CN116020474A - Hydrogenation catalyst, preparation method and application thereof, and method for preparing succinic anhydride by hydrogenation of maleic anhydride - Google Patents

Abstract

The present invention relates to the technical field of catalysts, in particular to a hydrogenation catalyst, its preparation method and application, and a method for producing succinic anhydride by hydrogenation of maleic anhydride. The hydrogenation catalyst includes a carrier and an active component loaded on the carrier , the active component contains: Ni element, Sn element, Ca element and/or Ba element; the carrier contains SiO ₂ ; in the hydrogenation catalyst, the total weight of the hydrogenation catalyst is based on the oxidation In terms of material, the content of Ni element is 10-40wt%, the content of Sn element is 5-15wt%, the content of Ca element and/or Ba element is 0.5-5wt%, and the content of carrier is 20-80wt%. The hydrogenation catalyst of the invention still has high catalytic activity and succinic anhydride selectivity under low-temperature reaction, and the preparation process is simple, and can be applied to continuous large-scale production.

Description

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

technical field

The present invention relates to the technical field of catalysts, in particular, to a catalyst for the production of succinic anhydride by liquid-phase hydrogenation of maleic anhydride and a preparation method thereof, and the application of the catalyst for the production of succinic anhydride by liquid-phase hydrogenation of maleic anhydride, And a method for preparing succinic anhydride by liquid-phase hydrogenation of maleic anhydride.

Background technique

Succinic anhydride, also known as succinic anhydride, is an important organic synthesis intermediate and fine chemical raw material, and is widely used in food, surfactant, paint, medicine, agriculture, plastics and other fields. Moreover, succinic acid, the hydrolysis product of succinic anhydride, is the main raw material of polybutylene succinate biodegradable materials. With the emphasis and development of the country's environmental protection policy, the demand for succinic acid is increasing day by day. Therefore, 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.

At present, the production methods of succinic anhydride used in industry include: biological fermentation method, electrochemical method and catalytic hydrogenation method of maleic anhydride. Among them, although the biological fermentation method is environmentally friendly, the production cost of this method is high and the product purity is low, which is difficult to meet the needs of industrial production; the production scale of the electrochemical method is small, and it is difficult to meet the growing market demand; the maleic anhydride hydrogenation method has a process The advantages of simple process, convenient operation, high equipment utilization rate, low operating cost and high product purity are currently the most efficient process for producing succinic anhydride.

The maleic anhydride molecule has a C=C bond and two C=O bonds. Under certain catalytic conditions, the selective hydrogenation of the C=C bond can synthesize succinic anhydride; continue to hydrogenate one of the C=O bonds, γ-butyrolactone can be synthesized; followed by hydrogenation of another C=O bond, tetrahydrofuran can be synthesized. It can be seen that deep hydrogenation will reduce the selectivity of succinic anhydride, how to control the hydrogenation reaction in the C=C bond hydrogenation stage is the most important problem of maleic anhydride hydrogenation to prepare succinic anhydride, and it is necessary to find a suitable catalyst to improve Selectivity of succinic anhydride.

US5616730 discloses a kind of catalyst and the method for continuous production of succinic anhydride that are used to catalyze the hydrogenation of maleic anhydride to prepare succinic anhydride, this catalyst is with _SiO Loaded nickel, added Pd or Pt as auxiliary agent, in this processing condition, reaction The conditions are relatively harsh, and the reaction pressure is as high as 15 MPa, which requires special requirements for the reactor settings and materials, which limits its large-scale application.

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 the precious metal accounts for 3.0-10.0% by weight of the total weight of the catalyst, which greatly increases the production cost. , it is difficult to achieve industrialization.

CN109529850A discloses a kind of _SiO The preparation method and the application of the catalyst for preparing succinic anhydride by the hydrogenation of maleic anhydride supported Ni, the pressure of this catalyst in the liquid phase hydrogenation reaction is higher (5.0MPa), and can only be used It is used for batch synthesis reactions and cannot be applied to continuous large-scale production.

Contents of the invention

The purpose of the present invention is to overcome the catalyst activity and the selectivity of succinic anhydride existing in the prior art are low, and catalyst cost is high, technological process is complicated, can't be applied to the problem of continuous large-scale production, provide hydrogenation catalyst and its preparation Method and application and method of hydrogenation of maleic anhydride to succinic anhydride. The hydrogenation catalyst has the characteristics of high catalyst activity and selectivity, simple preparation process and low catalyst price, and can be applied to continuous large-scale industrial production.

