Nickel-based catalyst for maleic anhydride hydrogenation, preparation method and application thereof, and method for preparing succinic anhydride through maleic anhydride liquid phase hydrogenation

By developing a nickel-based catalyst containing aluminum oxide, nickel and phosphorus, the problem of insufficient catalytic performance and stability of the maleic anhydride hydrogenation in the prior art has been solved, and efficient succinic anhydride production has been achieved.

CN119897137APending Publication Date: 2025-04-29CHINA PETROLEUM & CHEMICAL CORP +1
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Patent Information

Application Number
CN202311402556.9
Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Filing Date
2023-10-26
Publication Date
2025-04-29

AI Technical Summary

Technical Problem

In the prior art, the catalytic performance of the maleic anhydride hydrogenation is poor and the catalyst stability is poor, making it difficult to meet the demand for succinic anhydride production.

Method used

A nickel-based catalyst is developed, including an alumina support, an inorganic compound of nickel and a phosphorus inorganic compound, and a catalyst with nanoscale active components is prepared by a specific preparation method.

Benefits of technology

The nickel-based catalyst exhibits excellent catalytic performance and stability in the preparation of succinic anhydride with a hydrothermal agent, which solves the problems of poor catalytic performance and poor stability.

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Abstract

The invention relates to the field of catalysts, in particular to a nickel-based catalyst for maleic anhydride hydrogenation, a preparation method and application of the nickel-based catalyst and a method for preparing butanedioic anhydride through maleic anhydride liquid-phase hydrogenation.The nickel-based catalyst comprises an aluminum oxide carrier, an inorganic compound of nickel and an inorganic compound of phosphorus; in the nickel-based catalyst, based on the total weight of the nickel-based catalyst, the content of the aluminum oxide is 50-85 wt.%; the content of the inorganic compound of nickel is 10-40 wt.%; the content of an inorganic compound of phosphorus is 1-30 wt.%. The nickel-based catalyst for maleic anhydride hydrogenation provided by the invention shows excellent catalytic performance and stability in a reaction for preparing succinic anhydride through maleic anhydride hydrogenation, and is a novel maleic anhydride hydrogenation catalyst with good performance.
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Description

Technical Field

[0001] The invention relates to the technical field of catalysts, and in particular to a nickel-based catalyst for hydrogenation of maleic anhydride, a preparation method and application thereof, and a method for preparing succinic anhydride by liquid-phase hydrogenation of maleic anhydride. Background Art

[0002] Succinic anhydride is a food processing aid specified in national standards. It is a synthetic raw material for medicines, pesticides, esters and resins, and an intermediate for synthesizing organic compounds in the organic industry.

[0003] In recent years, with the widespread application of biodegradable materials, the demand for succinic acid as one of the monomers has increased year by year. The production capacity and quality requirements of succinic anhydride, the raw material for synthesizing succinic acid, have also gradually increased.

[0004] At present, the production methods of succinic anhydride used in industry include: biological fermentation, succinic acid dehydration and maleic anhydride catalytic hydrogenation. Among them, although the biological fermentation method is environmentally friendly, the purification process of this method is complex and the product yield is low, which is difficult to meet the needs of large-scale industrial production; the succinic acid dehydration method has a low technical threshold, but the production scale is small and the product quality is low, which is difficult to meet the supply of high-purity succinic anhydride raw material market; the maleic anhydride hydrogenation method has the advantages of simple process flow, convenient operation, high equipment utilization, low operating cost and high product purity, and is the most promising succinic anhydride production process.

[0005] Patent CN103769117B discloses a catalyst with cobalt / nickel as active metal supported by activated carbon, which is used for the synthesis of maleic anhydride hydrogenation to prepare succinic anhydride. The catalyst is simultaneously added with other metal additives, and the preparation process is complicated, and in the hydrogenation reaction, the reaction temperature is high. Patent 104399469A discloses a catalyst with aluminum oxide as a carrier and nickel as an active component. Although the preparation process of the catalyst is simple, it can only be used for intermittent synthesis reaction in the synthesis process for preparing succinic anhydride by hydrogenation of maleic anhydride, and cannot be applied to continuous large-scale production. Patent 105833863A discloses a supported catalyst, and the selection of active metal is precious metal palladium, which increases the preparation cost of the catalyst, and in the large-scale industrial production of catalytic hydrogenation to prepare succinic anhydride, the corresponding production cost will also be increased.

