A nickel-based catalyst, a preparation method and application thereof
By using a simple preparation method for nickel-based catalysts, the problems of complex preparation and high cost of nickel-based catalysts are solved, and high catalytic performance is achieved. It is suitable for the hydrogenation reaction of isophthalonitrile, maleic anhydride and pyridine compounds, and meets the needs of industrialization.
Patent Information
- Application Number
- CN202311131796.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-09-04
- Publication Date
- 2025-12-30
- Estimated Expiration
- 2043-09-04
AI Technical Summary
Existing methods for preparing nickel-based catalysts are complex and involve high costs and cumbersome operations in catalytic hydrogenation reactions, making it difficult to meet the needs of industrial production.
Nickel-based catalysts were prepared by co-current dropwise addition and calcination using nickel sulfate hexahydrate, anhydrous magnesium sulfate, and anhydrous sodium carbonate as raw materials. The catalyst component ratios are adjustable, including the main active component NiO, the co-active component MgO, and the inert component SiO2. The catalysts are suitable for the hydrogenation reactions of isophthalonitrile, maleic anhydride, and pyridine compounds.
The preparation process is simple, the catalyst has a specific surface area of over 300 m²/g, excellent catalytic activity, and is suitable for a variety of hydrogenation reactions, meeting the requirements of industrial production.
Abstract
Description
Technical Field
[0001] This invention belongs to the field of catalytic reaction technology, specifically relating to a nickel-based catalyst, its preparation method, and its application. Background Technology
[0002] Catalytic hydrogenation, a key technology in modern chemical industry, plays a vital role in the production of biopharmaceuticals and fine chemicals. While traditional chemical reduction methods are known to be mild and highly selective, they suffer from drawbacks such as environmental unfriendliness and cumbersome operation. Catalytic hydrogenation, however, is a highly efficient and convenient reduction method that effectively solves these problems. Catalytic hydrogenation not only aligns with the principles of efficiency in sustainable development but also with atom economy, thus possessing significant research value. In catalytic hydrogenation reactions, catalysts play a crucial role. Catalysts in hydrogenation reactions mainly fall into two categories: noble metal catalysts and non-noble metal catalysts. Among non-noble metal catalysts, nickel-based catalysts are widely used in the catalytic field due to their high catalytic activity, high mechanical strength, insensitivity to poisons, simple preparation methods, low cost, and ease of recycling.
[0003] There are many methods for preparing nickel-based catalysts, each with its own characteristics and different application fields. Patent CN 103418395B discloses a gel method for preparing nickel-based catalysts, using a mixture of alumina sol and silica sol as a carrier precursor, adding a nickel-ammonia complex and an auxiliary agent solution to obtain a mixed sol. The sol is then aged to obtain a gel, which is washed, dried, shaped, calcined, and reduced to obtain the desired nickel-based catalyst. Patent CN 109529850 A discloses a nickel-silicon catalyst, its preparation method, and its application. The catalyst preparation method involves first preparing a nickel-ammonia complex, then adding a silicon source dropwise to the complex, and finally obtaining the catalyst by ammonia stripping. The catalyst is used in the selective hydrogenation of maleic anhydride to succinic anhydride, requiring a reactor pressure of 2-6 MPa, which is relatively high. Patent CN 113398932 A discloses a method for preparing diamines by hydrogenation of dinitriles. The catalyst is prepared by precipitation. The active component of the catalyst is Ni and / or its oxides, the co-active component is Mg and / or its oxides, and the support is selected from alumina, silica, and molecular sieves. Patent CN104549291 B provides a method for preparing a nickel-aluminum catalyst, in which nickel and aluminum salts are dissolved and dispersed in ethanol for liquid-phase reaction, and a catalyst with an ordered mesoporous structure is obtained by calcination.