In order to achieve the above object, the first aspect of the present invention provides a hydrogenation catalyst, which is characterized in that the hydrogenation catalyst includes a carrier and an active component loaded on the carrier, and the active component contains: Ni element, Sn element , Ca element and/or Ba element; the carrier contains SiO ₂ ;

In the hydrogenation catalyst, based on the total weight of the hydrogenation catalyst, in terms of oxides, the content of Ni element is 10-40wt%, the content of Sn element is 5-15wt%, and the content of Ca element and/or Ba element 0.5-5wt%, and the carrier content is 20-80wt%.

The second aspect of the present invention provides a method for preparing a hydrogenation catalyst, characterized in that the method is a co-precipitation method, comprising the following steps:

(1) The precursor compound containing Ni, the precursor compound of the carrier and the first solvent are first mixed to obtain the first mixed solution, and the precursor compound of the carrier contains SiO ₂ ; the solution of the precursor compound containing Sn is mixed with the The first mixed solution is mixed for the second time to obtain the second mixed solution;

(2) carrying out the first contact reaction with the second mixed solution and the alkali solution to obtain a precipitate;

(3) After the precipitate is filtered, washed, dried and pulverized, a powder matrix catalyst is obtained;

(4) mixing and molding the powder base catalyst with the Ca-containing precursor compound and/or the Ba-containing precursor compound, and obtaining a hydrogenation catalyst after roasting;

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

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

The fourth aspect of the present invention provides an application of the above-mentioned hydrogenation catalyst and/or the preparation method of the hydrogenation catalyst in the hydrogenation of maleic anhydride to succinic anhydride.

The fifth aspect of the present invention provides a method for producing 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 subjected to a second contact reaction to obtain the succinic anhydride ;

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 by a gas containing hydrogen.

The conditions for the reductive activation include: the temperature is 300-600°C, and the time is 0.5-20h.

Through the above technical scheme, the hydrogenation catalyst provided by the present invention and its preparation method and application and the method for hydrogenating maleic anhydride to succinic anhydride obtain the following beneficial effects:

The hydrogenation catalyst provided by the invention has high activity and selectivity, the conversion rate of maleic anhydride is ≥ 95%, and the selectivity of succinic anhydride is ≥ 90%;

Further, the preparation process of the hydrogenation catalyst is simple, the price of the catalyst is low, and the cost is saved.

Detailed ways

Neither the endpoints nor any values of the ranges disclosed herein are limited to such precise ranges or values, and these ranges or values are understood to include values approaching these ranges or values. For numerical ranges, between the endpoints of each range, between the endpoints of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, these values Ranges should be considered as specifically disclosed herein.

The first aspect of the present invention provides a hydrogenation catalyst, characterized in that the hydrogenation catalyst includes a carrier and an active component loaded on the carrier, and the active component contains: Ni element, Sn element, Ca element and/or or Ba element; the carrier contains SiO ₂ ;

In the hydrogenation catalyst, based on the total weight of the hydrogenation catalyst, in terms of oxides, the content of Ni element is 10-40wt%, the content of Sn element is 5-15wt%, and the content of Ca element and/or Ba element 0.5-5wt%, and the carrier content is 20-80wt%.

In the present invention, when the hydrogenation catalyst satisfies the above range, it has higher catalytic activity and selectivity.

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

The second aspect of the present invention provides a method for preparing a hydrogenation catalyst, characterized in that the method is a co-precipitation method, comprising the following steps:

(1) The precursor compound containing Ni, the precursor compound of the carrier and the first solvent are first mixed to obtain the first mixed solution, and the precursor compound of the carrier contains SiO ₂ ; the solution of the precursor compound containing Sn is mixed with the The first mixed solution is mixed for the second time to obtain the second mixed solution;

(2) carrying out the first contact reaction with the second mixed solution and the alkali solution to obtain a precipitate;

(3) After the precipitate is filtered, washed, dried and pulverized, a powder matrix catalyst is obtained;

(4) mixing the powder base catalyst with a Ca-containing precursor compound and/or a Ba-containing precursor compound, and obtaining a hydrogenation catalyst after roasting;

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

In the present invention, the hydrogenation catalyst prepared by the co-precipitation method can have higher catalytic activity and succinic anhydride selectivity, and the preparation process is simple.