[0006] At present, there are many prior arts for preparing succinic anhydride by hydrogenating maleic anhydride. However, the prior arts generally have defects such as high catalyst preparation cost and poor catalytic performance.

[0007] Therefore, it is of practical significance to develop a new catalyst with high catalytic activity to meet the production needs of succinic anhydride. Summary of the invention

[0008] In order to solve the technical problems of poor catalytic performance and poor catalyst stability in the prior art for hydrogenation of maleic anhydride, the present invention provides a nickel-based catalyst for hydrogenation of maleic anhydride, a preparation method and application thereof, and a method for preparing succinic anhydride by liquid-phase hydrogenation of maleic anhydride. The nickel-based catalyst for hydrogenation of maleic anhydride has good catalytic performance and stability in the process of catalyzing liquid-phase hydrogenation of maleic anhydride.

[0009] In order to achieve the above object, the first aspect of the present invention provides a nickel-based catalyst for hydrogenation of maleic anhydride, wherein the nickel-based catalyst comprises an alumina carrier, an inorganic compound of nickel and an inorganic compound of phosphorus;

[0010] In the nickel-based catalyst, based on the total weight of the nickel-based catalyst, the content of aluminum oxide is 50-85wt.%, preferably 55-80wt.%; the content of the inorganic nickel compound is 10-40wt.%, preferably 12-35wt.%; the content of the inorganic phosphorus compound is 1-30wt.%, preferably 5-15wt.%.

[0011] A second aspect of the present invention provides a method for preparing a nickel-based catalyst for hydrogenation of maleic anhydride, the preparation method comprising the following steps:

[0012] S1: adding trimethyl phosphate into deionized water and stirring and heating to obtain a first solution;

[0013] S2: adding nickel salt to the first solution and stirring and dispersing the mixture to obtain a second solution;

[0014] S3: After drying the alumina carrier, add it into the second solution and perform impregnation, drying and calcination in sequence to obtain a nickel-based catalyst.

[0015] The third aspect of the present invention provides a nickel-based catalyst prepared by the above-mentioned preparation method.

[0016] The fourth aspect of the present invention provides the use of the above nickel-based catalyst in the reaction of preparing succinic anhydride by hydrogenating maleic anhydride.

[0017] A fifth aspect of the present invention provides a method for preparing succinic anhydride by liquid phase hydrogenation of maleic anhydride, the method comprising: in the presence of an activated catalyst, hydrogen and maleic anhydride are contacted to react to obtain the succinic anhydride;

[0018] The activated catalyst is obtained by reducing and activating the above-mentioned nickel-based catalyst in a gas containing hydrogen.

[0019] The beneficial technical effects of the present invention are:

[0020] (1) The nickel-based catalyst for hydrogenation of maleic anhydride provided by the present invention exhibits excellent catalytic performance and stability in the reaction of hydrogenating maleic anhydride to prepare succinic anhydride, and is a new maleic anhydride hydrogenation catalyst with good performance.

[0021] (2) The active component crystals of the nickel-based catalyst for hydrogenation of maleic anhydride provided by the present invention are nano-scale and evenly distributed, and have catalytic active centers with good dispersion.

[0022] (3) The method for preparing the nickel-based catalyst for hydrogenation of maleic anhydride provided by the present invention prepares a new nickel-based catalyst by changing the traditional catalyst preparation process and composition. The catalyst exhibits excellent catalytic performance and stability in the reaction of hydrogenating maleic anhydride to prepare succinic anhydride.

[0023] Other features and advantages of the present invention will be described in detail in the following detailed description. DETAILED DESCRIPTION

[0024] The specific embodiments of the present invention are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention, and are not used to limit the present invention.

