Hydrogenation catalyst, preparation method and application thereof, and method for preparing succinic anhydride by hydrogenating maleic anhydride

Abstract

The present invention relates to the field of catalyst technology, and specifically to a hydrogenation catalyst, a preparation method and application thereof, and a method for hydrogenating maleic anhydride to produce succinic anhydride. The hydrogenation catalyst comprises a carrier and an active component supported on the carrier, the active component containing: Ni, Sn, Ca and / or Ba; the carrier contains SiO2; the hydrogenation catalyst has a Ni content of 10-40wt%, a Sn content of 5-15wt%, a Ca and / or Ba content of 0.5-5wt%, and a carrier content of 20-80wt%, based on the total weight of the hydrogenation catalyst and calculated as oxides. The hydrogenation catalyst of the present invention still has high catalytic activity and succinic anhydride selectivity under low-temperature reaction conditions, and the preparation process is simple, so it can be applied to continuous large-scale production.

Description

Technical Field

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

[0002] Succinic anhydride, also known as succinic anhydride, is an important organic synthesis intermediate and fine chemical raw material, widely used in food, surfactants, coatings, pharmaceuticals, agriculture, plastics, and other fields. Furthermore, succinic acid, the hydrolysis product of succinic anhydride, is the primary raw material for biodegradable materials such as polybutylene succinate. With the country's increasing emphasis on and development of environmental protection policies, the demand for succinic acid is increasing. Consequently, the demand for succinic anhydride is also increasing year by year, especially for high-purity succinic anhydride, which has a high degree of external dependence.

[0003] Currently, the industrially used methods for producing succinic anhydride include biofermentation, electrochemical methods, and catalytic hydrogenation of maleic anhydride. While biofermentation is environmentally friendly, it suffers from high production costs and low product purity, making it difficult to meet industrial production needs. Electrochemical methods are also limited in scale, making them difficult to meet the growing market demand. Maleic anhydride hydrogenation offers advantages such as a simple process flow, convenient operation, high equipment utilization, low operating costs, and high product purity, making it the most efficient process for producing succinic anhydride.

[0004] Maleic anhydride molecules have one C=C bond and two C=O bonds. Under certain catalytic conditions, selective hydrogenation of the C=C bonds can produce succinic anhydride. Further hydrogenation of one of the C=O bonds can produce γ-butyrolactone, and subsequent hydrogenation of the other C=O bond can produce tetrahydrofuran. Therefore, extensive hydrogenation reduces the selectivity of succinic anhydride. Controlling the hydrogenation reaction during the C=C bond hydrogenation stage is the primary challenge in producing succinic anhydride from maleic anhydride, and finding suitable catalysts to improve the selectivity of succinic anhydride is crucial.

[0005] US5616730 discloses a catalyst for catalytic hydrogenation of maleic anhydride to prepare succinic anhydride and a method for continuous production of succinic anhydride. The catalyst is SiO2-loaded nickel with Pd or Pt added as an auxiliary agent. The process conditions are relatively harsh, with a reaction pressure as high as 15 MPa, requiring special requirements for the reactor setting and material, which limits its large-scale application.

[0006] In the methods disclosed in US1541210 and EP0691335, the precious metal Pd is selected as the main active component to prepare the catalyst. Although the hydrogenation selectivity is high, the amount of precious metal used accounts for 3.0-10.0% by weight of the total weight of the catalyst, which greatly increases the production cost and is difficult to achieve industrialization.

[0007] CN109529850A discloses a method for preparing a SiO2-loaded Ni catalyst for hydrogenating maleic anhydride to produce succinic anhydride and its application. The catalyst is used in liquid-phase hydrogenation reactions at a relatively high pressure (5.0 MPa) and can only be used for intermittent synthesis reactions, and cannot be applied to continuous large-scale production. Summary of the Invention

[0008] The present invention aims to overcome the problems of low catalyst activity and succinic anhydride selectivity in the prior art, high catalyst cost, complex process flow, and inability to be applied to continuous large-scale production. The present invention provides a hydrogenation catalyst, a preparation method and application thereof, and a method for hydrogenating maleic anhydride to produce succinic anhydride. The hydrogenation catalyst has high catalyst activity and selectivity, a simple preparation process, and a low catalyst cost, and can be applied to continuous large-scale industrial production.

[0009] In order to achieve the above object, the first aspect of the present invention provides a hydrogenation catalyst, characterized in that the hydrogenation catalyst comprises a carrier and an active component supported on the carrier, the active component comprising: Ni element, Sn element, Ca element and / or Ba element; the carrier comprises SiO2;

[0010] In the hydrogenation catalyst, based on the total weight of the hydrogenation catalyst, calculated as oxide, the Ni element content is 10-40wt%, the Sn element content is 5-15wt%, the Ca element and / or Ba element content is 0.5-5wt%, and the carrier content is 20-80wt%.

