Preparation of a composite carrier catalyst and use thereof

Abstract

The application provides a preparation of a composite carrier catalyst and application thereof, and comprises the following steps: S1, first ball milling of an active raw material, wherein a binder is added in the first ball milling process to obtain component A, and the catalyst carrier comprises alumina, cerium oxide and lanthanum oxide; a plurality of catalyst carriers are mixed and then subjected to second ball milling, wherein nitric acid solution is added in the second ball milling process to obtain component B, and component A and component B are mixed and subjected to third ball milling to obtain a mixture; S2, the mixture is subjected to kneading and granulation, and the granulated material is calcined to obtain a precursor; and S3, the precursor is subjected to reduction and passivation to obtain the composite carrier catalyst. The application loads the active raw material through a multi-stage ball milling process, and the loading amount of the active component of the obtained catalyst is far higher than that of the impregnation method, and meanwhile, the defects caused by the introduction of impurities due to the use of lye in the coprecipitation method are completely avoided, so that the advantages of high loading amount and high purity are combined, and the obtained catalyst has excellent activity and stability, and the process is green and environmentally friendly.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of catalysts, more particularly to a preparation of a composite carrier catalyst and application thereof. BACKGROUND

[0002] 1,4-Butanediol (BDO) is a high value-added basic chemical raw material and an organic synthesis intermediate. Butynediol hydrogenation reaction is an important step in the production of 1,4-butanediol by Reppe method. The process is a complex continuous reaction. The purpose of hydrogenation is to convert a small amount of 1,4-butene diol and 4-hydroxybutyraldehyde and acetal impurities generated by isomerization of 1,4-butene diol into 1,4-butanediol. The essence is the hydrogenation of unsaturated functional groups such as "C=C" and "C=0". Therefore, the effect of hydrogenation is crucial to control yield and quality. In the hydrogenation industry, a supported nickel catalyst is generally selected, and the carrier is alumina or the like. The catalyst has an important influence on the hydrogenation reaction. At present, the composite carrier catalyst is mainly prepared by co-precipitation and impregnation. The preparation process is complex. Moreover, in the process of loading by impregnation, the active metal components cannot be completely impregnated and adsorbed. Many of them only stay on the surface of the carrier, resulting in a large loss of active metal components and a large waste of metal salts. The activity and stability of the catalyst are also poor. Although the co-precipitation method can load more metal active components, sodium ions are wrapped in the catalyst during the precipitation process. A large amount of wastewater needs to be used for washing, and the sodium ions cannot be completely removed by washing. The high residual sodium ions affect the selectivity of some high-quality catalysts and do not meet the green and environmentally friendly chemical concept.

[0003] Therefore, further improvement and development are needed. SUMMARY

[0004] In view of various deficiencies of the prior art, in order to solve the above problems, a preparation of a composite carrier catalyst and application thereof are proposed, and the following technical solutions are provided.

[0005] A preparation of a composite carrier catalyst, the preparation method comprises the following steps,

[0006] S1: First ball milling of active raw materials, adding a binder during the first ball milling process to obtain component A; mixing the catalyst carrier and then second ball milling, adding nitric acid solution during the second ball milling process to obtain component B; mixing component A and component B, and third ball milling to obtain a mixture, wherein the catalyst carrier comprises alumina, cerium oxide and lanthanum oxide;

[0007] S2: Kneading and granulating the mixture, and then calcining the granulated material to obtain a precursor;

[0008] S3: Reducing and passivating the precursor to obtain a composite carrier catalyst.

[0009] Further, the first ball mill adopts a grinding ball diameter of 5-10mm, the first ball mill temperature is 80-90℃, the first ball mill time is 4-8h;The second ball mill adopts a grinding ball diameter of 10-15mm, the second ball mill temperature is 60-80℃, the second ball mill time is 8-12h;The third ball mill adopts a grinding ball diameter of 3-6mm, the third ball mill temperature is 60-80℃, the third ball mill time is 4-8h.

[0010] Further, the nitric acid solution is a 1-5wt% dilute nitric acid solution, the mass of the nitric acid solution is 2-3% of the total mass of the catalyst carrier, and the nitric acid solution is added when the second ball milling is carried out for 3-5h.

[0011] Further, the binder is added when the water content of the active raw material is less than ≤6% during the first ball milling process.

[0012] Further, the active raw material is nickel nitrate hexahydrate, and the binder is amaranth powder.

[0013] Further, the raw material includes 500-600 parts of nickel nitrate hexahydrate, 600-800 parts of aluminum oxide, 60-120 parts of cerium oxide, 60-120 parts of lanthanum oxide, and 4-6 parts of amaranth powder by mass.

[0014] Further, in the S2 step, the granulated material is first dried, the drying temperature is 120-160℃, and the drying time is 3-5h.