[0025] The present invention provides a nickel-based catalyst for hydrogenation of maleic anhydride, wherein the nickel-based catalyst comprises an alumina carrier, an inorganic compound of nickel and an inorganic compound of phosphorus;

[0026] In the nickel-based catalyst, based on the total weight of the nickel-based catalyst, the content of aluminum oxide is 50-85wt.%, preferably 55-80wt.%; the content of the inorganic nickel compound is 10-40wt.%, preferably 12-35wt.%; the content of the inorganic phosphorus compound is 1-30wt.%, preferably 5-15wt.%.

[0027] In the present invention, the nickel-based catalyst for hydrogenation of maleic anhydride shows excellent catalytic performance and stability in the reaction of preparing succinic anhydride by hydrogenation of maleic anhydride, and is a novel maleic anhydride hydrogenation catalyst with good performance.

[0028] According to a preferred embodiment of the present invention, the inorganic compound of nickel is nickel oxide and / or nickel salt, and its precursor is selected from at least one of nickel nitrate, nickel sulfate, nickel chloride, nickel acetate and basic nickel carbonate, preferably nickel nitrate.

[0029] According to a preferred embodiment of the present invention, the inorganic phosphorus compound is phosphorus oxide, preferably phosphorus pentoxide, and its precursor is any one of trimethyl phosphate, triethyl phosphate, tributyl phosphate and diammonium hydrogen phosphate, preferably trimethyl phosphate.

[0030] According to the present invention, preferably, the specific surface area of ​​the alumina carrier is 80-200m 2 / g, preferably 100-180m 2 / g.

[0031] According to the present invention, preferably, the most probable pore size range of the alumina carrier is 8-20 nm, preferably 10-18 nm.

[0032] In the present invention, the active component crystal grains of the nickel-based catalyst for hydrogenation of maleic anhydride are nano-scale, evenly distributed, and have catalytic active centers with good dispersibility.

[0033] The present invention also provides a method for preparing a nickel-based catalyst for hydrogenation of maleic anhydride, the preparation method comprising the following steps:

[0034] S1: adding trimethyl phosphate into deionized water and stirring and heating to obtain a first solution;

[0035] S2: adding nickel salt to the first solution and stirring and dispersing the mixture to obtain a second solution;

[0036] S3: After drying the alumina carrier, add it into the second solution and perform impregnation, drying and calcination in sequence to obtain a nickel-based catalyst.

[0037] In the present invention, the preparation method of the nickel-based catalyst for hydrogenation of maleic anhydride is prepared by changing the traditional catalyst preparation process and composition to prepare a new nickel-based catalyst, which exhibits excellent catalytic performance and stability in the reaction of hydrogenating maleic anhydride to prepare succinic anhydride.

[0038] According to a preferred embodiment of the present invention, the amount of trimethyl phosphate used is such that the content of phosphorus-containing inorganic compounds in the nickel-based catalyst is 1-30 wt.%, preferably 5-15 wt.%.

[0039] Preferably, the inorganic phosphorus compound is phosphorus pentoxide.

[0040] According to a preferred embodiment of the present invention, the molar ratio of trimethyl phosphate to deionized water is 1:1-3, preferably 1:1.2-2.

[0041] According to a preferred embodiment of the present invention, the temperature of stirring and heating is 30-70°C, preferably 40-60°C.

[0042] According to the present invention, the nickel salt is used in an amount such that the content of the nickel-containing inorganic compound in the nickel-based catalyst is 10-40 wt.%, preferably 12-35 wt.%.

[0043] According to a preferred embodiment of the present invention, the inorganic compound of nickel is nickel oxide and / or nickel salt.

[0044] According to the present invention, preferably, the nickel salt is selected from at least one of nickel nitrate, nickel sulfate, nickel chloride, nickel acetate and basic nickel carbonate, preferably selected from nickel nitrate.

[0045] According to the present invention, the stirring and dispersing is performed using a stirrer; the stirring and dispersing rate is 50-500 rpm, preferably 100-300 rpm; and the time is 5-120 minutes, preferably 15-60 minutes.

[0046] According to a preferred embodiment of the present invention, the specific surface area of ​​the alumina carrier is 80-200m 2 / g, preferably 100-180m 2 / g.