[0011] A second aspect of the present invention provides a method for preparing a hydrogenation catalyst, characterized in that the method is a coprecipitation method, comprising the following steps:

[0012] (1) a Ni-containing precursor compound, a carrier precursor compound, and a first solvent are first mixed to obtain a first mixed solution, wherein the carrier precursor compound contains SiO2; a Sn-containing precursor compound solution is second mixed with the first mixed solution to obtain a second mixed solution;

[0013] (2) subjecting the second mixed solution to a first contact reaction with an alkaline solution to obtain a precipitate;

[0014] (3) The precipitate is filtered, washed, dried, and crushed to obtain a powdered matrix catalyst;

[0015] (4) mixing the powdered matrix catalyst with a Ca-containing precursor compound and / or a Ba-containing precursor compound to form a mixture, and calcining the mixture to obtain a hydrogenation catalyst;

[0016] Wherein, in the hydrogenation catalyst, based on the total weight of the hydrogenation catalyst, calculated as oxide, the Ni element content is 10-40wt%, the Sn element content is 5-15wt%, the Ca element and / or Ba element content is 0.5-5wt%, and the carrier content is 20-80wt%.

[0017] The third aspect of the present invention provides a hydrogenation catalyst prepared by the above method.

[0018] A fourth aspect of the present invention provides an application of the above-mentioned hydrogenation catalyst and / or the method for preparing the hydrogenation catalyst in hydrogenating maleic anhydride to produce succinic anhydride.

[0019] A fifth aspect of the present invention provides 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 undergo a second contact reaction to obtain the succinic anhydride;

[0020] Wherein, the activated catalyst is obtained by reducing and activating the above-mentioned hydrogenation catalyst and / or the hydrogenation catalyst obtained by the above-mentioned preparation method with a gas containing hydrogen.

[0021] The reduction activation conditions include: temperature of 300-600° C. and time of 0.5-20 h.

[0022] Through the above technical solution, the hydrogenation catalyst provided by the present invention, its preparation method and application, and the method for hydrogenating maleic anhydride to produce succinic anhydride achieve the following beneficial effects:

[0023] The hydrogenation catalyst provided by the present invention has high activity and selectivity, with a maleic anhydride conversion rate of ≥95% and a succinic anhydride selectivity of ≥90%;

[0024] Furthermore, the hydrogenation catalyst preparation process is simple, the catalyst is inexpensive, and costs are saved. DETAILED DESCRIPTION

[0025] The endpoints of the ranges and any values ​​disclosed herein 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 endpoints of each range, the endpoints of each range and 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 to be specifically disclosed herein.

[0026] The first aspect of the present invention provides a hydrogenation catalyst, characterized in that the hydrogenation catalyst comprises a carrier and an active component supported on the carrier, wherein the active component comprises: Ni element, Sn element, Ca element and / or Ba element; the carrier comprises SiO2;

[0027] In the hydrogenation catalyst, based on the total weight of the hydrogenation catalyst, calculated as oxide, the Ni element content is 10-40wt%, the Sn element content is 5-15wt%, the Ca element and / or Ba element content is 0.5-5wt%, and the carrier content is 20-80wt%.

[0028] In the present invention, when the hydrogenation catalyst meets the above range, it has higher catalytic activity and selectivity.

[0029] According to the present invention, in the hydrogenation catalyst, based on the total weight of the hydrogenation catalyst, calculated as oxide, the Ni element content is 17-28wt%, the Sn element content is 7-12wt%, the Ca and / or Ba element content is 1-3wt%, and the carrier content is 40-75wt%.

[0030] A second aspect of the present invention provides a method for preparing a hydrogenation catalyst, characterized in that the method is a coprecipitation method, comprising the following steps:

[0031] (1) a Ni-containing precursor compound, a carrier precursor compound, and a first solvent are first mixed to obtain a first mixed solution, wherein the carrier precursor compound contains SiO2; a Sn-containing precursor compound solution is second mixed with the first mixed solution to obtain a second mixed solution;

[0032] (2) subjecting the second mixed solution to a first contact reaction with an alkaline solution to obtain a precipitate;

[0033] (3) The precipitate is filtered, washed, dried, and crushed to obtain a powdered matrix catalyst;

[0034] (4) mixing the powdered matrix catalyst with a Ca-containing precursor compound and / or a Ba-containing precursor compound, forming the mixture, and calcining the mixture to obtain a hydrogenation catalyst;

[0035] Wherein, in the hydrogenation catalyst, based on the total weight of the hydrogenation catalyst, calculated as oxide, the Ni element content is 10-40wt%, the Sn element content is 5-15wt%, the Ca element and / or Ba element content is 0.5-5wt%, and the carrier content is 20-80wt%.