[0015] Further, in the S2 step, the calcination process is gradient temperature calcination, and the calcination process is as follows: heating to 200-300℃ for 3h, holding for 3-4h;Heating to 300-400℃ for 3h, holding for 3-4h;Heating to 400-500℃ for 3h, holding for 3-4h.

[0016] The application also provides a composite carrier catalyst and an application of the prepared composite carrier catalyst, which is applied to butyne diol hydrogenation reaction.

[0017] Due to the adoption of the above technical scheme, the application has the following beneficial technical effects:

[0018] 1. The application provides a preparation of a composite carrier catalyst, which loads active raw materials through a multi-stage ball milling process, and the catalyst prepared by the method has a metal active component load far exceeding the conventional impregnation method, completely avoids the defects of introducing sodium ions and other impurities caused by the use of lye in the coprecipitation method, has the advantages of high load and high purity, and has excellent activity and stability of the obtained catalyst, and the process is green and environmentally friendly.

[0019] 2.The catalyst prepared by the multi-stage ball milling process and the step-by-step calcination procedure has suitable particle fineness, pore structure and active center distribution, and when applied to the butyne glycol hydrogenation reaction, exhibits excellent catalytic activity, selectivity and long-term running stability, can efficiently convert unsaturated impurities into the target product 1,4-butanediol, and effectively improves the product quality and reaction yield.

[0020] 3.The catalyst has a certain carrier and metal ratio, introduces rare earth metals lanthanum and cerium, improves the strength of the carrier, has more active centers, and improves the dispersion degree of nickel metal, and therefore exhibits excellent stability in the butyne glycol hydrogenation catalytic reaction. DETAILED DESCRIPTION

[0021] In order to make the personnel in the art better understand the technical solutions of the present application, the technical solutions of the present application will be described clearly and completely below in combination with the embodiments of the present application, and other similar embodiments obtained by the personnel in the art without creative labor on the basis of the embodiments in the present application shall all belong to the protection scope of the present application.

[0022] A preparation method of a composite carrier catalyst, comprising the following steps,

[0023] S1: the active raw material is subjected to first ball milling, and a binder is added in the first ball milling process to obtain component A; the catalyst carrier is mixed and then subjected to second ball milling, and nitric acid solution is added in the second ball milling process to obtain component B; component A and component B are mixed, and third ball milling is performed to obtain a mixture material, wherein the catalyst carrier comprises alumina, ceria and lanthanum oxide;

[0024] S2: the mixture material is subjected to kneading and granulation, and the granulated material is subjected to calcination to obtain a precursor;

[0025] S3: the precursor is subjected to reduction and passivation to obtain the composite carrier catalyst.

[0026] In the S1 step, the mesh number of the active component in component A is ≤1000 meshes, and the moisture content of the active component is ≤4%, in the S3 step, the reduction temperature is controlled at 400-500°C, the hydrogen flow rate is 200-500ml / min, after reduction, the temperature is reduced to room temperature, then 1% oxygen-containing nitrogen mixed gas is introduced for passivation, and the passivation time is 3h. The method for detecting the water content is to take a small amount of sample, and directly titrate and detect by the Karl Fischer method.

[0027] The application provides a preparation method of a composite carrier catalyst, and an active material is loaded through a multi-stage ball milling process.

[0028] The diameter of the grinding ball used in the first ball milling is 5-10 mm, the first ball milling temperature is 80-90 DEG C, and the first ball milling time is 4-8 h; the diameter of the grinding ball used in the second ball milling is 10-15 mm, the second ball milling temperature is 60-80 DEG C, and the second ball milling time is 8-12 h; the diameter of the grinding ball used in the third ball milling is 3-6 mm, the third ball milling temperature is 60-80 DEG C, and the third ball milling time is 4-8 h. The application limits the diameter, temperature and time parameters of the grinding ball of each of the three ball millings. The differentiated and refined ball milling condition design makes the first stage adopt medium ball diameter and high temperature ball milling, which is beneficial to the preliminary activation of the active material and the preliminary combination with the binder; the second stage adopts large ball diameter, moderate temperature and long time ball milling, which can effectively pre-activate and modify the mixed carrier and optimize the surface properties thereof; and the third stage adopts small ball diameter for final mixing ball milling, so as to ensure that all components are in a superfine (2800-3200 mesh) and uniform dispersion state. The parameter combination collectively guarantees excellent uniformity and reaction activity of the final material.