[0047] According to a preferred embodiment of the present invention, the most probable pore size of the alumina carrier is in the range of 8-20 nm, preferably 10-18 nm.

[0048] According to the present invention, the temperature for drying the alumina carrier may be 160-200° C., preferably 170-190° C.; the time for drying may be 1-5 h, preferably 2-4 h.

[0049] According to the present invention, the volume of the second solution is preferably greater than or equal to the pore volume of the alumina support after drying. More preferably, the volume of the second solution is equal to the pore volume of the alumina support after drying, that is, equal volume impregnation is performed. In step S2, the water absorption rate of the alumina support can be measured first, and then the second solution can be fixed to the required volume based on the water absorption rate of the alumina support.

[0050] The drying temperature may be 90-120°C, preferably 100-110°C.

[0051] The drying time may be 1-24 hours, preferably 6-12 hours.

[0052] The calcination temperature may be 350-550°C, preferably 400-500°C.

[0053] The calcination time may be 1-8 hours, preferably 2-6 hours.

[0054] The present invention also provides a nickel-based catalyst prepared by the above-mentioned preparation method.

[0055] The present invention further provides the use of the nickel-based catalyst in the reaction of preparing succinic anhydride by hydrogenating maleic anhydride.

[0056] Finally, the present invention provides a method for preparing succinic anhydride by liquid phase hydrogenation of maleic anhydride, the method comprising: in the presence of an activated catalyst, hydrogen and maleic anhydride are contacted to react to obtain the succinic anhydride;

[0057] The activated catalyst is obtained by reducing and activating the above-mentioned nickel-based catalyst in a gas containing hydrogen.

[0058] Preferably, the reduction activation temperature is 350-450° C. and the time is 1-8 h.

[0059] Furthermore, the hydrogen content in the hydrogen-containing gas is 5-100% by volume.

[0060] The gas containing hydrogen may be hydrogen or a mixed gas of hydrogen and nitrogen.

[0061] Preferably, the gas space velocity of the hydrogen is 10-40h -1 .

[0062] According to the present invention, preferably, the temperature of the contact reaction is 60-150° C. and the pressure is 1-3 MPa.

[0063] Furthermore, the molar ratio of hydrogen to maleic anhydride used in the contact reaction is 10-30:1.

[0064] According to the present invention, the maleic anhydride is preferably present in the form of a maleic anhydride solution, and the concentration of the maleic anhydride solution is 10-30% by weight.

[0065] The solvent of the maleic anhydride solution may be selected from at least one of tetrahydrofuran, γ-butyrolactone, cyclohexane and 1,4-dioxane.

[0066] Furthermore, the liquid hourly space velocity of maleic anhydride is 0.1-0.5h -1 .

[0067] In the present invention, there is no limitation on the equipment used in the method of preparing succinic anhydride by hydrogenating maleic anhydride, as long as the reaction can be achieved, for example, it can be carried out in a fixed bed reactor.

[0068] The present invention is further described below in conjunction with embodiments, but the scope of the present invention is not limited to these embodiments.

[0069] In an embodiment of the present invention, the method for evaluating the performance of the nickel-based catalyst for hydrogenation of maleic anhydride provided by the present invention comprises:

[0070] (a) In a stainless steel fixed bed reactor, the nickel-based catalyst for hydrogenation of maleic anhydride provided by the present invention is reduced with a mixture of nitrogen and hydrogen at a temperature of 350-450° C. for 1-8 h to obtain an activated catalyst, wherein the hydrogen content in the mixture is 5-100% by volume and the hydrogen space velocity is 10-40 h -1 ;

[0071] (b) in the presence of the activated catalyst, hydrogen and maleic anhydride solution are heated to 60-150° C., at a pressure of 1-3 MPa, and at a liquid hourly space velocity of maleic anhydride of 0.1-0.5 h -1A contact reaction is carried out under the following conditions to obtain a reaction product, wherein the molar ratio of hydrogen to maleic anhydride is 10-30:1, the solvent of the maleic anhydride solution is selected from at least one of tetrahydrofuran, γ-butyrolactone, cyclohexane and 1,4-dioxane, and the concentration of the maleic anhydride solution is 10-30% by weight;

[0072] (c) condensing the reaction product of step (b) to obtain a liquid product, and analyzing the content of each component in the liquid product by gas chromatography.