[0036] In the present invention, the hydrogenation catalyst prepared by the coprecipitation method can make the catalytic activity and the succinic anhydride selectivity higher, and the preparation process is simple.

[0037] In the present invention, in step (1), there is no particular limitation on the specific conditions of the first mixing, as long as the Ni-containing precursor compound and the precursor compound of the carrier can be fully and uniformly mixed.

[0038] In the present invention, there is no limitation on the first solvent, which is preferably at least one of water, deionized water or distilled water.

[0039] In the present invention, the Sn-containing precursor compound solution is preferably added later, so that the Sn-containing precursor compound solution can be fully dispersed in the first mixed liquid, thereby making the components of the prepared hydrogenation catalyst more evenly mixed.

[0040] According to the present invention, in the hydrogenation catalyst, based on the total weight of the hydrogenation catalyst, calculated as oxide, the Ni element content is 17-28wt%, the Sn element content is 7-12wt%, the Ca and / or Ba element content is 1-3wt%, and the carrier content is 40-75wt%.

[0041] According to the present invention, the Ni-containing precursor compound is a soluble nickel salt, preferably at least one of nickel nitrate, nickel sulfate, nickel chloride and nickel acetate.

[0042] Furthermore, the Sn-containing precursor compound is a soluble tin salt, preferably potassium stannate and / or sodium stannate.

[0043] Furthermore, the precursor compound of the carrier is selected from acidic silica sol and / or alkaline silica sol, preferably acidic silica sol.

[0044] In the present invention, the hydrogenation catalyst contains a Ca-containing precursor compound and / or a Ba-containing precursor compound, which can effectively reduce the acid center of the catalyst and inhibit the occurrence of side reactions during the reaction, so that the reaction has the characteristics of high maleic anhydride conversion rate and high succinic anhydride selectivity.

[0045] Furthermore, the Ca-containing precursor compound is CaCO.

[0046] Furthermore, the Ba-containing precursor compound is BaCO3.

[0047] According to the present invention, in step (1), the second mixing conditions include: temperature 40-90° C., and stirring time 0.5-10 h.

[0048] According to the present invention, in step (2), the pH value of the first contact reaction system is controlled to be 5-8.

[0049] According to the present invention, the alkaline solution is at least one of aqueous ammonia, ammonium carbonate solution and ammonium bicarbonate solution.

[0050] According to the present invention, in step (2), the conditions of the first contact reaction include: temperature of 40-90° C., and reaction time of 0.5-10 h.

[0051] According to the present invention, in step (3), the drying conditions include: temperature of 100-120° C. and time of 10-20 h.

[0052] According to the present invention, in step (4), the calcination conditions include: temperature of 300-600° C. and time of 10-20 h.

[0053] Furthermore, in step (4), the calcination conditions include: temperature of 450-550°C and time of 2-6h.

[0054] According to a preferred embodiment of the present invention:

[0055] (1) In the presence of deionized water, nickel nitrate and silica sol are first mixed to obtain a first mixed solution; and potassium stannate aqueous solution and the first mixed solution are second mixed at 40-90° C., and stirred for 1-4 hours to obtain a second mixed solution;

[0056] (2) subjecting the second mixed solution and the alkaline solution to a first contact reaction at 40-90° C. for 0.5-3 h to obtain a precipitate;

[0057] (3) The precipitate is filtered, washed, dried at 100-120° C. for 10-20 h, and then crushed to obtain a powdered matrix catalyst;

[0058] (4) The powdered matrix catalyst is mixed with CaCO3 and / or BaCO3 to form a mixture, and then calcined at 450-600°C for 10-20h to obtain a hydrogenation catalyst.

[0059] The third aspect of the present invention provides a hydrogenation catalyst prepared by the above method.

[0060] In the present invention, the hydrogenation catalyst obtained by the above preparation method has higher catalytic activity and selectivity, and is more conducive to application in large-scale industrial production.

[0061] A fourth aspect of the present invention provides an application of the above-mentioned hydrogenation catalyst and / or the method for preparing the hydrogenation catalyst in hydrogenating maleic anhydride to produce succinic anhydride.

[0062] A fifth aspect of the present invention provides 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 undergo a second contact reaction to obtain the succinic anhydride;

[0063] Wherein, the activated catalyst is obtained by reducing and activating the above-mentioned hydrogenation catalyst and / or the hydrogenation catalyst obtained by the above-mentioned preparation method with a gas containing hydrogen.

