molecular sieve particles in the two-dimensional direction gradually increases. According to experimental observations, as the stirring temperature increases, the hydrolysis rate of tetraethyl orthosilicate in the solution accelerates, and silicates are prompted to aggregate rapidly. Higher stirring temperatures promote the axial growth of SBA-15 molecular sieve particles, increase the length of SBA-15 molecular sieve particles, and shorten the time from clarification to the appearance of white precipitates in the solution. This phenomenon may be due to the different surface tensions of the amphiphilic block copolymer species and the silicate species. Therefore, the higher the temperature, the greater the aspect ratio of the material obtained. When the required amount of CTAB (hexadecyltrimethylammonium bromide) co-surfactant is added, the particle morphology of the SBA-15 molecular sieve is spherical.

[0142] (3) Analysis of catalyst morphology and structure under temperature influence

[0143] The SBA-15 molecular sieves prepared in Examples 16 and 17 and Comparative Examples 1 and 2 were characterized by SEM:

[0144] SEM images of SBA-15 molecular sieves with different morphologies Figure 1 As shown, the image clearly shows the structure of SBA-15 molecular sieve, and the surfaces of SC, SR, and SL materials have obvious ordered stripes and small fragments attached.

[0145] N 2 Low temperature physical adsorption and desorption characterization (BET):

[0146] N 2 Adsorption is a commonly used method to characterize the pore properties of support materials and catalysts. Figure 2 N of SBA-15 molecular sieves with different morphologies 2 Adsorption-desorption isotherms and pore size distribution curves. Figure 2 It can be seen from a and c that, except for the spherical shape, the SBA-15 molecular sieves of different morphologies all present typical type IV isotherms (the isotherm type is the physical adsorption isotherm type specified by the International Union of Pure and Applied Chemistry), and there is an H1 type hysteresis loop, indicating that the synthesized mesoporous material has a high degree of order and a uniform pore size distribution. 2 The adsorption-desorption isotherm is a type I isotherm, but there is an obvious hysteresis loop, which is caused by the hysteresis loop formed by a small amount of mesoporous structure in the structure.

[0147] In addition, from Figure 2 N of Ni / SBA-15 molecular sieves with different morphologies 2It can also be obtained from the adsorption - desorption isotherm diagram that Ni / SC, Ni / SR, and Ni / SL also exhibit typical type - IV isotherms and H1 - type hysteresis loops, and the mesoporous materials have high order and uniform pore size distributions.

[0148] Table 3 shows the structural properties of zeolites with different morphologies and the corresponding catalysts calculated from the 2 adsorption - desorption isotherm (where S BET is the multi - point BET specific surface area; S Micro is the internal specific surface area by the t - plot method; S Meso is the external specific surface area by the t - plot method; V Total is the single - point total pore volume; D HK is the most probable pore diameter of micropores by the HK method; D BJH is the most probable pore diameter of mesopores by the BJH method). Among them, SS has the highest specific surface area (760.54 m 2 / g), and the specific surface areas of SC, SR, and SL are 432.78 m 2 / g, 568.12 m 2 / g, and 430.62 m 2 / g, respectively. The pore sizes of SBA - 15 zeolites with different morphologies follow the order: SS (1.78 nm) < SC (7.74 nm) < SR (7.77 nm) < SL (8.85 nm). The above data indicate that a high synthesis temperature is conducive to increasing the pore size of pure SBA - 15 zeolites. After loading the active metal components, the specific surface area, pore volume, and pore size of the Ni / SC, Ni / SR, Ni / SL, and Ni / SS catalysts will decrease because the active components cover part of the pores and specific surface area.

[0149] Table 3

[0150]

[0151] (4) Hydrogenation performance analysis of catalysts with different morphologies

[0152] Hydrogenation reaction conditions: reaction temperature is 40 °C, reaction pressure is 1.0 MPa, space velocity is 18 h -1 ⁻¹, hydrogen / hydrocarbon ratio is 160 (v / v), the feed flow rate of C4 is 0.3 mL / min, the catalyst loading is 1.0 mL, and the Ni loading is 1.5 wt.% (calculated as Ni).