[0004] Although there are many methods for preparing nickel-based catalysts, they have always been a focus and hot topic of research due to their low preparation cost and wide range of applications. Summary of the Invention
[0005] This invention provides a nickel-based catalyst, its preparation method, and its application. The preparation method is simple and suitable for industrial production. The catalyst obtained includes a main active component NiO, a co-active component MgO, and an inert component SiO2. The proportions of each component are adjustable, and the specific surface area can reach 300 m². 2 With a concentration of 1 g or higher, it exhibits excellent catalytic performance in the hydrogenation reactions of isophthalonitrile, maleic anhydride, and pyridine compounds.
[0006] To achieve the above objectives, the technical solution of the present invention is as follows:
[0007] This invention provides a method for preparing a nickel-based catalyst, the method comprising the following steps:
[0008] (1) Dissolve nickel sulfate hexahydrate and anhydrous magnesium sulfate in water to obtain material A;
[0009] (2) Dissolve anhydrous sodium carbonate in water to obtain material B;
[0010] (3) Heat the water glass to above 80°C to obtain material C;
[0011] (4) Add material A and material B to the reactor in parallel under stirring at room temperature, stir, and heat to 80-95℃;
[0012] (5) Add material C to the reactor, heat the material in the reactor until it boils, maintain for 5-30 minutes and then stop heating;
[0013] (6) Add water to the kettle to cool the material to below 60°C. The material is then discharged from the kettle, filtered, and washed until there are no sulfate ions in the filtrate.
[0014] (7) The filter cake is dried and calcined to obtain a nickel-based catalyst.
[0015] In the above technical solution, the amount of anhydrous sodium carbonate used is 1.1-1.5 times the total molar amount of nickel sulfate hexahydrate and anhydrous magnesium sulfate.
[0016] In the above technical solution, further, in step (4), the dripping speed is controlled so that material A and material B are dripped within 30 minutes; the stirring speed is greater than 100 rpm.
[0017] In the above technical solution, further, in step (7), the drying temperature is 90-110℃ and the time is 6-24h; the calcination temperature is 400-600℃ and the time is 4-10h.
[0018] In another aspect, the present invention provides a nickel-based catalyst, which is prepared by the above method and comprises a main active component NiO, a co-active component MgO, and an inert component SiO2.
[0019] In the above technical solution, the mass ratio of each component of the catalyst is NiO:MgO:SiO2 = 1.5-4:0.004-0.02:1.
[0020] The present invention also provides the application of the above-mentioned nickel-based catalyst in the hydrogenation reaction of isophthalonitrile, the hydrogenation reaction of maleic anhydride, and the hydrogenation reaction of pyridine compounds.
[0021] In the above technical solution, the solvent for the hydrogenation reaction of isophthalonitrile is N,N-dimethylformamide, the reaction temperature is 80-150℃, the reaction pressure is 2-6 MPa, and the mass hourly space velocity of isophthalonitrile is 0.2-0.5 h⁻¹. -1 The molar ratio of hydrogen to isophthalonitrile is 15-30.
[0022] In the above technical solution, the solvent for the hydrogenation reaction of maleic anhydride is γ-butyrolactone, the reaction temperature is 80-200℃, the reaction pressure is 0.2-2MPa, and the mass hourly space velocity of maleic anhydride is 0.3-1.0h. -1 The molar ratio of hydrogen to maleic anhydride is 15-30.
[0023] In the above technical solution, the hydrogenation reaction of the pyridine compound is further wherein the reaction temperature is 140-250℃, the reaction pressure is 2-4 MPa, and the feed mass hourly space velocity is 0.3-0.8 h⁻¹. -1 The molar ratio of hydrogen to pyridine compounds is 5-25; the pyridine compounds include any one of pyridine, 3,5-dimethylpyridine, 2,6-dimethylpyridine, and 2,3-dimethylpyridine.
[0024] The beneficial effects of this invention are as follows:
[0025] 1. This invention provides a method for preparing a nickel-based catalyst, which is simple and suitable for industrial production.