[0029] In the S2 step, the calcination process is gradient temperature calcination, and the calcination process is as follows: the temperature is raised to 200-300 DEG C for 3 h, and then the temperature is kept for 3-4 h; the temperature is raised to 300-400 DEG C for 3 h, and then the temperature is kept for 3-4 h; and the temperature is raised to 400-500 DEG C for 3 h, and then the temperature is kept for 3-4 h. The application adopts a multi-stage gradient temperature calcination system, and through setting three temperature rising and keeping stages of 200-300 DEG C, 300-400 DEG C and 400-500 DEG C, physical and chemical changes such as decomposition of the binder, decomposition of the active material and oxide phase conversion in the material can be orderly and gently carried out. The mild calcination method is beneficial to forming a catalyst precursor with reasonable pore size distribution, moderate crystal size and stable structure, and avoids problems such as sintering of the active component, collapse of the pore channel or excessive internal stress caused by rapid temperature rising, so as to improve the activity and durability of the final catalyst.

[0030] The application also provides a composite carrier catalyst prepared by the preparation method and application of the composite carrier catalyst.

[0031] The composite carrier catalyst is applied to the reaction of catalyzing butynediol hydrogenation, the reaction temperature is 120-150 DEG C, and the pressure is 3-12 MPa.

[0032] Example 1

[0033] S1: Take 520g of nickel nitrate hexahydrate, dry it in vacuum at 50℃ for 5 hours to remove part of the crystal water. Put the dried nickel nitrate hexahydrate into a No. 1 ball mill, carry out the first ball milling, control the first ball milling temperature at 85℃, use the grinding ball with a diameter of 8mm, take sample to detect the water content of the material during the first ball milling, when the water content is reduced to about 6%, add 5g of sesbania powder into the No. 1 ball mill, continue to ball mill. The total time of the first ball milling is 6 hours, and component A is obtained. Take 100g of lanthanum oxide, 100g of cerium oxide and 700g of aluminum oxide, mix them and then put them into a No. 2 ball mill, control the second ball milling temperature at 70℃, use the grinding ball with a diameter of 12mm, carry out the second ball milling, after 4h of ball milling, add 27g of dilute nitric acid solution (concentration 3%), continue to ball mill for 6h, and keep the temperature at 70℃. The total time of the second ball milling is 10 hours, and component B is obtained. Put component A and component B into a No. 3 ball mill, control the third ball milling temperature at 70℃, use the grinding ball with a diameter of 4mm, continue to carry out the third ball milling, and the third ball milling time is 6 hours, until the particle size of the mixed material reaches about 3000 meshes, stop the ball milling, and the mixed material is obtained.

[0034] S2: Put the mixed material into an extruder to carry out extrusion granulation, dry the catalyst precursor after the extrusion granulation at 140℃ for 4h, and then carry out calcination by gradient temperature rising: rise the temperature to 250℃ for 3h, keep the temperature for 3h; rise the temperature to 350℃ for 3h, keep the temperature for 3h; rise the temperature to 450℃ for 3h, keep the temperature for 3h, and then cool down to obtain the precursor.

[0035] S3: Put the precursor into a tube furnace to carry out hydrogen reduction, control the reduction temperature at 450℃, after the reduction is completed, reduce it to room temperature, then pass in the nitrogen mixed gas containing 1% oxygen to carry out passivation, after 3h of passivation, package the catalyst for use.

[0036] Example 2

[0037] S1: Take 520 g of nickel nitrate hexahydrate, and dry it in vacuum at 50°C for 5 hours to remove part of the crystal water. Put the dried nickel nitrate hexahydrate into a No. 1 ball mill, and perform the first ball milling at a temperature of 90°C, using balls with a diameter of 10 mm. During the first ball milling, take samples to detect the water content of the material. When the water content is reduced to about 6%, add 5 g of sesbania powder into the No. 1 ball mill, and continue the ball milling. The total time of the first ball milling is 4 hours, and component A is obtained. Take 100 g of lanthanum oxide, 100 g of cerium oxide, and 700 g of aluminum oxide, mix them, and then put them into a No. 2 ball mill. Control the temperature of the second ball milling at 80°C, and use balls with a diameter of 15 mm. Perform the second ball milling for 3 hours, then add 27 g of dilute nitric acid solution (concentration 3%) and continue the ball milling for 5 hours while maintaining the temperature at 80°C. The total time of the second ball milling is 8 hours, and component B is obtained. Put component A and component B into a No. 3 ball mill, control the temperature of the third ball milling at 80°C, and use balls with a diameter of 6 mm. Continue the third ball milling for 4 hours until the particle size of the mixture reaches about 3200 mesh, and then stop the ball milling. The mixture is obtained.

[0038] S2: Put the mixture into an extruder to perform the extrusion granulation. Dry the catalyst precursor after the extrusion granulation at 140°C for 4 hours, and then perform the calcination by gradient heating: heat to 250°C for 3 hours, maintain the temperature for 3 hours; heat to 350°C for 3 hours, maintain the temperature for 3 hours; heat to 450°C for 3 hours, maintain the temperature for 3 hours, and then cool down. The precursor is obtained.