[0064] In the present invention, the equipment used for the second contact reaction is not limited, as long as it can achieve the reaction, for example, it can be carried out in a slurry bed or suspension bed reactor.

[0065] According to the present invention, the reduction activation conditions include: temperature of 300-600° C. and time of 0.5-20 h.

[0066] In the present invention, there is no limitation on the environment for the reduction activation of the hydrogenation catalyst, as long as the activation can be performed.

[0067] According to the present invention, the conditions for the second contact reaction include: a molar ratio of the hydrogen to the maleic anhydride of 10-30:1, a temperature of 40-70° C., a time of 1-6 h, and a pressure of 1-5 MPa.

[0068] Furthermore, the mass ratio of the activation catalyst to the maleic anhydride is 0.01-0.05:1.

[0069] According to the present invention, the maleic anhydride solution contains a second solvent, and the second solvent is at least one of tetrahydrofuran, 1,4-dioxane and γ-butyrolactone.

[0070] According to a preferred embodiment of the present invention:

[0071] (a) In a slurry bed reactor, the above hydrogenation catalyst is heated at 400-600°C with a mixture of nitrogen and hydrogen (the hydrogen content in the mixture is 50% by volume and the hydrogen space velocity is 100h / min). -1 ) reducing for 3-10 hours to activate and obtain an activated catalyst;

[0072] (b) in the presence of the activated catalyst, conducting a second contact reaction with hydrogen and a maleic anhydride solution (the solvent is selected from at least one of tetrahydrofuran, 1,4-dioxane, and γ-butyrolactone, and the maleic anhydride solution has a concentration of 10-30 wt %) at 60-150° C. and a pressure of 1-5 MPa, wherein the molar ratio of the activated catalyst to the maleic anhydride is 0.01-0.05:1;

[0073] (c) condensing the product after the reaction in step (b) to obtain a liquid product, and analyzing the content of each component in the liquid product by gas chromatography. Wherein, the maleic anhydride conversion rate and the selectivity of the succinic anhydride are 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 will be described in detail below through examples.

[0080] The pressures used in the present invention are all absolute pressures.

[0081] The SiO2 content in the silica sol used below was 25% by weight.

[0082] Unless otherwise specified, the raw materials used in the following examples and comparative examples are all commercially available products.

[0083] In the following preparation examples and comparative preparation examples, the composition and content of the hydrogenation catalyst were obtained by XRF testing.

[0084] The following preparation examples are used to illustrate the hydrogenation catalyst and its preparation method of the present invention.

[0085] Preparation Example 1

[0086] (1) Weigh 233.55 g of Ni(NO3)2·6H2O and 828 g of acidic silica sol and dissolve them in 2000 mL of deionized water to obtain a first mixed solution; dissolve 53.56 g of K2Sn(OH)6 in 250 mL of deionized water; place the first mixed solution in a reactor, add K2Sn(OH)6 to the first mixed solution under stirring at 70°C, and stir for 2 h to obtain a second mixed solution;

[0087] (2) adding 10 wt % ammonium bicarbonate solution to the second mixed solution of step (1), controlling the pH value to 7.2, and stirring at 65° C. for 1 hour to obtain a precipitate;

[0088] (3) The precipitate in step (2) was filtered, washed, dried at 120° C. for 12 hours, mixed with 10.71 g of CaCO 3 , and calcined in a muffle furnace at 550° C. for 4 hours to obtain hydrogenation catalyst S1.

[0089] Based on the total weight of the hydrogenation catalyst S1, the hydrogenation catalyst S1 contains 20 wt% of NiO, 9 wt% of SnO2, 69 wt% of SiO2, and 2 wt% of CaO.

[0090] Preparation Example 2

[0091] (1) 315.3 g of Ni(NO3)2·6H2O and 696 g of acidic silica sol were mixed and dissolved in 2000 mL of deionized water to obtain a first mixed solution; 71.41 g of K2Sn(OH)6 was dissolved in 250 mL of deionized water; the first mixed solution was placed in a reactor, and potassium stannate aqueous solution was added to the first mixed solution under stirring at 70°C and stirred for 2 h to obtain a second mixed solution;

[0092] (2) adding 10 wt % ammonium bicarbonate solution to the second mixed solution of step (1), controlling the pH value to 7.2, and stirring at 65° C. for 1 hour to obtain a precipitate;

[0093] (3) The precipitate in step (2) was filtered, washed, dried at 120° C. for 12 hours, mixed with 16.07 g of CaCO 3 , and calcined in a muffle furnace at 550° C. for 4 hours to obtain hydrogenation catalyst S2.