[0026] 2. The catalyst prepared by this invention comprises a main active component NiO, a co-active component MgO, and an inert component SiO2. The proportions of each component are adjustable, and the specific surface area can reach 300 m². 2 With a concentration of over / g, this catalyst can be applied to a variety of hydrogenation reactions and exhibits excellent catalytic activity. Detailed Implementation
[0027] The following examples are intended to enable those skilled in the art to more fully understand the present invention, but do not limit the invention in any way.
[0028] The specific surface area of the catalyst was measured by the BET specific surface area test method using a Micron 2460 instrument.
[0029] The raw materials used in the catalyst preparation process and the hydrogenation raw materials are selected from any commercially available reagents or industrial-grade raw materials. Unless otherwise specified, the purity of the raw materials shall not be less than 98%.
[0030] Example 1
[0031] The catalyst preparation method includes the following steps:
[0032] (1) Dissolve 527.9g of nickel sulfate hexahydrate and 2.3g of anhydrous magnesium sulfate in 900g of deionized water to obtain material A;
[0033] (2) Dissolve 250g of anhydrous sodium carbonate in 1000g of deionized water to obtain material B;
[0034] (3) Heat 199.5g of water glass (silicon dioxide content 25.06%, the same below) to 82℃ to obtain material C;
[0035] (4) At room temperature, add material A and material B in parallel droplet into the glass reactor, control the dropping rate, and complete the dropping within 30 minutes. Then heat the materials to 80°C.
[0036] (5) Quickly add material C into the reactor, heat the material in the reactor until it boils, maintain for 15 minutes, and then stop heating;
[0037] (6) Add water to cool the material to below 60°C, remove from the reactor, filter, wash, and wash until no SO4 is detected in the filtrate when tested with 2% barium nitrate solution. 2- ;
[0038] (7) Dry at 100℃ and calcine at 450℃ for 6 hours to obtain a nickel-based catalyst, denoted as C-1. The specific surface area of the catalyst was measured to be 323 m². 2 / g.
[0039] reaction:
[0040] Catalyst C-1 was tableted and sieved into 20-40 mesh particles. 4g of catalyst was loaded into the middle section of a fixed-bed reaction tube, with inert quartz sand at both ends. The catalyst was first reduced at 400℃ for 6 hours under a hydrogen atmosphere, followed by a reaction at 110℃ and 3 MPa. The mass hourly space velocity (WHSV) of the feedstock, isophthalonitrile, was 0.3 h⁻¹. -1The molar ratio of hydrogen to isophthalonitrile (referred to as the "hydrogen-to-oil ratio") was 15:1, and the solvent was N,N-dimethylformamide. After the reaction proceeded for 24 hours, samples were taken and quantitative analysis was performed using gas chromatography. The conversion rate of isophthalonitrile was 99.9%, and the selectivity of the product m-phenylenediamine was 99.5%.
[0041] Example 2
[0042] The catalyst preparation method includes the following steps:
[0043] (1) Dissolve 439.9g of nickel sulfate hexahydrate and 3.0g of anhydrous magnesium sulfate in 900g of deionized water to obtain material A;
[0044] (2) Dissolve 215g of anhydrous sodium carbonate in 860g of deionized water to obtain material B;
[0045] (3) Heat 199.5g of water glass to 82℃ to obtain material C;
[0046] (4) At room temperature, add material A and material B in parallel droplet into the glass reactor, control the dropping rate, and complete the dropping within 30 minutes. Then heat the materials to 80°C.
[0047] (5) Quickly add material C into the reactor, heat the material in the reactor until it boils, maintain for 15 minutes, and then stop heating;
[0048] (6) Add water to cool the material to below 60°C, remove from the reactor, filter, wash, and wash until no SO4 is detected in the filtrate when tested with 2% barium nitrate solution. 2- ;
[0049] (7) Dry at 100℃ and calcine at 450℃ for 6 hours to obtain a nickel-based catalyst, denoted as C-2.
[0050] reaction:
[0051] The reaction process was the same as in Example 1, with C-2 as the catalyst. After 24 hours of reaction, samples were taken and quantitative analysis was performed using gas chromatography. The conversion rate of isophthalonitrile was 99.5%, and the selectivity of the product m-phenylenediamine was 99.8%.