In the present invention, in step (1), the specific conditions for the first mixing are not particularly limited, as long as the Ni-containing precursor compound and the carrier precursor compound can be fully and uniformly mixed.

In the present invention, there is no limitation on the first solvent, and it is preferably at least one of water, deionized water or distilled water.

In the present invention, it is preferable to add the Sn-containing precursor compound solution later, so that the Sn-containing precursor compound solution can be fully dispersed in the first mixed liquid, and then the components in the prepared hydrogenation catalyst can be mixed more uniformly.

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

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.

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

Further, the precursor compound of the carrier is selected from acidic silica sol and/or alkaline silica sol, preferably acidic silica sol.

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, suppress the occurrence of side reactions in the reaction process, and make the reaction have a high conversion rate of maleic anhydride , High selectivity of succinic anhydride.

Further, the Ca-containing precursor compound is CaCO.

Further, the Ba-containing precursor compound is BaCO ₃ .

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

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

According to the present invention, the alkaline solution is at least one of ammonia water, ammonium carbonate solution and ammonium bicarbonate solution.

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

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

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

Further, in step (4), the calcination conditions include: the temperature is 450-550°C, and the time is 2-6h.

According to a preferred embodiment of the present invention:

(1) In the presence of deionized water, nickel nitrate and silica sol are mixed for the first time to obtain the first mixed solution; and at 40-90° C., the potassium stannate aqueous solution is mixed with the first mixed solution Two mixing, after stirring for 1-4h, the second mixed solution is obtained;

(2) performing the first contact reaction with the second mixed solution and the alkali solution at 40-90° C. for 0.5-3 hours to obtain a precipitate;

(3) The precipitate is filtered, washed, dried at 100-120°C for 10-20 hours, and then pulverized to obtain a powder matrix catalyst;

(4) After mixing and molding the powder matrix catalyst with CaCO ₃ and/or BaCO ₃ , calcining at 450-600° C. for 10-20 h to obtain a hydrogenation catalyst.

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

In the present invention, the hydrogenation catalyst obtained by the above-mentioned preparation method has higher catalytic activity and selectivity, and is more favorable to be applied in large-scale industrial production.

The fourth aspect of the present invention provides an application of the above-mentioned hydrogenation catalyst and/or the preparation method of the hydrogenation catalyst in the hydrogenation of maleic anhydride to succinic anhydride.

The fifth aspect of the present invention provides a method for producing 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 subjected to a second contact reaction to obtain the succinic anhydride ;

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 by a gas containing hydrogen.

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

According to the present invention, the reductive activation conditions include: the temperature is 300-600°C, and the time is 0.5-20h.

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

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

Further, the mass ratio of the activated catalyst to the maleic anhydride is 0.01-0.05:1.

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.

According to a preferred embodiment of the present invention:

(a) In a slurry bed reactor, reduce the above-mentioned hydrogenation catalyst with a mixture of nitrogen and hydrogen (the hydrogen content in the mixture is 50% by volume, and the hydrogen space velocity is 100h ^-1 ) at 400-600°C for 3-10h Activating to obtain an activated catalyst;

(b) In the presence of the activated catalyst, hydrogen and maleic anhydride solution (solvent is selected from at least one of tetrahydrofuran, 1.4-dioxane and γ-butyrolactone, the maleic anhydride solution concentration is 10-30% by weight ), the second contact reaction is carried out at 60-150°C under a pressure of 1-5MPa, and the molar ratio of activated catalyst to maleic anhydride is 0.01-0.05:1;

(c) condensing the reacted product in step (b) to obtain a liquid product, and analyzing the contents of each component in the liquid product by gas chromatography. Wherein, the selectivity of described maleic anhydride conversion rate and described succinic anhydride is calculated by following formula:

Maleic anhydride conversion=(Mo-Ma)/Mo×100%

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

Wherein, Mo—the amount of substance of raw material maleic anhydride, mol;

Ma—the amount of the remaining material of maleic anhydride after the reaction, mol;

Mi—the amount of succinic anhydride generated after the reaction, mol.