[0153] The performance of Ni / SBA-15 catalysts with different morphologies in the selective hydrogenation of acetylenic C4 hydrocarbons is shown in Table 4 (product distribution after hydrogenation reaction) and Table 5 (conversion of dienes + alkynes and selectivity of butenes). The content of dienes + alkynes and olefins in the products of Ni / SL catalysis is the lowest, indicating high conversion and serious over-hydrogenation. The long-range two-dimensional pores of the strip-shaped support material cause the reactants and products to stay in the pores for too long, making them easily adsorbed by the active components and undergo secondary hydrogenation reactions, and the olefins in the raw materials will also be hydrogenated. The content of dienes + alkynes in the products of the Ni / SR catalyst is relatively low, while the butene content is higher than that of the raw materials, indicating that the catalyst has a certain selectivity for butenes. After calculation, the conversion of dienes + alkynes is 64.58% and the selectivity of butenes is 78.37%, ensuring that the olefins in the raw materials are not hydrogenated to butane, showing relatively excellent comprehensive catalytic performance. The cumulative oligomer content of all morphology catalysts is <0.001% after 8 hours of reaction. In summary, for the purpose of converting dienes + alkynes in C4 hydrocarbons as much as possible and minimizing the reaction of butenes in the raw materials, the Ni / SR catalyst has the best hydrogenation selectivity and certain activity, and is a catalyst with good comprehensive performance for the selective hydrogenation of C4 hydrocarbons to butenes.

[0154] Table 4

[0155] Number Diolefin + alkyne content / % Butene content / % Butane content / % Ni / SC 1.48％ 69.28％ 29.17％ Ni / SR 0.99％ 69.23％ 29.58％ Ni / SS 0.90％ 64.16％ 34.84％ Ni / SL 0.0002％ 5.43％ 94.42％

[0156] Table 5

[0157] Number Diolefin + alkyne conversion rate / % Butene selectivity / % Ni / SC 55.32％ 27.00％ Ni / SR 64.58％ 78.37％ Ni / SS 67.83％ 0 Ni / SL 99.99％ 0

[0158] (5) Regulation of the particle size of SBA-15 molecular sieve

[0159] Although the columnar catalyst structure has a certain selectivity for the hydrogenation of acetylenic C4 hydrocarbons, it is at the cost of losing some activity. To further improve the catalytic activity and selectivity, the particle size of the columnar catalyst is finely adjusted.

[0160] Referring to the preparation process of Example 17, by changing the shear force, the stirring in the preparation process of the second mixed solution is carried out at stirring speeds of 900 r / min, 600 r / min, 300 r / min, and 0 r / min respectively to obtain SBA-15 molecular sieves with different sizes and prepare Ni / SBA-15 catalysts. According to different stirring speeds, the prepared mesoporous materials of SBA-15 molecular sieves with different sizes are denoted as S900, S600, S300, and S0 respectively, and their corresponding nickel-based catalysts are named Ni / S900, Ni / S600, Ni / S300, and Ni / S0.

[0161] Formation mechanism of SBA-15 molecular sieves with different sizes: The particle size of columnar SBA-15 molecular sieves was regulated by simply changing the stirring rate (shearing force) during the synthesis process. After adding tetraethyl orthosilicate dropwise, the silicon source would hydrolyze and aggregate, and gradually form micelles with the template P123. At this time, the dynamic shearing force of stirring would accelerate the hydrolysis rate of tetraethyl orthosilicate and enhance the solubilization effect of micelles. As the shearing force increased, the micelles gradually enlarged, resulting in an increase in the particle size of the finally obtained molecular sieves.

[0162] (6) Analysis of the morphology and structure of the catalyst under the influence of shearing force

[0163] SEM characterization:

[0164] The SEM images of SBA-15 molecular sieves with different sizes are as Figure 3 shown. The images clearly show that all materials are columnar, with obvious ordered stripes on the surface of the materials and small fragments attached. After measurement, the average particle lengths are 583 nm (S900), 414 nm (S600), 352 nm (S300), and 205 nm (S0), respectively.

[0165] N 2 Low-temperature physical adsorption and desorption characterization (BET):

[0166] N 2 Adsorption is a commonly used characterization method for characterizing the pore properties of carrier materials and catalysts. Figure 4 are the N 2 adsorption-desorption isotherms and pore size distribution curves of SBA-15 molecular sieves with different sizes and Ni / SBA-15 catalysts. As can be seen from Figure 4 a and c, SBA-15 molecular sieves with different sizes all show typical type-IV isotherms and have H1-type hysteresis loops, indicating that the synthesized mesoporous materials have high order and uniform pore size distribution.

[0167] In addition, from the N 2 adsorption-desorption isotherms and corresponding pore size distribution diagrams of Ni / SBA-15 catalysts with different sizes, it can also be concluded that they also show typical type-IV isotherms and H1-type hysteresis loops, and the mesoporous materials have high order and uniform pore size distribution. The detailed structural characteristics of SBA-15 molecular sieves with different sizes and Ni / SBA-15 catalysts after loading Ni are shown in Table 6.