[0052] Example 3
[0053] The catalyst has a mass ratio of NiO:MgO:SiO2 = 3:0.015:1, and its preparation method includes the following steps:
[0054] (1) Dissolve 527.9g of nickel sulfate hexahydrate and 2.3g of anhydrous magnesium sulfate in 900g of deionized water to obtain material A;
[0055] (2) Dissolve 250g of anhydrous sodium carbonate in 1000g of deionized water to obtain material B;
[0056] (3) Heat 199.5g of water glass to 92℃ to obtain material C;
[0057] (4) At room temperature, add material A and material B in parallel dropwise into the glass reactor, control the dropping rate, and complete the dropping within 30 minutes. Then heat the materials to 90°C.
[0058] (5) Quickly add material C into the reactor, heat the material in the reactor until it boils, maintain for 15 minutes, and then stop heating;
[0059] (6) Add water to cool the material to below 60°C, remove from the reactor, filter, wash, and wash until no SO4 is detected in the filtrate when tested with 2% barium nitrate solution. 2- ;
[0060] (7) Dry at 100℃ and calcine at 450℃ for 6 hours to obtain a nickel-based catalyst, designated C-3. The specific surface area of the catalyst was measured to be 331 m². 2 / g.
[0061] reaction:
[0062] The reaction process was the same as in Example 1, with C-3 as the catalyst. After 24 hours of reaction, samples were taken and quantitative analysis was performed using gas chromatography. The conversion rate of isophthalonitrile was 99.9%, and the selectivity of the product m-phenylenediamine was 99.7%.
[0063] Example 4
[0064] Catalyst preparation: Same as in Example 1
[0065] reaction:
[0066] Catalyst C-1 was tableted and sieved into 20-40 mesh particles. 4g of catalyst was loaded into the middle section of a fixed-bed reaction tube, with inert quartz sand at both ends. The catalyst was first reduced at 400℃ for 6 hours under a hydrogen atmosphere, followed by a reaction at 120℃ and 3 MPa. The mass hourly space velocity (WHSV) of the feedstock, isophthalonitrile, was 0.4 h⁻¹. -1 The molar ratio of hydrogen to isophthalonitrile was 20:1, and the solvent was N,N-dimethylformamide. After 24 hours of reaction, samples were taken and quantitative analysis was performed using gas chromatography. The conversion rate of isophthalonitrile was 99.9%, and the selectivity of the product m-phenylenediamine was 99.7%.
[0067] Example 5
[0068] The catalyst preparation method includes the following steps:
[0069] (1) Dissolve 404.7g of nickel sulfate hexahydrate and 0.75g of anhydrous magnesium sulfate in 900g of deionized water to obtain material A;
[0070] (2) Dissolve 155g of anhydrous sodium carbonate in 620g of deionized water to obtain material B;
[0071] (3) Heat 199.5g of water glass to 82℃ to obtain material C;
[0072] (4) At room temperature, add material A and material B in parallel droplet into the glass reactor, control the dropping rate, and complete the dropping within 30 minutes. Then heat the materials to 80°C.
[0073] (5) Quickly add material C into the reactor, heat the material in the reactor until it boils, maintain for 15 minutes, and then stop heating;
[0074] (6) Add water to cool the material to below 60°C, remove from the reactor, filter, wash, and wash until no SO4 is detected in the filtrate when tested with 2% barium nitrate solution. 2- ;
[0075] (7) Dry at 100℃ and calcine at 450℃ for 6 hours to obtain a nickel-based catalyst, denoted as C-4. The specific surface area of the catalyst was measured to be 345 m². 2 / g.