The present invention will be described in detail below by way of examples.

All pressures used in the present invention are absolute pressures.

The content of _SiO2 in the silica sol used below was 25% by weight.

Unless otherwise specified, the raw materials used in the following examples and comparative examples are commercially available.

In the following preparation examples and comparative preparation examples, the composition and content of the hydrogenation catalyst were obtained through XRF testing.

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

Preparation Example 1

(1) Weigh 233.55g Ni(NO ₃ ) ₂ ·6H ₂ O, 828g acidic silica sol and dissolve in 2000mL deionized water to obtain the first mixed solution; 53.56g K ₂ Sn(OH) ₆ is dissolved in 250mL deionized water; put the first mixed solution into a reaction kettle, and add K ₂ Sn(OH) ₆ into the first mixed solution under stirring at 70°C, and stir for 2 hours to obtain the second mixed solution;

(2) Add 10wt% ammonium bicarbonate solution to the second mixed solution in step (1), control the pH value to 7.2, and stir at 65° C. for 1 hour to obtain a precipitate;

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

Based on the total weight of the hydrogenation catalyst S1, the hydrogenation catalyst S1 contains 20 wt% of NiO, 9 wt% of SnO ₂ , 69 wt% of SiO ₂ and 2 wt% of CaO.

Preparation example 2

(1) Weigh 315.3g Ni(NO ₃ ) ₂ ·6H ₂ O, 696g acidic silica sol and dissolve in 2000mL deionized water to obtain the first mixed solution; 71.41g K ₂ Sn(OH) ₆ is dissolved in 250mL deionized In water; put the first mixed solution into a reaction kettle, and under stirring at 70° C., add an aqueous solution of potassium stannate to the first mixed solution, and stir for 2 hours to obtain a second mixed solution;

(2) Add 10wt% ammonium bicarbonate solution to the second mixed solution in step (1), control the pH value to 7.2, and stir at 65° C. for 1 hour to obtain a precipitate;

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

Based on the total weight of the hydrogenation catalyst S2, the hydrogenation catalyst S2 contains 27wt% NiO, 12wt% _{SnO2 ,} 58wt% SiO2 and 3wt% CaO.

Preparation example 3

(1) Weigh 210.2g Ni(NO ₃ ) ₂ ·6H ₂ O, 888g acidic silica sol and dissolve in 2000mL deionized water to obtain the first mixed solution; 41.66g K ₂ Sn(OH) ₆ is dissolved in 250mL deionized In water; put the first mixed solution into a reaction kettle, and under stirring at 70° C., add an aqueous solution of potassium stannate to the first mixed solution, and stir for 2 hours to obtain a second mixed solution;

(2) Add 10wt% ammonium bicarbonate solution to the second mixed solution in step (1), control the pH value to 7.2, and stir at 65° C. for 1 hour to obtain a precipitate;

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

Based on the total weight of the hydrogenation catalyst S3, the hydrogenation catalyst S3 contains 18 wt% of NiO, 7 wt% of SnO ₂ , 74 wt% of SiO ₂ and CaO1 wt%.

Preparation Example 4

Consistent with Preparation Example 1, the difference is that CaCO ₃ is replaced by BaCO ₃ to obtain hydrogenation catalyst S4.

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

Preparation Example 5

(1) Weigh 128.45g Ni(NO ₃ ) ₂ ·6H ₂ O, 984g acidic silica sol and dissolve in 2000mL deionized water to obtain the first mixed solution; 35.70g K ₂ Sn(OH) ₆ is dissolved in 250mL deionized In water; put the first mixed solution into a reaction kettle, and under stirring at 70° C., add an aqueous solution of potassium stannate to the first mixed solution, and stir for 2 hours to obtain a second mixed solution;

(2) Add 10wt% ammonium bicarbonate solution to the second mixed solution in step (1), control the pH value to 7.2, and stir at 65° C. for 1 hour to obtain a precipitate;

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

Based on the total weight of the hydrogenation catalyst S5, the hydrogenation catalyst S5 contains 11 wt% of NiO, 6 wt% of SnO ₂ , 82 wt% of SiO ₂ and CaO1 wt%.