[0094] Based on the total weight of the hydrogenation catalyst S2, the hydrogenation catalyst S2 contains 27 wt% of NiO, 12 wt% of SnO2, 58 wt% of SiO2, and 3 wt% of CaO.

[0095] Preparation Example 3

[0096] (1) Weigh 210.2 g of Ni(NO3)2·6H2O and 888 g of acidic silica sol and dissolve them in 2000 mL of deionized water to obtain a first mixed solution; dissolve 41.66 g of K2Sn(OH)6 in 250 mL of deionized water; place the first mixed solution in a reactor, add potassium stannate aqueous solution to the first mixed solution under stirring at 70°C, and stir for 2 h to obtain a second mixed solution;

[0097] (2) adding 10 wt % ammonium bicarbonate solution to the second mixed solution of step (1), controlling the pH value to 7.2, and stirring at 65° C. for 1 hour to obtain a precipitate;

[0098] (3) The precipitate in step (2) was filtered, washed, dried at 120° C. for 12 hours, mixed with 5.35 g of CaCO 3 , and calcined in a muffle furnace at 550° C. for 4 hours to obtain hydrogenation catalyst S3.

[0099] Based on the total weight of the hydrogenation catalyst S3, the hydrogenation catalyst S3 contains 18 wt% of NiO, 7 wt% of SnO2, 74 wt% of SiO2, and 1 wt% of CaO.

[0100] Preparation Example 4

[0101] The same as Preparation Example 1, except that CaCO3 is replaced by BaCO3, to obtain hydrogenation catalyst S4.

[0102] Based on the total weight of the hydrogenation catalyst S4, the hydrogenation catalyst S4 contains: NiO 20 wt%, SnO 2 9 wt%, SiO 2 68 wt%, and BaO 3 wt%.

[0103] Preparation Example 5

[0104] (1) Weigh 128.45 g of Ni(NO3)2·6H2O and 984 g of acidic silica sol and dissolve them in 2000 mL of deionized water to obtain a first mixed solution; dissolve 35.70 g of K2Sn(OH)6 in 250 mL of deionized water; place the first mixed solution in a reactor, add potassium stannate aqueous solution to the first mixed solution under stirring at 70°C, and stir for 2 h to obtain a second mixed solution;

[0105] (2) adding 10 wt % ammonium bicarbonate solution to the second mixed solution of step (1), controlling the pH value to 7.2, and stirring at 65° C. for 1 hour to obtain a precipitate;

[0106] (3) The precipitate in step (2) was filtered, washed, dried at 120° C. for 12 hours, mixed with 5.35 g of CaCO 3 , and calcined in a muffle furnace at 550° C. for 4 hours to obtain hydrogenation catalyst S5.

[0107] Based on the total weight of the hydrogenation catalyst S5, the hydrogenation catalyst S5 contains 11 wt% of NiO, 6 wt% of SnO2, 82 wt% of SiO2, and 1 wt% of CaO.

[0108] Preparation Example 6

[0109] (1) Weigh 443.75 g of Ni(NO3)2·6H2O and 516 g of acidic silica sol and dissolve them in 2000 mL of deionized water to obtain a first mixed solution; dissolve 83.32 g of K2Sn(OH)6 in 250 mL of deionized water; place the first mixed solution in a reactor, add potassium stannate aqueous solution to the first mixed solution under stirring at 70°C, and stir for 2 h to obtain a second mixed solution;

[0110] (2) adding 10 wt % ammonium bicarbonate solution to the second mixed solution of step (1), controlling the pH value to 7.2, and stirring at 65° C. for 1 hour to obtain a precipitate;

[0111] (3) The precipitate in step (2) was filtered, washed, dried at 120° C. for 12 hours, mixed with 26.78 g of CaCO 3 , and calcined in a muffle furnace at 550° C. for 4 hours to obtain hydrogenation catalyst S6.

[0112] Based on the total weight of the hydrogenation catalyst S6, the hydrogenation catalyst S6 contains 38 wt% of NiO, 14 wt% of SnO2, 43 wt% of SiO2, and 5 wt% of CaCO3.

[0113] Preparation Example 7

[0114] The same as Preparation Example 1, except that in step (1), K2Sn(OH)6 was added to the first mixed solution under stirring at 50°C and stirred for 3 hours to obtain a second mixed solution. The other steps were the same as Preparation Example 1 to prepare hydrogenation catalyst S7.

[0115] Based on the total weight of the hydrogenation catalyst S7, the hydrogenation catalyst S7 contains 21 wt% of NiO, 10 wt% of SnO2, 67 wt% of SiO2, and 2 wt% of CaO.