[0076] reaction:
[0077] Catalyst C-4 was tableted and sieved into 20-40 mesh particles. 4g of catalyst was loaded into the middle section of a fixed-bed reaction tube, with inert quartz sand at both ends. The catalyst was first reduced at 400℃ for 6 hours under a hydrogen atmosphere, and then the reaction was carried out at 100℃ and 0.8 MPa. The mass hourly space velocity (WHSV) of the feedstock maleic anhydride was 0.6 h⁻¹. -1 The molar ratio of hydrogen to maleic anhydride was 20:1, and the solvent was γ-butyrolactone. After 24 hours of reaction, samples were taken and quantitative analysis was performed using gas chromatography. The conversion rate of maleic anhydride was 99.9%, and the selectivity of the product succinic anhydride was 99.8%.
[0078] Example 6
[0079] The catalyst preparation method includes the following steps:
[0080] (1) Dissolve 615.8g of nickel sulfate hexahydrate and 1.5g of anhydrous magnesium sulfate in 900g of deionized water to obtain material A;
[0081] (2) Dissolve 320g of anhydrous sodium carbonate in 1280g of deionized water to obtain material B;
[0082] (3) Heat 199.5g of water glass to 82℃ to obtain material C;
[0083] (4) At room temperature, add material A and material B in parallel droplet into the glass reactor, control the dropping rate, and complete the dropping within 30 minutes. Then heat the materials to 80°C.
[0084] (5) Quickly add material C into the reactor, heat the material in the reactor until it boils, maintain for 15 minutes, and then stop heating;
[0085] (6) Add water to cool the material to below 60°C, remove from the reactor, filter, wash, and wash until no SO4 is detected in the filtrate when tested with 2% barium nitrate solution. 2- ;
[0086] (7) Dry at 100℃ and calcine at 500℃ for 6 hours to obtain a nickel-based catalyst, designated C-5. The specific surface area of the catalyst was measured to be 317 m². 2 / g.
[0087] reaction:
[0088] Catalyst C-5 was tableted and sieved into 20-40 mesh particles. 4g of catalyst was loaded into the middle section of a fixed-bed reaction tube, with inert quartz sand at both ends. The catalyst was first reduced at 400℃ for 6 hours under a hydrogen atmosphere, and then the reaction was carried out at 150℃ and 2.5 MPa, with a mass hourly space velocity (WHSV) of 0.5 h⁻¹ for the pyridine feedstock. -1 The molar ratio of hydrogen to pyridine was 8:1. After 24 hours of reaction, samples were taken and quantitative analysis was performed using gas chromatography. The pyridine conversion rate was 99.6%, and the selectivity of the product piperidine was 98.6%.
[0089] Example 7
[0090] The catalyst preparation method includes the following steps:
[0091] (1) Dissolve 615.8g of nickel sulfate hexahydrate and 1.8g of anhydrous magnesium sulfate in 900g of deionized water to obtain material A;
[0092] (2) Dissolve 320g of anhydrous sodium carbonate in 1280g of deionized water to obtain material B;
[0093] (3) Heat 199.5g of water glass to 82℃ to obtain material C;
[0094] (4) At room temperature, add material A and material B in parallel droplet into the glass reactor, control the dropping rate, and complete the dropping within 30 minutes. Then heat the materials to 80°C.
[0095] (5) Quickly add material C into the reactor, heat the material in the reactor until it boils, maintain for 15 minutes, and then stop heating;
[0096] (6) Add water to cool the material to below 60°C, remove from the reactor, filter, wash, and wash until no SO4 is detected in the filtrate when tested with 2% barium nitrate solution. 2- ;
[0097] (7) Dry at 100℃ and calcine at 500℃ for 6 hours to obtain a nickel-based catalyst, denoted as C-6.
[0098] reaction:
[0099] Catalyst C-6 was tableted and sieved into 20-40 mesh particles. 4g of catalyst was loaded into the middle section of a fixed-bed reaction tube, with inert quartz sand at both ends. The catalyst was first reduced at 400℃ for 6 hours under a hydrogen atmosphere, followed by a reaction at 190℃ and 3.0 MPa. The mass hourly space velocity (WHSV) of the feedstock 3,5-dimethylpyridine was 0.5 h⁻¹. -1 The molar ratio of hydrogen to 3,5-dimethylpyridine was 10:1. After 24 hours of reaction, samples were taken and quantitative analysis was performed using gas chromatography. The conversion rate of 3,5-dimethylpyridine was 99.7%, and the selectivity of the product 3,5-dimethylpiperidine was 99.3%.