[0039] S3: Put the precursor into a tube furnace to perform the hydrogen reduction at a temperature of 450°C. After the reduction, reduce the temperature to room temperature, then pass the nitrogen mixed gas containing 1% oxygen to perform the passivation for 3 hours, and then package the catalyst for use.

[0040] Example 3

[0041] S1: Take 520 g of nickel nitrate hexahydrate, and dry it at 50°C under vacuum for 5 hours to remove part of the crystal water. Put the dried nickel nitrate hexahydrate into a No. 1 ball mill, and perform first ball milling at a temperature of 80°C, using grinding balls with a diameter of 5 mm. During the first ball milling, take samples to detect the water content of the material. When the water content is reduced to about 6%, add 5 g of sesbania powder into the No. 1 ball mill, and continue ball milling. The total time of the first ball milling is 8 hours, and component A is obtained. Take 100 g of lanthanum oxide, 100 g of cerium oxide, and 700 g of aluminum oxide, mix them, and then put them into a No. 2 ball mill. Control the temperature of the second ball milling at 60°C, and use grinding balls with a diameter of 10 mm. Perform second ball milling, and after 5 hours of ball milling, add 27 g of dilute nitric acid solution (concentration of 3%) and continue ball milling for 7 hours while maintaining the temperature at 60°C. The total time of the second ball milling is 12 hours, and component B is obtained. Mix components A and B into a No. 3 ball mill, control the temperature of the third ball milling at 60°C, and use grinding balls with a diameter of 3 mm. Continue third ball milling for 8 hours until the particle size of the mixture reaches about 3000 mesh, and then stop the ball milling. The mixture is obtained.

[0042] S2: Put the mixture into an extruder to perform extrusion granulation. The catalyst precursor after the extrusion granulation is first dried at 140°C for 4 hours, and then calcined by gradient heating: heating to 250°C for 3 hours, maintaining the temperature for 3 hours; heating to 350°C for 3 hours, maintaining the temperature for 3 hours; heating to 450°C for 3 hours, maintaining the temperature for 3 hours, and then cooling. The precursor is obtained.

[0043] S3: Put the precursor into a tube furnace to perform hydrogen reduction at a temperature of 450°C. After the reduction is completed, the temperature is reduced to room temperature, and then 1% oxygen-containing nitrogen mixed gas is introduced for passivation. After 3 hours of passivation, the catalyst is packaged and ready for use.

[0044] Example 4

[0045] S1: Take 520 g of nickel nitrate hexahydrate, and dry it in vacuum at 50°C for 5 hours to remove part of the crystal water. Put the dried nickel nitrate hexahydrate into a No. 1 ball mill, and perform the first ball milling at a temperature of 85°C, using grinding balls with a diameter of 8 mm. During the first ball milling, take samples to detect the water content of the material. When the water content is reduced to about 6%, add 5 g of sesbania powder into the No. 1 ball mill, and continue the ball milling. The total time of the first ball milling is 6 hours, and component A is obtained. Take 100 g of lanthanum oxide, 100 g of cerium oxide, and 700 g of aluminum oxide, mix them, and then put them into a No. 2 ball mill. Control the temperature of the second ball milling at 70°C, and use grinding balls with a diameter of 12 mm. Perform the second ball milling for 4 hours, then add 27 g of dilute nitric acid solution (concentration 3%), and continue the ball milling for 6 hours while maintaining the temperature at 70°C. The total time of the second ball milling is 10 hours, and component B is obtained. Mix component A and component B into a No. 3 ball mill, control the temperature of the third ball milling at 70°C, and use grinding balls with a diameter of 4 mm. Continue the third ball milling for 6 hours until the particle size of the mixture reaches about 3000 meshes, and then stop the ball milling. The mixture is obtained.

[0046] S2: Put the mixture into an extruder to perform the extrusion granulation. Dry the catalyst precursor after the extrusion granulation at 140°C for 4 hours, and then perform the calcination by gradient temperature rising: rise the temperature to 200°C for 3 hours, and maintain the temperature for 4 hours; rise the temperature to 300°C for 3 hours, and maintain the temperature for 3 hours; rise the temperature to 400°C for 3 hours, and maintain the temperature for 3 hours. Cool down to obtain the precursor.

[0047] S3: Put the precursor into a tube furnace to perform the hydrogen reduction at a temperature of 450°C. After the reduction, cool down to room temperature, then pass in the nitrogen mixed gas containing 1% oxygen to perform the passivation for 3 hours. Package the catalyst for use.