[0168] Table 6 shows the structural properties of molecular sieves with different sizes and corresponding catalysts calculated from the N 2 adsorption-desorption isotherms. All materials have a specific surface area of 500 m 2 / g to 600 m 2 / g high specific surface area and mesopore aperture of 7 nm to 10 nm. As the particle size of SBA-15 molecular sieve decreases, the pore size generally shows an increasing trend. After loading the active metal components, the specific surface area, pore volume and pore size of the catalyst will all decrease, because the active components cover part of the pores and specific surface area.

[0169] Table 6

[0170]

[0171] (7) Hydrogenation performance analysis of Ni / SBA-15 catalysts with different lengths

[0172] Reaction conditions: reaction temperature is 40 °C, reaction pressure is 1.0 MPa, space velocity is 18 h -1 , hydrogen / hydrocarbon ratio is 160 (v / v), C4 feed flow rate is 0.3 mL / min, catalyst loading is 1.0 mL, Ni loading is 1.5 wt.% (calculated as Ni).

[0173] The product distributions of selective hydrogenation of acetylenic C4 over Ni / SBA-15 catalysts with different sizes are shown in Table 7, Table 8 and Figure 5 as follows. As the catalyst particles decrease, the content of dienes + alkynes in the hydrogenation products decreases, that is, the conversion rate increases. The alkene content: Ni / S900 > Ni / S600 > Ni / S0 > Ni / S300. Among them, the alkene contents of Ni / S0 and Ni / S300 are much lower than those in the raw material, that is, the selectivity decreases or even the alkenes in the raw material also undergo hydrogenation, indicating that over-hydrogenation occurs in all catalysts, but the hydrogenation is more intense on Ni / S0 and Ni / S300 catalysts, and Ni / S300 suddenly deactivates after 7 hours of reaction. Within 8 hours of reaction time, the activity and selectivity of Ni / S900 catalyst first increase and then decrease, and reach the best performance at 6 hours, with the conversion rate of dienes + alkynes being 64.58% and the selectivity of butene being 78.37%; the activity of Ni / S600 catalyst continuously increases, and the selectivity first increases and then is basically stable, and reaches the best performance at 6 hours, with the conversion rate of dienes + alkynes being 77.62% and the selectivity of butene being 62.11%. The cumulative oligomer amount of all catalysts is <0.001% after 8 hours of reaction. In summary, aiming to convert dienes + alkynes in C4 hydrocarbons as much as possible and minimize the reaction of butenes in the raw material, in terms of the three aspects of hydrogenation activity, selectivity and stability, Ni / S600 catalyst is a catalyst with better comprehensive performance for hydrogenating C4 hydrocarbons to butenes.

[0174] Table 7

[0175] Number Diolefin + alkyne content / % Butene content / % Butane content / % Ni / S900 0.99％ 69.23％ 29.58％ Ni / S600 0.63％ 69.17％ 30.14％ Ni / S300 0.01％ 0.22％ 99.63％ Ni / S0 0.001％ 0.97％ 98.90％

[0176] Table 8

[0177] Number Diolefin + alkyne conversion rate / % Butene selectivity / % Ni / S900 64.58％ 78.37％ Ni / S600 77.62％ 62.11％ Ni / S300 97.92％ 0 Ni / S0 99.97％ 0

[0178] In summary, the present invention provides a columnar SBA-15 molecular sieve and a Ni / SBA-15 catalyst prepared based on the columnar SBA-15 molecular sieve, which has a large specific surface area and a concentrated pore size distribution. The Ni / SBA-15 catalyst of the present invention can convert dienes + alkynes in C4 hydrocarbons as much as possible and butene in the raw material does not react as much as possible in the selective hydrogenation reaction of C4 hydrocarbons rich in alkynes, has excellent comprehensive catalytic performance, low cost, and is green and environmentally friendly.

[0179] The above technical features respectively constitute the embodiments of the present invention, which have strong adaptability and implementation effects. Non-essential technical features can be added or subtracted according to actual needs to meet the requirements of different situations.

Claims

1. A columnar SBA-15 molecular sieve, characterized in that Prepared as follows: In the first step, a required amount of P123, concentrated hydrochloric acid and water are mixed and stirred until P123 is completely dissolved to obtain a first mixed solution; The second step is to add a required amount of silicon source ethyl orthosilicate to the first mixed solution, and stir to obtain a second mixed solution; The third step is to perform hydrothermal crystallization on the second mixed solution to obtain a molecular sieve containing a template; In the fourth step, the molecular sieve containing the template is calcined at high temperature to obtain a columnar SBA-15 molecular sieve.