[0100] Example 8
[0101] Catalyst preparation: Same as in Example 7.
[0102] reaction:
[0103] Catalyst C-6 was compressed into tablets and sieved into 20-40 mesh particles. 4g of catalyst was loaded into the middle section of a fixed-bed reaction tube, with inert quartz sand at both ends. The catalyst was first reduced at 400℃ for 6 hours under a hydrogen atmosphere, followed by a reaction at 190℃ and 2.0 MPa. The mass hourly space velocity (WHSV) of the feedstock 2,6-dimethylpyridine was 0.5 h⁻¹. -1 The molar ratio of hydrogen to 2,6-dimethylpyridine was 20:1. After 24 hours of reaction, samples were taken and quantitative analysis was performed using gas chromatography. The conversion rate of 2,6-dimethylpyridine was 99.7%, and the selectivity of the product 2,6-dimethylpiperidine was 99.5%.
[0104] Example 9
[0105] Catalyst preparation: Same as in Example 7.
[0106] reaction:
[0107] Catalyst C-6 was tableted and sieved into 20-40 mesh particles. 4g of catalyst was loaded into the middle section of a fixed-bed reaction tube, with inert quartz sand at both ends. The catalyst was first reduced at 400℃ for 6 hours under a hydrogen atmosphere, followed by a reaction at 200℃ and 3.0 MPa. The mass hourly space velocity (WHSV) of the feedstock 2,3-dimethylpyridine was 0.75 h⁻¹.-1 The molar ratio of hydrogen to 2,3-dimethylpyridine was 15:1. After 24 hours of reaction, samples were taken and quantitative analysis was performed using gas chromatography. The conversion rate of 2,3-dimethylpyridine was 99.9%, and the selectivity of the product 2,3-dimethylpiperidine was 99.8%.
[0108] Comparative Example 1
[0109] The catalyst preparation method includes the following steps:
[0110] (1) Dissolve 527.9g of nickel sulfate hexahydrate and 2.3g of anhydrous magnesium sulfate in 900g of deionized water, then add 199.5g of water glass and mix well to obtain material A;
[0111] (2) Dissolve 250g of anhydrous sodium carbonate in 1000g of deionized water to obtain material B;
[0112] (3) Add material B dropwise to material A. After the process is complete, heat the material in the vessel until it boils and maintain the temperature for 15 minutes. Then stop heating.
[0113] (4) Add water to cool the material to below 60°C, remove from the reactor, filter, wash, and wash until no SO4 is detected in the filtrate when tested with 2% barium nitrate solution. 2- ;
[0114] (5) Dry at 100℃ and calcine at 450℃ for 6 hours to obtain a nickel-based catalyst, denoted as D-1. The specific surface area of the catalyst was measured to be 202 m². 2 / g.
[0115] reaction:
[0116] The reaction process was the same as in Example 1, with catalyst D-1. After 24 hours of reaction, samples were taken and quantitative analysis was performed using gas chromatography. The conversion rate of isophthalonitrile was 94.1%, and the selectivity of the product m-phenylenediamine was 99.8%.
[0117] Comparative Example 2
[0118] The catalyst preparation method includes the following steps:
[0119] (1) Dissolve 615.8g of nickel sulfate hexahydrate and 1.8g of anhydrous magnesium sulfate in 900g of deionized water to obtain material A;
[0120] (2) Dissolve 320g of anhydrous sodium carbonate in 1280g of deionized water to obtain material B;
[0121] (3) Heat 199.5g of water glass to 62℃ to obtain material C;
[0122] (4) At room temperature, add material A and material B in parallel droplet to the glass reactor, control the dropping rate, and complete the dropping within 30 minutes. Then heat the materials to 60°C.