[0116] Preparation Example 8

[0117] The method is consistent with Preparation Example 1, except that in step (3), the calcination condition is replaced with calcination at 450°C for 6 hours. The other steps are consistent with Preparation Example 1, and hydrogenation catalyst S8 is prepared.

[0118] Based on the total weight of the hydrogenation catalyst S8, the hydrogenation catalyst S8 contains 19 wt% of NiO, 8 wt% of SnO2, 69 wt% of SiO2, and 2 wt% of CaO.

[0119] Preparation Example 9

[0120] The method is consistent with Preparation Example 1, except that in step (3), CaCO3 is replaced by a mixture of BaCO3 and CaCO3, keeping the total amount the same, wherein the mass ratio of CaCO3 to BaCO3 is 1:1, and the other steps are consistent with Preparation Example 1 to prepare hydrogenation catalyst S9.

[0121] Based on the total weight of the hydrogenation catalyst S9, the hydrogenation catalyst S9 contains NiO 20 wt%, SnO 29 wt%, SiO 269 wt%, CaO 1 wt%, BaO 1 wt%.

[0122] Comparative Preparation Example 1

[0123] (1) Weighing 233.55 g of Ni(NO3)2·6H2O and 936 g of acidic silica sol and dissolving them in 2000 mL of deionized water to obtain a first mixed solution;

[0124] (2) placing the first mixed solution into a reaction kettle, adding 10 wt % ammonium bicarbonate solution to the first mixed solution under stirring at 70° C., controlling the pH value to 7.2, and stirring at 65° C. for 1 hour to obtain a precipitate;

[0125] (3) The precipitate in step (2) was filtered, washed, dried at 120° C. for 12 hours, mixed with 10.71 g of CaCO 3 , and calcined in a muffle furnace at 550° C. for 4 hours to obtain hydrogenation catalyst CS1.

[0126] Based on the total weight of the hydrogenation catalyst CS1, the hydrogenation catalyst CS1 contains 20 wt% NiO, 78 wt% SiO2, and 2 wt% CaO2.

[0127] Comparative Preparation Example 2

[0128] (1) Weigh 233.55 g of Ni(NO3)2·6H2O and 852 g of acidic silica sol and dissolve them in 2000 mL of deionized water to obtain a first mixed solution; dissolve 53.56 g of K2Sn(OH)6 in 250 mL of deionized water; place the first mixed solution in a reactor, add K2Sn(OH)6 to the first mixed solution under stirring at 70°C, and stir for 2 h to obtain a second mixed solution;

[0129] (2) adding 10 wt % ammonium bicarbonate solution to the second mixed solution of step (1), controlling the pH value to 7.2, and stirring at 65° C. for 1 hour to obtain a precipitate;

[0130] (3) The precipitate in step (2) was filtered, washed, dried at 120° C. for 12 hours, and calcined in a muffle furnace at 550° C. for 4 hours to obtain hydrogenation catalyst CS2.

[0131] Based on the total weight of the hydrogenation catalyst CS2, the hydrogenation catalyst CS2 contains 20 wt% of NiO, 9 wt% of SnO2, and 71 wt% of SiO2.

[0132] Preparation Comparative Example 3

[0133] (1) 93.42 g of Ni(NO3)2·6H2O and 984 g of acidic silica sol were mixed and dissolved in 2000 mL of deionized water to obtain a first mixed solution; 53.56 g of K2Sn(OH)6 was dissolved in 250 mL of deionized water; the first mixed solution was placed in a reactor, and potassium stannate aqueous solution was added to the first mixed solution under stirring at 70°C and stirred for 2 h to obtain a second mixed solution;

[0134] (2) adding 10 wt % ammonium bicarbonate solution to the second mixed solution of step (1), controlling the pH value to 7.2, and stirring at 65° C. for 1 hour to obtain a precipitate;

[0135] (3) The precipitate in step (2) was filtered, washed, dried at 120° C. for 12 hours, mixed with 5.36 g of CaCO 3 , and calcined in a muffle furnace at 550° C. for 4 hours to obtain hydrogenation catalyst CS 3 .

[0136] Based on the total weight of the hydrogenation catalyst CS3, the hydrogenation catalyst CS3 contains 8 wt% NiO, 9 wt% SnO, 82 wt% SiO, and 1 wt% CaO.

[0137] The following examples are used to illustrate the application of the hydrogenation catalyst of the present invention and the method for hydrogenating maleic anhydride to produce succinic anhydride.