Preparation example 6

(1) Weigh 443.75g Ni(NO ₃ ) ₂ ·6H ₂ O, 516g acidic silica sol and dissolve in 2000mL deionized water to obtain the first mixed solution; 83.32g K ₂ Sn(OH) ₆ is dissolved in 250mL deionized In water; put the first mixed solution into a reaction kettle, and under stirring at 70° C., add an aqueous solution of potassium stannate to the first mixed solution, and stir for 2 hours to obtain a second mixed solution;

(2) Add 10wt% ammonium bicarbonate solution to the second mixed solution in step (1), control the pH value to 7.2, and stir at 65° C. for 1 hour to obtain a precipitate;

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

Based on the total weight of the hydrogenation catalyst S6, the hydrogenation catalyst S6 contains 38 wt% of NiO, 14 wt% of SnO ₂ , 43 wt% of SiO ₂ and 5 wt% of CaCO ₃ .

Preparation Example 7

Consistent with Preparation Example 1, the difference is that in step (1), under stirring at 50°C, K ₂ Sn(OH) ₆ was added to the first mixed solution, and stirred for 3 hours to obtain the second mixed solution, and the other steps were the same as Consistent with Preparation Example 1, the hydrogenation catalyst S7 was prepared.

Based on the total weight of the hydrogenation catalyst S7, the hydrogenation catalyst S7 contains 21wt% NiO, 10wt% _SnO2 , 67wt% _SiO2 and 2wt% CaO.

Preparation example 8

Consistent with Preparation Example 1, the difference is that in step (3), the calcination condition was replaced by calcination at 450° C. for 6 hours, and other steps were consistent with Preparation Example 1 to prepare hydrogenation catalyst S8.

Based on the total weight of the hydrogenation catalyst S8, the hydrogenation catalyst S8 contains 19 wt% of NiO, 8 wt% of SnO ₂ , 69 wt% of SiO ₂ and 2 wt% of CaO.

Preparation Example 9

Consistent with Preparation Example 1, the difference is that _in step (3), _CaCO is replaced by a mixture of BaCO and _CaCO to keep the total amount the same, wherein the mass ratio of CaCO to _BaCO is 1:1 _, and the other steps Consistent with Preparation Example 1, hydrogenation catalyst S9 was prepared.

Based on the total weight of the hydrogenation catalyst S9, the hydrogenation catalyst S9 contains NiO20wt%, _SnO2 9wt%, _SiO2 69wt%, CaO1wt%, BaO1wt%

Comparative Preparation Example 1

(1) Weigh 233.55g of Ni(NO ₃ ) ₂ ·6H ₂ O and 936g of acidic silica sol and dissolve them in 2000mL of deionized water to obtain the first mixed solution;

(2) Put the first mixed solution into the reaction kettle, under stirring at 70°C, add 10wt% ammonium bicarbonate solution into the first mixed solution, control the pH value to 7.2, and stir at 65°C for 1 hour, get sediment;

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

Based on the total weight of the hydrogenation catalyst CS1, the hydrogenation catalyst CS1 contains 20wt% NiO, 78wt% _SiO2 and CaO2 wt%.

Comparative Preparation Example 2

(1) Weigh 233.55g Ni(NO ₃ ) ₂ ·6H ₂ O, 852g acidic silica sol and dissolve in 2000mL deionized water to obtain the first mixed solution; 53.56g K ₂ Sn(OH) ₆ is dissolved in 250mL deionized water; put the first mixed solution into a reaction kettle, and add K ₂ Sn(OH) ₆ into the first mixed solution under stirring at 70°C, and stir for 2 hours to obtain the second mixed solution;

(2) Add 10wt% ammonium bicarbonate solution to the second mixed solution in step (1), control the pH value to 7.2, and stir at 65° C. for 1 hour to obtain a precipitate;

(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 the hydrogenation catalyst CS2.

Based on the total weight of the hydrogenation catalyst CS2, the hydrogenation catalyst CS2 contains 20 wt% of NiO, 9 wt% of SnO ₂ and 71 wt% of SiO ₂ .