[0123] (5) Quickly add material C into the reactor, maintain 60°C for 15 minutes, and then stop heating;
[0124] (6) After the material is discharged from the reactor, it is filtered and washed until no SO4 is detected in the filtrate when tested with 2% barium nitrate solution. 2- ;
[0125] (7) Dry at 100℃ and calcine at 500℃ for 6 hours to obtain a nickel-based catalyst, denoted as D-2.
[0126] reaction:
[0127] The reaction process was the same as in Example 1, with catalyst D-2. After 24 hours of reaction, samples were taken and quantitative analysis was performed using gas chromatography. The conversion rate of 2,6-dimethylpyridine was 95.9%, and the selectivity of the product 2,6-dimethylpiperidine was 99.0%.
[0128] The above-described embodiments are merely illustrative of the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement it accordingly. They should not be construed as limiting the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.
Claims
1. A process for the preparation of a nickel-based catalyst, characterized in that, The method comprises the following steps: (1) dissolving nickel sulfate hexahydrate and anhydrous magnesium sulfate in water to obtain material A; (2) dissolving anhydrous sodium carbonate in water to obtain material B; (3) heating water glass to above 80℃ to obtain material C; (4) adding material A and material B into a reaction kettle in parallel dropwise under stirring at room temperature, stirring, and heating to 80-95℃; (5) adding material C into the reaction kettle, heating to boiling of the material in the kettle, and stopping heating after maintaining for 5-30 min; (6) adding water into the kettle to cool the material to below 60℃, discharging the material from the kettle, filtering, and washing until no sulfate ion exists in the filtrate; (7) drying and calcining the filter cake to obtain a nickel-based catalyst. The catalyst comprises a main active component NiO, an auxiliary active component MgO, and an inert component SiO2. The mass ratio of the components of the catalyst is NiO:MgO:SiO2=1.5-4:0.004-0.02:
1.
2. The method of making a nickel-based catalyst according to claim 1, wherein, The amount of anhydrous sodium carbonate is 1.1-1.5 times the total moles of nickel sulfate hexahydrate and anhydrous magnesium sulfate.
3. The method of making a nickel-based catalyst of claim 1, wherein, In step (4), material A and material B are added dropwise within 30 min; the stirring speed is greater than 100 rpm.
4. The method of making a nickel-based catalyst of claim 1, wherein, In step (7), the drying temperature is 90-110℃, and the time is 6-24 h; The calcining temperature is 400-600℃, and the time is 4-10 h.
5. Application of the nickel-based catalyst prepared by the preparation method of any one of claims 1-4 in hydrogenation reaction of isophthalonitrile, hydrogenation reaction of maleic anhydride, and hydrogenation reaction of pyridine compounds.
6. Use according to claim 5, characterized in that, The solvent for the reaction of the isophthalonitrile hydrogenation is N,N-dimethylformamide, the reaction temperature is 80-150 DEG C, the reaction pressure is 2-6 MPa, the isophthalonitrile mass space velocity is 0.2-0.5 h -1 , and the molar ratio of hydrogen to isophthalonitrile is 15-30.
7. Use according to claim 5, characterized in that, The solvent of the maleic anhydride hydrogenation reaction is gamma-butyrolactone, the reaction temperature is 80-200 DEG C, the reaction pressure is 0.2-2 MPa, the mass space velocity of maleic anhydride is 0.3-1.0 h -1 , and the molar ratio of hydrogen to maleic anhydride is 15-30.
8. Use according to claim 5, characterized in that, The reaction temperature of the hydrogenation reaction of the pyridine compound is 140-250℃, the reaction pressure is 2-4MPa, the mass space velocity of raw material is 0.3-0.8h -1 , and the molar ratio of hydrogen to the pyridine compound is 5-25; the pyridine compound includes any one of pyridine, 3,5-dimethylpyridine, 2,6-dimethylpyridine and 2,3-dimethylpyridine.
Citation Information
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