[0048] Example 5

[0049] S1: Take 520 g of nickel nitrate hexahydrate, and dry it in vacuum at 50°C for 5 hours to remove part of the crystal water. Put the dried nickel nitrate hexahydrate into a No. 1 ball mill, and perform the first ball milling at a temperature of 85°C, using grinding balls with a diameter of 8 mm. During the first ball milling, take samples to detect the water content of the material. When the water content is reduced to about 6%, add 5 g of sesbania powder into the No. 1 ball mill, and continue the ball milling. The total time of the first ball milling is 6 hours, and component A is obtained. Take 100 g of lanthanum oxide, 100 g of cerium oxide, and 700 g of aluminum oxide, mix them, and then put them into a No. 2 ball mill. Control the temperature of the second ball milling at 70°C, and use grinding balls with a diameter of 12 mm. Perform the second ball milling for 4 hours, and then add 27 g of dilute nitric acid solution (concentration of 3%) into the No. 2 ball mill, and continue the ball milling for 6 hours while maintaining the temperature at 70°C. The total time of the second ball milling is 10 hours, and component B is obtained. Mix component A and component B, and put them into a No. 3 ball mill. Control the temperature of the third ball milling at 70°C, and use grinding balls with a diameter of 4 mm. Continue the third ball milling for 6 hours, until the particle size of the mixture reaches about 3000 mesh, and then stop the ball milling. The mixture is obtained.

[0050] S2: Put the mixture into an extruder to perform the extrusion granulation. Dry the catalyst precursor after the extrusion granulation at 140°C for 4 hours, and then perform the calcination by gradient heating: heat to 300°C for 3 hours, and maintain the temperature for 4 hours; heat to 400°C for 3 hours, and maintain the temperature for 4 hours; heat to 500°C for 3 hours, and maintain the temperature for 4 hours. Cool down, and the precursor is obtained.

[0051] S3: Put the precursor into a tube furnace to perform the hydrogen reduction, and control the reduction temperature at 450°C. After the reduction is completed, reduce the temperature to room temperature, and then pass the nitrogen mixed gas containing 1% oxygen to perform the passivation. After the passivation is performed for 3 hours, the catalyst is packaged and ready for use.

[0052] Example 6

[0053] S1: Take 500g of nickel nitrate hexahydrate, and dry it in vacuum at 50°C for 5 hours to remove part of the crystal water. Put the dried nickel nitrate hexahydrate into a No. 1 ball mill, and perform the first ball milling at a temperature of 85°C, using grinding balls with a diameter of 8mm. During the first ball milling, take samples to detect the water content of the material. When the water content is reduced to about 6%, add 4g of sesbania powder into the No. 1 ball mill, and continue the ball milling. The total time of the first ball milling is 6 hours, and component A is obtained. Take 60g of lanthanum oxide, 60g of cerium oxide, and 600g of aluminum oxide, mix them, and then put them into a No. 2 ball mill. Control the temperature of the second ball milling at 70°C, and use grinding balls with a diameter of 12mm. Perform the second ball milling, and after 4 hours, add 14.4g of dilute nitric acid solution (concentration of 3%), and continue the ball milling for 6 hours while maintaining the temperature at 70°C. The total time of the second ball milling is 10 hours, and component B is obtained. Mix component A and component B, and put them into a No. 3 ball mill. Control the temperature of the third ball milling at 70°C, and use grinding balls with a diameter of 4mm. Continue the third ball milling for 6 hours, until the particle size of the mixture reaches about 3000 meshes, and then stop the ball milling. The mixture is obtained.

[0054] S2: Put the mixture into an extruder to perform the extrusion granulation. Dry the catalyst precursor after the extrusion granulation at 120°C for 3 hours, and then perform the calcination by gradient heating: heat to 250°C for 3 hours, maintain the temperature for 3 hours; heat to 350°C for 3 hours, maintain the temperature for 3 hours; heat to 450°C for 3 hours, maintain the temperature for 3 hours, and then cool down. The precursor is obtained.

[0055] S3: Put the precursor into a tube furnace to perform the hydrogen reduction, and control the reduction temperature at 450°C. After the reduction is completed, reduce the temperature to room temperature, then pass the nitrogen mixed gas containing 1% oxygen to perform the passivation, and after 3 hours of passivation, the catalyst is packaged for use.