Prepare comparative example 3

(1) Weigh 93.42g Ni(NO ₃ ) ₂ ·6H ₂ O, 984g acidic silica sol and dissolve in 2000mL deionized water to obtain the first mixed solution; 53.56g K ₂ Sn(OH) ₆ is dissolved in 250mL deionized In water; put the first mixed solution into a reaction kettle, and under stirring at 70° C., add an aqueous solution of potassium stannate to the first mixed solution, and stir for 2 hours to obtain a second mixed solution;

(2) Add 10wt% ammonium bicarbonate solution to the second mixed solution in step (1), control the pH value to 7.2, and stir at 65° C. for 1 hour to obtain a precipitate;

(3) The precipitate in step (2) was filtered, washed, dried at 120°C for 12 hours, then mixed with 5.36g of CaCO ₃ to form, and calcined in a muffle furnace at 550°C for 4 hours to obtain the hydrogenation catalyst CS3.

Based on the total weight of the hydrogenation catalyst CS3, the hydrogenation catalyst CS3 contains 8 wt% of NiO, 9 wt% of SnO ₂ , 82 wt% of SiO ₂ and 1 wt% of CaO.

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

Example 1

(a) In a slurry bed reactor, weigh 1.2 g of the above-mentioned hydrogenation catalyst and reduce it with a mixture of nitrogen and hydrogen (the hydrogen content in the mixture is 50% by volume, and the hydrogen space velocity is 400h ^-1 ) at 450°C for 6h. Activation to obtain an activated catalyst;

(b) In the presence of the activated catalyst, hydrogen and 500g maleic anhydride solution (the solvent is tetrahydrofuran maleic anhydride solution with a concentration of 20% by weight) are carried out at 60°C and 2MPa for the second contact reaction;

(c) condensing the reacted product in step (b) to obtain a liquid product, and analyzing the contents of each component in the liquid product by gas chromatography. The conversion rate of maleic anhydride and the selectivity of succinic anhydride are calculated by the following formula, and the specific results are shown in Table 1.

Wherein, the selectivity of described maleic anhydride conversion rate and described succinic anhydride is calculated by following formula:

Maleic anhydride conversion=(Mo-Ma)/Mo×100%

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

Wherein, Mo—the amount of substance of raw material maleic anhydride, mol;

Ma—the amount of the remaining material of maleic anhydride after the reaction, mol;

Mi—the amount of succinic anhydride generated after the reaction, mol.

Example 2-9

Proceed according to the method of Example 1, except that the hydrogenation catalysts prepared in Preparation Examples 2-9 were used instead of the hydrogenation catalysts prepared in Preparation Example 1 above, and the others were the same as in Example 1. The conversion rate of maleic anhydride and the selectivity of succinic anhydride are shown in Table 1 for specific results.

Comparative example 1-3

Proceed according to the method of Example 1, except that the hydrogenation catalysts prepared in Comparative Preparation Examples 1-3 were used instead of the hydrogenation catalysts prepared in the above Preparation Example 1, and the others were the same as in Example 1. The conversion rate of maleic anhydride and the selectivity of succinic anhydride are shown in Table 1 for specific results.

Table 1

Conversion rate of maleic anhydride (%) 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

As can be seen from Table 1, when the hydrogenation catalyst containing Ni-Sn-Si-Ca/Ba element of the present invention is applied to the liquid-phase catalytic hydrogenation of maleic anhydride to produce succinic anhydride, it has higher catalytic activity and the selection of succinic anhydride sex.

By the comparison of the data of Examples 1-3 and Examples 5 and 6, it can be seen that the effects of Examples 1-3 are better than Examples 5 and 6, so it can be seen that when the content of active components in the catalyst meets the preferred range, the catalytic activity of the prepared hydrogenation catalyst and the selectivity of succinic anhydride are better.

As can be seen from Example 1 and Comparative Example 1, Comparative Example 1 is due to not introducing the Sn element, under the same reaction conditions as 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%.

From Example 1 and Comparative Example 2, it can be seen that the comparative example does not introduce Ca or Ba elements, and under the same reaction conditions as the present invention, the selectivity of succinic anhydride is significantly reduced.

The preferred embodiments of the present invention have been described in detail above, however, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the disclosed content of the present invention. All belong to the protection scope of the present invention.