[0138] Example 1

[0139] (a) In a slurry bed reactor, 1.2 g of the above hydrogenation catalyst was weighed and heated at 450° C. with a mixture of nitrogen and hydrogen (the hydrogen content in the mixture was 50% by volume and the hydrogen space velocity was 400 h / min). -1 ) was reduced for 6 h for activation to obtain an activated catalyst;

[0140] (b) in the presence of the activated catalyst, hydrogen and 500 g of maleic anhydride solution (solvent: tetrahydrofuran maleic anhydride solution with a concentration of 20 wt%) are subjected to a second contact reaction at 60° C. and 2 MPa;

[0141] (c) condensing the product after the reaction in step (b) to obtain a liquid product, and analyzing the content of each component in the liquid product by gas chromatography. The conversion rate of maleic anhydride and the selectivity of succinic anhydride were calculated by the following formulas, and the specific results are shown in Table 1.

[0142] The maleic anhydride conversion rate and the succinic anhydride selectivity are calculated by the following formula:

[0143] Maleic anhydride conversion rate = (Mo-Ma) / Mo×100%

[0144] Selectivity of succinic anhydride = Mi / (Mo-Ma)×100%

[0145] Wherein, Mo is the amount of maleic anhydride, mol;

[0146] Ma—the amount of maleic anhydride remaining after the reaction, mol;

[0147] Mi—the amount of succinic anhydride produced after the reaction, mol.

[0148] Examples 2-9

[0149] The method of Example 1 was followed, except that the hydrogenation catalysts prepared in Preparation Examples 2-9 were used instead of the hydrogenation catalyst prepared in Preparation Example 1. The conversion of maleic anhydride and the selectivity of succinic anhydride are shown in Table 1.

[0150] Comparative Examples 1-3

[0151] The method of Example 1 was followed, except that the hydrogenation catalysts prepared in Comparative Preparation Examples 1-3 were used instead of the hydrogenation catalyst prepared in Preparation Example 1. The conversion of maleic anhydride and the selectivity of succinic anhydride are shown in Table 1.

[0152] Table 1

[0153] Maleic anhydride conversion rate (%) Succinic anhydride selectivity (%) Example 1 100 99.6 Example 2 100 96.8 Example 3 99.5 97.5 Example 4 100 98.3 Example 5 96.7 95.1 Example 6 100 92.8 Example 7 100 98.9 Example 8 100 99.2 Example 9 100 99.3 Comparative Example 1 99.8 88.3 Comparative Example 2 99.5 88.9 Comparative Example 3 83.2 91.3

[0154] As can be seen from Table 1, the hydrogenation catalyst containing Ni-Sn-Si-Ca / Ba elements of the present invention has high catalytic activity and selectivity for succinic anhydride when applied to liquid-phase catalytic hydrogenation of maleic anhydride to produce succinic anhydride.

[0155] From the data comparison of Examples 1-3 and Examples 5 and 6, it can be seen that the effects of Examples 1-3 are better than those of Examples 5 and 6. Therefore, when the content of the active component in the catalyst meets the preferred range of this application, the catalytic activity and selectivity of the prepared hydrogenation catalyst for succinic anhydride are better.

[0156] It can be seen from Example 1 and Comparative Example 1 that, since no Sn element is introduced in Comparative Example 1, under the same reaction conditions as those of the present invention, the selectivity of succinic anhydride is significantly reduced, while in Example 1, the selectivity of succinic anhydride is as high as 99.6%.

[0157] It can be seen from Example 1 and Comparative Example 2 that, since no Ca or Ba elements were introduced into the comparative example, under the same reaction conditions as those of the present invention, the selectivity of succinic anhydride was significantly reduced.

[0158] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A hydrogenation catalyst, characterized in that The hydrogenation catalyst comprises a carrier and an active component supported on the carrier, wherein the active component comprises: Ni element, Sn element, Ca element and / or Ba element; the carrier comprises SiO2; In the hydrogenation catalyst, based on the total weight of the hydrogenation catalyst, the Ni content, calculated as oxide, is 10-40wt%, the Sn content is 5-15wt%, the Ca and / or Ba content is 0.5-5wt%, and the carrier content is 20-80wt%. The method for preparing the hydrogenation catalyst is a co-precipitation method, comprising the following steps: (1) a Ni-containing precursor compound, a carrier precursor compound, and a first solvent are first mixed to obtain a first mixed solution, wherein the carrier precursor compound contains SiO2; a Sn-containing precursor compound solution is second mixed with the first mixed solution to obtain a second mixed solution; (2) subjecting the second mixed solution to a first contact reaction with the alkaline solution to obtain a precipitate; (3) The precipitate is filtered, washed, dried, and crushed to obtain a powdered matrix catalyst; (4) The powdered matrix catalyst is mixed with a Ca-containing precursor compound and / or a Ba-containing precursor compound to form a mixture, and then calcined to obtain a hydrogenation catalyst.