[0056] Example 7

[0057] S1: Take 600 g of nickel nitrate hexahydrate and dry it at 50°C under vacuum for 5 hours to remove part of the crystal water. Add the dried nickel nitrate hexahydrate to a No. 1 ball mill and perform the first ball milling, controlling the first ball milling temperature at 85°C, using 8 mm diameter grinding balls. During the first ball milling, take samples to detect the water content of the material. When the water content is reduced to about 6%, add 6 g of sesbania powder to the No. 1 ball mill and continue ball milling. The total first ball milling time is 6 hours, and component A is obtained. Take 120 g of lanthanum oxide, 120 g of cerium oxide, and 800 g of aluminum oxide, mix them, and then add them to a No. 2 ball mill. Control the second ball milling temperature at 70°C, and use 12 mm diameter grinding balls to perform the second ball milling. After 4 hours of ball milling, add 31.2 g of dilute nitric acid solution (concentration 3%) and continue ball milling for 6 hours while maintaining the temperature at 70°C. The total second ball milling time is 10 hours, and component B is obtained. Mix components A and B in a No. 3 ball mill, control the third ball milling temperature at 70°C, and use 4 mm diameter grinding balls to continue the third ball milling. The third ball milling time is 6 hours, and the ball milling is stopped until the particle size of the mixed material reaches about 3000 mesh, and the mixed material is obtained.

[0058] S2: Put the mixed material into an extruder to perform extrusion and granulation. The catalyst precursor after extrusion and granulation is first dried at 160°C for 3 hours, and then gradient heating is performed for calcination: the temperature is raised to 250°C for 3 hours, maintained for 3 hours; the temperature is raised to 350°C for 3 hours, maintained for 3 hours; the temperature is raised to 450°C for 3 hours, maintained for 3 hours, and then cooled down to obtain the precursor.

[0059] S3: Put the precursor into a tube furnace for hydrogen reduction, controlling the reduction temperature at 450°C. After the reduction is completed, the temperature is reduced to room temperature, and then a nitrogen mixed gas containing 1% oxygen is introduced for passivation. After 3 hours of passivation, the catalyst is packaged for use.

[0060] Comparative Example 1

[0061] S1: Take 520 g of nickel nitrate hexahydrate and dry it at 50°C under vacuum for 5 hours to remove part of the crystal water. Add the dried nickel nitrate hexahydrate to a No. 1 ball mill and perform the first ball milling, controlling the ball milling temperature at 85°C, using 8 mm diameter grinding balls. The ball milling time is 6 hours. During the ball milling, take samples to detect the water content of the material. When the water content is reduced to about 6%, add 5 g of sesbania powder to the No. 1 ball mill and continue ball milling. Take 100 g of lanthanum oxide, 100 g of cerium oxide, and 700 g of aluminum oxide, mix them, and then add them to the No. 1 ball mill. After 4 hours of ball milling, add 27 g of dilute nitric acid solution (concentration 3%) and continue ball milling for 6 hours while maintaining the temperature at 70°C. Continue ball milling, and the ball milling time is 6 hours. Stop the ball milling until the particle size of the mixed material reaches about 3000 mesh, and the mixed material is obtained.

[0062] S2: The mixed material is sent into an extruder for extruding and granulating. The catalyst precursor after extruding and granulating is dried at 140℃ for 4h, and then calcined by gradient temperature rising: rising to 250℃ for 3h, holding for 3h; rising to 350℃ for 3h, holding for 3h; rising to 450℃ for 3h, holding for 3h, and cooling, to obtain the precursor.

[0063] S3: The precursor is added into a tube furnace for hydrogen reduction, and the reduction temperature is controlled at 450℃. After the reduction is completed, it is cooled to room temperature, and then 1% oxygen-containing nitrogen mixed gas is introduced for passivation. After passivation for 3h, the catalyst is packaged for use.

[0064] Comparative Example 2

[0065] S1: 520g of nickel nitrate hexahydrate is vacuum dried at 50℃ for 5h to remove part of the crystal water. The dried nickel nitrate hexahydrate is added into a No. 1 ball mill for first ball milling, the first ball milling temperature is controlled at 85℃, 8mm diameter grinding balls are used, and the first ball milling time is 6h. During the first ball milling, the sample is taken for detecting the water content of the material. When the water content is reduced to about 6%, 5g of sesbania powder is added into the No. 1 ball mill for continuous ball milling. The total first ball milling time is 6h, to obtain component A. 100g of lanthanum oxide, 100g of cerium oxide and 700g of aluminum oxide are mixed and added into a No. 2 ball mill. The second ball milling temperature is controlled at 70℃, 12mm diameter grinding balls are used, 27g of dilute nitric acid solution (concentration 3%) is added after ball milling for 4h, and the ball milling is continued for 6h while the temperature is maintained at 70℃. The total second ball milling time is 10h, to obtain component B. Components A and B are mixed into a No. 3 ball mill, the third ball milling temperature is controlled at 70℃, 4mm diameter grinding balls are used, and the third ball milling is continued for 6h until the particle size of the mixed material reaches about 3000 meshes, and the ball milling is stopped, to obtain the mixed material.