[0073] The maleic anhydride conversion and the selectivity of the succinic anhydride were calculated by the following formula:

[0074] Maleic anhydride conversion rate = (Mo-Ma) / Mo×100%;

[0075] Selectivity of succinic anhydride = Mi / (Mo-Ma) × 100%;

[0076] Wherein, Mo is the amount of maleic anhydride, mol;

[0077] Ma—the amount of maleic anhydride remaining after the reaction, mol;

[0078] Mi—the amount of succinic anhydride produced after the reaction, mol.

[0079] The present invention is further described below through examples and comparative examples.

[0080] The raw materials used in the examples and comparative examples of the present application are all commercially available.

[0081] Example 1

[0082] (1) Weigh 100 g of alumina carrier (specific surface area 150 m 2 / g, the most probable pore size is 15, dried at 180℃ for 3 hours, and the water absorption rate is 95%;

[0083] (2) Weigh 21.9 g of trimethyl phosphate and 4.2 g of deionized water (the molar ratio of water to trimethyl phosphate is 1.5), stir and heat to 50° C. to obtain solution I;

[0084] (3) Weigh 108.3 g of nickel nitrate hexahydrate, stir and disperse it into solution I, and then dilute the solution to 95 ml to obtain solution II;

[0085] (4) adding the aforementioned alumina support to the aforementioned solution II and impregnating them in equal volumes;

[0086] (5) drying the catalyst prepared above for 12 hours, and then calcining it at 450° C. to obtain catalyst S1;

[0087] In catalyst S1, based on the total weight of the catalyst, the content of NiO component, calculated as oxides, is 20 wt %, the content of P2O5 is 8 wt %, and the content of Al2O3 is 72 wt %.

[0088] Example 2

[0089] Catalyst S2 of Example 2 is prepared by a method similar to that of catalyst S1 of Example 1, except that the molar ratio of water to trimethyl phosphate in step (2) is 1.2, the hydrolysis temperature is 60°C, and in addition, the amount of raw materials added is adjusted so that in catalyst S2, based on the total weight of the catalyst, the content of NiO component is 15 weight%, the content of P2O5 is 12 weight%, and the content of Al2O3 is 73 weight%.

[0090] Example 3

[0091] Catalyst S3 of Example 3 is prepared by a method similar to that of Catalyst S1 of Example 1, except that the molar ratio of water to trimethyl phosphate in step (2) is 1.8, the hydrolysis temperature is 40°C, and in addition, the amount of raw materials added is adjusted so that in Catalyst S3, the content of NiO component is 25% by weight, the content of P2O5 is 15% by weight, and the content of Al2O3 is 60% by weight, calculated as oxides, based on the total weight of the catalyst.

[0092] Example 4

[0093] Catalyst S4 of Example 4 is prepared by a method similar to that of catalyst S1 of Example 1, except that the molar ratio of water to trimethyl phosphate in step (2) is 2, and the hydrolysis temperature is 40°C. In addition, the amount of raw materials added is adjusted so that in catalyst S4, the content of NiO component is 30 weight %, the content of P2O5 is 12 weight %, and the content of Al2O3 is 58 weight %, calculated as oxides, based on the total weight of the catalyst.

[0094] Example 5

[0095] Catalyst S5 of Example 5 is prepared by a method similar to that of Catalyst S1 of Example 1, except that the molar ratio of water to trimethyl phosphate in step (2) is 1.5, the hydrolysis temperature is 60°C, and in addition, the amount of raw materials added is adjusted so that in Catalyst S5, the content of NiO component is 35 weight %, the content of P2O5 is 8 weight %, and the content of Al2O3 is 57 weight %, calculated as oxides, based on the total weight of the catalyst.