Claims (12)

1. A hydrogenation catalyst, characterized in that, the hydrogenation catalyst comprises a carrier and an active component loaded on the carrier, and the active component contains: Ni element, Sn element, Ca element and/or Ba element; The carrier contains SiO ₂ ; In the hydrogenation catalyst, based on the total weight of the hydrogenation catalyst, in terms of oxides, the content of Ni element is 10-40wt%, the content of Sn element is 5-15wt%, and the content of Ca element and/or Ba element 0.5-5wt%, and the carrier content is 20-80wt%. 2. The hydrogenation catalyst according to claim 1, wherein, in the hydrogenation catalyst, based on the total weight of the hydrogenation catalyst, in terms of oxides, the Ni element content is 17-28wt%, the Sn element The content is 7-12wt%, the Ca and/or Ba element content is 1-3wt%, and the carrier content is 40-75wt%. 3. a method for preparing hydrogenation catalyst, is characterized in that, described method is co-precipitation method, comprises the following steps: (1) The precursor compound containing Ni, the precursor compound of the carrier and the first solvent are first mixed to obtain the first mixed solution, and the precursor compound of the carrier contains SiO ₂ ; the solution of the precursor compound containing Sn is mixed with the The first mixed solution is mixed for the second time to obtain the second mixed solution; (2) carrying out the first contact reaction with the second mixed solution and the alkali solution to obtain a precipitate; (3) After the precipitate is filtered, washed, dried and pulverized, a powder matrix catalyst is obtained; (4) mixing and molding the powder matrix catalyst with the Ca-containing precursor compound and/or the Ba-containing precursor compound, and obtaining a hydrogenation catalyst after roasting; Wherein, in the hydrogenation catalyst, based on the total weight of the hydrogenation catalyst, the Ni element content is 10-40wt%, the Sn element content is 5-15wt%, and the Ca element and/or Ba The 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, in terms of oxides, the Ni element content is 17-28wt%, and the Sn element content is 7-12wt%, Ca and/or Ba element content is 1-3wt%, carrier content is 40-75wt%. 5. The method according to claim 3 or 4, wherein the Ni-containing precursor compound is a soluble nickel salt, preferably at least one of nickel nitrate, nickel sulfate, nickel chloride and nickel acetate; The Sn-containing precursor compound is a soluble tin salt, preferably potassium stannate and/or sodium stannate; The precursor compound of the carrier is selected from acidic silica sol and/or alkaline silica sol, preferably acidic silica sol; Preferably, the Ca-containing precursor compound is CaCO ₃ ; Preferably, the Ba-containing precursor compound is BaCO ₃ . 6. The method according to any one of claims 3-5, wherein in step (1), the conditions for the second mixing include: a temperature of 40-90° C., and a stirring time of 0.5-10 h. 7. The method according to any one of claims 3-6, wherein, in step (2), the pH value of the first contact reaction system is controlled to be 5-8; Preferably, the alkaline solution is at least one of ammonia water, ammonium carbonate solution and ammonium bicarbonate solution. 8. The method according to any one of claims 3-7, wherein, in step (2), the conditions of the first contact reaction include: the temperature is 40-90°C, and the reaction time is 0.5-10h; And/or, in step (3), the drying conditions include: the temperature is 100-120°C, and the time is 10-20h; And/or, in step (4), the calcination conditions include: the temperature is 300-600°C, preferably 450-550°C, and the time is 10-20h, preferably 2-6h. 9. The hydrogenation catalyst prepared by the method according to any one of claims 3-8. 10. the preparation method of the hydrogenation catalyst described in any one in claim 1,2 and 9 and/or the hydrogenation catalyst described in any one in claim 3-8 is in maleic anhydride liquid-phase hydrogenation and produces butanediol Application in acid anhydride reaction. 11. 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 carry out a second contact reaction to obtain the succinic anhydride; Wherein, the activated catalyst is the hydrogenation catalyst described in any one of claims 1, 2 and 9 and/or the hydrogenation catalyst obtained by the preparation method described in any one of claims 3-8 through the hydrogenation catalyst containing hydrogen The gas is reductively activated to obtain; The conditions for the reductive activation include: the temperature is 300-600°C, and the time is 0.5-20h. 12. The method according to claim 11, wherein the maleic anhydride exists 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: the molar ratio of the hydrogen to the maleic anhydride is 10-30:1, the temperature is 40-70°C, the time is 1-6h, and the pressure is 1-5MPa; And/or, the mass ratio of the activated catalyst to the maleic anhydride is 0.01-0.05:1.