[0066] S2: The mixed material is sent into an extruder for extruding and granulating. The catalyst precursor after extruding and granulating is dried at 140℃ for 4h, and then calcined by gradient temperature rising: rising to 250℃ for 3h, holding for 3h; rising to 350℃ for 3h, holding for 3h; rising to 450℃ for 3h, holding for 3h, and cooling, to obtain the precursor.

[0067] Comparative Example 3

[0068] S1: Take 520 g of nickel nitrate hexahydrate, and dry it in vacuum at 50°C for 5 hours to remove part of the crystal water. Put the dried nickel nitrate hexahydrate into a No. 1 ball mill, and perform the first ball milling. The temperature of the first ball milling is controlled at 85°C, the diameter of the milling ball is 8 mm, and the first ball milling time is 6 hours. During the first ball milling, take a sample to detect the water content of the material. When the water content is reduced to about 6%, add 5 g of sesbania powder into the No. 1 ball mill, and continue the ball milling. The total time of the first ball milling is 6 hours, and component A is obtained. Take 200 g of lanthanum oxide, 200 g of cerium oxide, and 400 g of aluminum oxide, mix them, and then put them into a No. 2 ball mill. The temperature of the second ball milling is controlled at 70°C, the diameter of the milling ball is 12 mm, and the second ball milling is performed for 4 hours. Then, add 24 g of dilute nitric acid solution (concentration of 3%) into the No. 2 ball mill, and continue the ball milling for 6 hours while maintaining the temperature at 70°C. The total time of the second ball milling is 10 hours, and component B is obtained. Mix components A and B, and put them into a No. 3 ball mill. The temperature of the third ball milling is controlled at 70°C, the diameter of the milling ball is 4 mm, and the third ball milling is continued for 6 hours until the particle size of the mixed material reaches about 3000 meshes. Then, stop the ball milling, and the mixed material is obtained.

[0069] S2: Put the mixed material into an extruder to perform the extrusion granulation. The catalyst precursor after the extrusion granulation is first dried at 140°C for 4 hours, and then calcined by gradient temperature rising: the temperature is raised to 250°C for 3 hours, maintained for 3 hours; the temperature is raised to 350°C for 3 hours, maintained for 3 hours; the temperature is raised to 450°C for 3 hours, maintained for 3 hours, and then cooled, and the precursor is obtained.

[0070] S3: Put the precursor into a tube furnace to perform the hydrogen reduction. The reduction temperature is controlled at 450°C, and then reduced to room temperature after the reduction is completed. Then, a nitrogen mixed gas containing 1% oxygen is introduced to perform the passivation for 3 hours, and then the catalyst is packaged for use.

[0071] Comparative Example 4

[0072] The catalyst prepared by the impregnation method in the prior art is selected, and the specific steps are as follows:

[0073] Take 100 g of lanthanum oxide, 100 g of cerium oxide, and 700 g of aluminum oxide, mix them uniformly, and then add 27 g of dilute nitric acid solution with a concentration of 3 wt% as a peptizing agent, and fully knead. Put the kneaded material into an extruder to perform the extrusion molding, dry it at 140°C for 4 hours, and then calcine it at 500°C for 3 hours, and the shaped carrier is obtained.

[0074] Take 520 g of nickel nitrate hexahydrate, dissolve it in a proper amount of deionized water, and prepare a nickel nitrate impregnation solution with a certain concentration. The above impregnation solution is uniformly impregnated into the cooled shaped carrier by using the equal-volume impregnation method. The impregnated material is left for 12 hours, and then dried at 120°C for 4 hours, and then calcined at 450°C for 3 hours, and the catalyst precursor is obtained.

[0075] The precursor was reduced in a tube furnace at 450°C under hydrogen atmosphere, and after the reduction was completed, the temperature was lowered to room temperature. The catalyst was passivated by introducing a mixture of 1% oxygen and nitrogen for 3 hours to obtain a catalyst prepared by the impregnation method.

[0076] Test Example 1

[0077] The butynediol one-stage hydrogenation reaction liquid 150 g was weighed into an autoclave, and 4 g of the catalyst prepared in Examples 1-7 and Comparative Examples 1-3 was added, respectively. The autoclave was closed, and nitrogen was replaced for 3 times. Hydrogen was introduced until the pressure reached 3 MPa. Then, the temperature was raised to 130°C, and after 2 hours of incubation, the temperature was lowered. The conversion rate, butynediol content, butenediol content, and tetrahydroxybutyral content were detected by sampling. The results are shown in Table 1 below.

[0078] Table 1 Test results of catalysts of Examples 1-7 and Comparative Examples 1-4

[0079]

[0080] Test Example 2

[0081] The catalysts obtained in Examples 1-7 and Comparative Examples 1-4 were tested for metal loading. 0.1 g of the catalyst sample was weighed, and mixed acid such as nitric acid and hydrochloric acid was added. The solution was digested by microwave digestion (200°C) until it was clear. After cooling, the solution was diluted and filtered. Then, the metal ions were detected by ICP equipment. The test results are shown in Table 2 below.