[0096] Example 6

[0097] Catalyst S6 of Example 6 is prepared by a method similar to that of catalyst S1 of Example 1, except that the molar ratio of water to trimethyl phosphate in step (2) is 1.2, and the hydrolysis temperature is 50°C. In addition, the amount of raw materials added is adjusted so that in catalyst S6, the content of NiO component is 15 weight%, the content of P2O5 is 5 weight%, and the content of Al2O3 is 80 weight%, calculated as oxides, based on the total weight of the catalyst.

[0098] Example 7

[0099] Catalyst S7 of Example 7 is prepared by a method similar to that of catalyst S1 of Example 1, except that the molar ratio of water to trimethyl phosphate in step (2) is 1.7, the hydrolysis temperature is 40°C, and in addition, the amount of raw materials added is adjusted so that in catalyst S7, the content of NiO component is 35 weight %, the content of P2O5 is 15 weight %, and the content of Al2O3 is 50 weight %, calculated as oxides, based on the total weight of the catalyst.

[0100] Comparative Example 1

[0101] Weigh 100 g of nickel nitrate hexahydrate, 5.99 g of P2O5, and 53.9 g of alumina carrier, add them to a kneader, stir and knead them thoroughly, add appropriate amount of dilute nitric acid and adhesive, and knead and extrude them into strips. Keep drying at 110°C for 12 hours. Then calcine at 450°C, and then press into tablets to obtain a catalyst to be used, which is recorded as DS1; the nickel oxide content accounts for 30% of the mass of the catalyst, the phosphorus oxide content accounts for 7% of the mass of the catalyst, and the alumina content accounts for 63% of the mass of the catalyst.

[0102] Comparative Example 2

[0103] The preparation method is the same as that of Comparative Example 1, except that the amount of raw materials added is adjusted so that in the catalyst DS2, the nickel oxide content accounts for 20% of the mass of the catalyst, the phosphorus oxide content accounts for 12% of the mass of the catalyst, and the aluminum oxide accounts for 62% of the mass of the catalyst.

[0104] Test Case

[0105] The catalysts prepared in the above examples and comparative examples were used to evaluate the catalyst performance using the evaluation method provided in this application. The conversion rate of maleic anhydride and the selectivity of succinic anhydride are shown in Table 1.

[0106] Table 1 Catalyst performance comparison

[0107] catalyst Maleic anhydride conversion rate (%) Succinic anhydride selectivity (%) S1 100.0 99.7 S2 99.8 98.9 S3 99.3 99.0 S4 99.1 99.2 S5 100.0 98.1 S6 99.6 99.3 S7 98.8 97.2 DS1 92.6 91.0 DS2 91.1 92.8

[0108] As can be seen from Table 1, Examples 1-7 have better activity and selectivity than Comparative Examples 1-2, among which Example 1 has the best activity and selectivity. The catalyst prepared by the present invention has good industrial application value.

[0109] The embodiments of the present invention have been described above, and the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and changes will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

[0110] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

Claims

1. A nickel-based catalyst for hydrogenation of maleic anhydride, characterized in that: The nickel-based catalyst comprises an alumina carrier, an inorganic compound of nickel and an inorganic compound of phosphorus; In the nickel-based catalyst, based on the total weight of the nickel-based catalyst, the content of aluminum oxide is 50-85wt.%, preferably 55-80wt.%; the content of the inorganic nickel compound is 10-40wt.%, preferably 12-35wt.%; and the content of the inorganic phosphorus compound is 1-30wt.%, preferably 5-15wt.%.

2. The nickel-based catalyst for hydrogenation of maleic anhydride according to claim 1, characterized in that The inorganic compound of nickel is nickel oxide and / or nickel salt, and its precursor is at least one selected from nickel nitrate, nickel sulfate, nickel chloride, nickel acetate and basic nickel carbonate, preferably nickel nitrate; The inorganic phosphorus compound is phosphorus oxide, preferably phosphorus pentoxide, and its precursor is any one of trimethyl phosphate, triethyl phosphate, tributyl phosphate and diammonium hydrogen phosphate, preferably trimethyl phosphate.