2. The hydrogenation catalyst according to claim 1, wherein In the hydrogenation catalyst, based on the total weight of the hydrogenation catalyst, calculated as oxide, the Ni element content is 17-28 wt%, the Sn element content is 7-12 wt%, the Ca and / or Ba element content is 1-3 wt%, and the carrier content is 40-75 wt%.

3. A method for preparing the hydrogenation catalyst according to claim 1 or 2, characterized in that: The method is a co-precipitation method, comprising the following steps: (1) a Ni-containing precursor compound, a carrier precursor compound, and a first solvent are first mixed to obtain a first mixed solution, wherein the carrier precursor compound contains SiO2; a Sn-containing precursor compound solution is second mixed with the first mixed solution to obtain a second mixed solution; (2) subjecting the second mixed solution to a first contact reaction with the alkaline solution to obtain a precipitate; (3) The precipitate is filtered, washed, dried, and crushed to obtain a powdered matrix catalyst; (4) mixing the powdered matrix catalyst with a Ca-containing precursor compound and / or a Ba-containing precursor compound to form a mixture, and calcining the mixture to obtain a hydrogenation catalyst; Wherein, in the hydrogenation catalyst, based on the total weight of the hydrogenation catalyst, calculated as oxide, the Ni element content is 10-40wt%, the Sn element content is 5-15wt%, the Ca element and / or Ba element content is 0.5-5wt%, and the carrier content is 20-80wt%.

4. The method according to claim 3, wherein: In the hydrogenation catalyst, based on the total weight of the hydrogenation catalyst, calculated as oxide, the Ni element content is 17-28 wt%, the Sn element content is 7-12 wt%, the Ca and / or Ba element content is 1-3 wt%, and the carrier content is 40-75 wt%.

5. The method according to claim 3 or 4, wherein: The Ni-containing precursor compound is a soluble nickel salt.

6. The method according to claim 3 or 4, wherein: The Ni-containing precursor compound is at least one of nickel nitrate, nickel sulfate, nickel chloride and nickel acetate.

7. The method according to claim 3 or 4, wherein: The Sn-containing precursor compound is a soluble tin salt.

8. The method according to claim 3 or 4, wherein: The Sn-containing precursor compound is potassium stannate and / or sodium stannate.

9. The method according to claim 3 or 4, wherein: The precursor compound of the support is selected from acidic silica sol and / or alkaline silica sol.

10. The method according to claim 3 or 4, wherein: The precursor compound of the carrier is acidic silica sol.

11. The method according to claim 3 or 4, wherein: The Ca-containing precursor compound is CaCO3.

12. The method according to claim 3 or 4, wherein: The Ba-containing precursor compound is BaCO3.

13. The method according to claim 3 or 4, wherein: In step (1), the second mixing conditions include: temperature 40-90°C, stirring time 0.5-10h.

14. The method according to claim 3 or 4, wherein In step (2), the pH value of the first contact reaction system is controlled to be 5-8.

15. The method according to claim 3 or 4, wherein: The alkaline solution is at least one of aqueous ammonia, ammonium carbonate solution and ammonium bicarbonate solution.

16. The method according to claim 3, wherein In step (2), the conditions of the first contact reaction include: temperature of 40-90°C, reaction time of 0.5-10h; And / or, in step (3), the drying conditions include: temperature of 100-120°C, time of 10-20h; And / or, in step (4), the calcination conditions include: temperature of 300-600°C and time of 10-20h.

17. The method according to claim 16, wherein: In step (4), the calcination conditions include: temperature of 450-550°C and time of 2-6 hours.

18. A hydrogenation catalyst prepared by the method according to any one of claims 3 to 17.

19. Use of the hydrogenation catalyst according to any one of claims 1, 2 and 18 in the liquid-phase hydrogenation of maleic anhydride to produce succinic anhydride.

20. 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 undergo a second contact reaction to obtain succinic anhydride; Wherein, the activated catalyst is obtained by reducing and activating the hydrogenation catalyst according to any one of claims 1, 2 and 18 through a gas containing hydrogen; The reduction activation conditions include: temperature of 300-600° C. and time of 0.5-20 h.

21. The method according to claim 20, wherein The maleic anhydride is present in the form of a maleic anhydride solution, and the concentration of the maleic anhydride solution is 10-30% by weight; The conditions of the second contact reaction include: a molar ratio of the hydrogen to the maleic anhydride of 10-30:1, a temperature of 40-70° C., a time of 1-6 h, and a pressure of 1-5 MPa; And / or, the mass ratio of the activation catalyst to the maleic anhydride is 0.01-0.05:1.