[0082] Table 2 Metal loading of catalysts obtained in Examples 1-7 and Comparative Examples 1-4

[0083]

[0084] The catalyst prepared in Example 1 has the best effect, the ball milling process and various parameters of the calcination process are changed in Examples 2-7 when preparing the catalyst, and the test results of the measured catalyst are slightly inferior to Example 1, but the results are better than each comparative example. Examples 1-7 all use the three-stage ball milling and gradient temperature calcination process described in the claims, and the test results show that the conversion rate of butyne diol is as high as 99.9% or more, and the impurity (butene diol, tetrahydroxy butyl aldehyde) content is very low. This shows that the process can successfully prepare a catalyst with high activity and high selectivity. Comparative Example 1 cancels the segmented ball milling and adds all the raw materials at one time. The conversion rate drops to 97.45%, the impurity content increases significantly (butene diol is 0.46%), and the remaining raw materials are not converted. This directly proves that the segmented ball milling is essential for the high dispersion and uniform combination of the active component and the carrier, and is a key step to obtain excellent catalytic performance. Comparative Example 2 uses rapid temperature calcination, which causes the precursor to break down and cannot be tested. This confirms that gradient temperature calcination is essential to maintain the integrity of the catalyst skeleton structure and avoid physical damage caused by internal stress. Example 1 and Comparative Example 4 use the same amount of feed, and the ICP test of the metal content of the final catalyst shows that the active metal particle nickel content is significantly different, the nickel content of Example 1 is 10.44%, which is significantly higher than the nickel content of 7.36% of the catalyst obtained by the traditional impregnation method (Comparative Example 4).

[0085] In addition, it should be understood that although the present specification is described in terms of embodiments, not every embodiment contains only one independent technical solution, and the description of the specification is only for the sake of clarity. The skilled person should consider the specification as a whole, and the technical solutions in each example can be appropriately combined to form other embodiments that the skilled person can understand.

Claims

1. A method for preparing a composite support catalyst for the hydrogenation of butynediol, characterized by, The preparation method comprises the following steps, S1: first ball milling of the active raw material, the first ball milling process adding a binder, obtaining component A; the binder is added when the water content of the active raw material in the first ball milling process is less than or equal to 6%, and the catalyst carrier is mixed and then subjected to second ball milling, the second ball milling process adding a nitric acid solution, obtaining component B, mixing component A and component B, and then performing third ball milling to obtain a mixture, the catalyst carrier comprising alumina, cerium oxide and lanthanum oxide, and the active raw material being nickel nitrate hexahydrate; S2: the mixture is subjected to kneading and granulation, and the granulated material is subjected to calcination to obtain a precursor; the calcination process is gradient temperature calcination, and the calcination process is as follows: heating to 200-300 DEG C for 3h, and then maintaining the temperature for 3-4h; heating to 300-400 DEG C for 3h, and then maintaining the temperature for 3-4h; heating to 400-500 DEG C for 3h, and then maintaining the temperature for 3-4h; S3: the precursor is subjected to reduction and passivation to obtain a composite carrier catalyst; The first ball milling adopts grinding balls with a diameter of 5-10mm, the first ball milling temperature is 80-90 DEG C, and the first ball milling time is 4-8h; the second ball milling adopts grinding balls with a diameter of 10-15mm, the second ball milling temperature is 60-80 DEG C, and the second ball milling time is 8-12h; the third ball milling adopts grinding balls with a diameter of 3-6mm, the third ball milling temperature is 60-80 DEG C, and the third ball milling time is 4-8h.

2. The production method according to claim 1, characterized by, The nitric acid solution is a 1-5wt% dilute nitric acid solution, the mass of the nitric acid solution is 2-3% of the total mass of the catalyst carrier, and the nitric acid solution is added when the second ball milling is performed for 3-5h.

3. The preparation method according to claim 1, characterized in that, The binder is amaranth powder.

4. The production method according to claim 3, characterized by, The raw materials include 500-600 parts of nickel nitrate hexahydrate, 600-800 parts of alumina, 60-120 parts of cerium oxide, 60-120 parts of lanthanum oxide, and 4-6 parts of amaranth powder in terms of mass fraction.

5. The preparation method according to claim 1, characterized in that, In the S2 step, the granulated material is first dried, the drying temperature is 120-160 DEG C, and the drying time is 3-5h.

6. Use of a composite support catalyst prepared according to the preparation method of any one of claims 1 to 5, characterized in that, The application is applied to the hydrogenation reaction of butynediol.

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