3. The nickel-based catalyst for hydrogenation of maleic anhydride according to any one of claims 1 to 2, characterized in that The specific surface area of ​​the alumina carrier is 80-200m 2 / g, preferably 100-180m 2 / g; The most probable pore diameter is 8-20 nm, preferably 10-18 nm.

4. A method for preparing a nickel-based catalyst for hydrogenation of maleic anhydride, characterized in that: The preparation method comprises the following steps: S1: adding trimethyl phosphate into deionized water and stirring and heating to obtain a first solution; S2: adding nickel salt to the first solution and stirring and dispersing the mixture to obtain a second solution; S3: After drying the alumina carrier, add it into the second solution and perform impregnation, drying and calcination in sequence to obtain a nickel-based catalyst.

5. The preparation method according to claim 4, characterized in that: The amount of trimethyl phosphate is such that the content of phosphorus-containing inorganic compounds in the nickel-based catalyst is 1-30 wt.%, preferably 5-15 wt.%; The inorganic compound of phosphorus is phosphorus pentoxide; The molar ratio of trimethyl phosphate to deionized water is 1:1-3, preferably 1:1.2-2; The temperature for stirring and heating is 30-70°C, preferably 40-60°C.

6. The preparation method according to claim 4, characterized in that: The nickel salt is used in an amount such that the content of the nickel-containing inorganic compound in the nickel-based catalyst is 10-40 wt.%, preferably 12-35 wt.%; The inorganic compound of nickel is nickel oxide and / or nickel salt; The nickel salt is selected from at least one of nickel nitrate, nickel sulfate, nickel chloride, nickel acetate and basic nickel carbonate, and is preferably selected from nickel nitrate.

7. The preparation method according to claim 4, characterized in that: The stirring and dispersing is performed using a stirrer; the stirring and dispersing speed is 50-500 rpm, preferably 100-300 rpm; the time is 5-120 minutes, preferably 15-60 minutes.

8. The preparation method according to claim 4, characterized in that: The specific surface area of ​​the alumina carrier is 80-200m 2 / g, preferably 100-180m 2 / g; The most probable pore diameter range is 8-20 nm, preferably 10-18 nm.

9. The preparation method according to claim 8, characterized in that: The temperature of the alumina carrier drying treatment is 160-200°C, preferably 170-190°C; the drying treatment time is 1-5h, preferably 2-4h; The volume of the second solution is greater than or equal to the pore volume of the alumina support after drying; The drying temperature is 90-120°C, preferably 100-110°C; The drying time is 1-24h, preferably 6-12h; The calcination temperature is 350-550°C, preferably 400-500°C; The calcination time is 1-8 hours, preferably 2-6 hours.

10. A nickel-based catalyst prepared according to the preparation method according to any one of claims 4 to 9.

11. Use of the nickel-based catalyst according to any one of claims 1 to 3 and 10 in the reaction of preparing succinic anhydride by hydrogenating maleic anhydride.

12. A method for preparing succinic anhydride by liquid phase hydrogenation of maleic anhydride, characterized in that: The method comprises: in the presence of an activated catalyst, hydrogen and maleic anhydride are contacted to react to obtain the succinic anhydride; The activated catalyst is obtained by reducing and activating the nickel-based catalyst described in any one of claims 1 to 3 and 10 in a gas containing hydrogen.

13. The method according to claim 12, characterized in that The reduction activation temperature is 350-450°C and the time is 1-8h; The hydrogen content in the hydrogen-containing gas is 5-100 volume %; The gas containing hydrogen is hydrogen or a mixture of hydrogen and nitrogen; The gas space velocity of the hydrogen is 10-40h -1 ; The contact reaction temperature is 60-150°C and the pressure is 1-3MPa; The molar ratio of hydrogen to maleic anhydride used in the contact reaction is 10-30:1; The maleic anhydride is present in the form of a maleic anhydride solution, and the concentration of the maleic anhydride solution is 10-30 weight %; The solvent of the maleic anhydride solution is selected from at least one of tetrahydrofuran, γ-butyrolactone, cyclohexane and 1,4-dioxane; The liquid hourly space velocity of maleic anhydride is 0.1-0.5h -1 .

Citation Information

Patent Citations

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