2. The columnar SBA-15 molecular sieve according to claim 1, characterized in that In the first step, the stirring temperature is 25°C to 45°C; or / and; in the first step, the molar ratio of silicon source tetraethyl orthosilicate, P123, concentrated hydrochloric acid and water is 1:0.015 to 0.019:5.8 to 6.2:135 to 140; or / and; in the second step, the stirring temperature is 25°C to 45°C, the stirring speed is 500r / min to 1000r / min, and the stirring time is 20h to 25h; or / and; in the third step, the temperature of hydrothermal crystallization is 110°C to 125°C, and the time is 20h to 25h; or / and; in the fourth step, the operation of calcining at high temperature is: placing the molecular sieve containing the template in a muffle furnace, heating it to 500°C to 600°C at a heating rate of 2°C / min, and then calcining at a constant temperature for 5.5h to 6.5h.

3. The columnar SBA-15 molecular sieve according to claim 2, characterized in that The columnar SBA-15 molecular sieve has a length of 300nm to 1100nm, a diameter of 75nm to 450nm, a pore size of 7nm to 10nm, and a pore volume of 1.0cm 3 / g to 1.7cm 3 / g, specific surface area is 400m 2 / g to 600m 2 / g, and the aspect ratio is 1.5 to 5.

4. The columnar SBA-15 molecular sieve according to claim 2 or 3, characterized in that In the first step, the stirring temperature is 38°C to 42°C; in the second step, the stirring temperature is 38°C to 42°C, and the stirring speed is 550r / min to 650r / min.

5. The columnar SBA-15 molecular sieve according to claim 3, characterized in that The columnar SBA-15 molecular sieve has a length of 350nm to 450nm, a diameter of 80nm to 120nm, and an aspect ratio of 3 to 5.

6. A method for preparing a columnar SBA-15 molecular sieve according to claim 2, characterized in that Follow these steps: In the first step, a required amount of P123, concentrated hydrochloric acid and water are mixed and stirred until P123 is completely dissolved to obtain a first mixed solution; The second step is to add a required amount of silicon source ethyl orthosilicate to the first mixed solution, and stir to obtain a second mixed solution; The third step is to perform hydrothermal crystallization on the second mixed solution to obtain a molecular sieve containing a template; In the fourth step, the molecular sieve containing the template is calcined at high temperature to obtain a columnar SBA-15 molecular sieve.

7. A method for preparing a Ni / SBA-15 catalyst using the columnar SBA-15 molecular sieve according to any one of claims 1 to 5 as a raw material, characterized in that Follow these steps: Step 1, dissolving a required amount of nickel salt in water to obtain a nickel salt solution; Step 2, adding the nickel salt solution to a required amount of columnar SBA-15 molecular sieve, mixing evenly, to obtain a reaction mixture; Step 3, subjecting the reaction mixture to ultrasonic treatment, standing, drying, calcination and reduction treatment in sequence to obtain a Ni / SBA-15 catalyst.

8. The method for preparing the Ni / SBA-15 catalyst according to claim 7, characterized in that The nickel salt is Ni(NO3)2·6H2O; the mass ratio of the nickel salt to the columnar SBA-15 molecular sieve is 0.060:1.0 to 0.090:1.0; or / and; the reaction mixture is subjected to ultrasonic treatment, standing, drying, roasting and reduction treatment in sequence to obtain a Ni / SBA-15 catalyst, including: ultrasonicating the reaction mixture for 20 minutes to 45 minutes, standing at room temperature for 10 hours to 14 hours, drying at 75°C to 85°C, and then placing it in a muffle furnace, the muffle furnace is heated to 540°C to 560°C at a heating rate of 2°C / min, and then constant temperature roasting is performed for 5.5 hours to 6.5 hours to obtain solid particles; the solid particles are reduced in a hydrogen atmosphere to obtain a Ni / SBA-15 catalyst.

9. A Ni / SBA-15 catalyst prepared according to the method for preparing the Ni / SBA-15 catalyst according to claim 7 or 8.

10. An application of the Ni / SBA-15 catalyst according to claim 9 in selective hydrogenation of alkyne-rich carbon four to butene, characterized in that The reaction conditions for selective hydrogenation of alkyne-rich carbon four to butene are: reaction temperature of 38°C to 42°C, reaction pressure of 0.8MPa to 1.2MPa, and volume space velocity of 14h -1 Until 22h -1 , the hydrogen / hydrocarbon ratio is 140 to 180; or / and; the raw material composition of the selective hydrogenation of alkyne-rich carbon four to butene includes, by mole percentage, the total amount of dienes and alkynes is 2% to 20%, butene is 60% to 70%, and butane is 22% to 31%.

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