CN111330580A

CN111330580A - Acid-resistant catalyst, preparation method thereof and application of acid-resistant catalyst in water-phase hydrogenation production of succinic acid

Info

Publication number: CN111330580A
Application number: CN202010161678.3A
Authority: CN
Inventors: 唐明兴; 李学宽; 周立公; 杨英
Original assignee: Shanxi Institute of Coal Chemistry of CAS
Current assignee: Shanxi Institute of Coal Chemistry of CAS
Priority date: 2020-03-10
Filing date: 2020-03-10
Publication date: 2020-06-26
Anticipated expiration: 2040-03-10
Also published as: CN111330580B

Abstract

The invention discloses a preparation method of an acid-resistant hydrogenation catalyst for producing succinic acid by hydrogenation of maleic acid aqueous solutionThe catalyst has the special physicochemical properties that the active components are highly dispersed on the carrier in the form of alloy or solid solution, the catalyst has hydrophilicity, the contact angle of the active components with water is less than 60 degrees, and the acid content of the catalyst is 0.01-2.0mmol NH₃The ratio of pore volume of the catalyst with the pore diameter of less than 1nm to the total pore volume is less than 50 percent, and the catalyst is prepared by adopting an impregnation method or a spraying method. The maleic acid hydrogenation process comprises the following steps: the reaction temperature is 20-300 ℃, the pressure is 1-10MPa, and the volume space velocity is 0.2-5h^‑1The hydrogen-oil volume ratio is 100-1000, the maleic acid is completely converted under the condition, and the succinic acid yield is not lower than 99.5 percent.

Description

Acid-resistant catalyst, preparation method thereof and application of acid-resistant catalyst in water-phase hydrogenation production of succinic acid

Technical Field

The invention discloses an acid-resistant catalyst and a preparation method thereof, and particularly relates to a preparation method of a succinic acid catalyst by aqueous phase hydrogenation. The invention also discloses the using process conditions of the catalyst.

Technical Field

In recent years, with the problem of environmental pollution caused by plastic wastes, the development of degradable bioplastics has become a hot point of research. Among them, polybutylene succinate (PBS) synthesized from succinic acid and 1, 4-butanediol is considered as one of the most excellent comprehensive properties among various biodegradable plastics. It is predicted that by 2020, the global PBS demand will reach 300 million tons per year and will also keep growing in two digits per year, the succinic acid demand for PBS production will reach 180 million tons and the 1, 4-butanediol demand will also reach 140 million tons.

The production method of the succinic acid mainly comprises the following steps: electrochemical reduction, biological fermentation and catalytic hydrogenation. The electrochemical reduction method takes maleic acid or anhydride thereof as raw material, and succinic acid is obtained by electrolytic reduction. In the 30 s of the 20 th century, the electrochemical reduction method has already realized the industrialized production, is the main technology of succinic acid production in China, but has the problems of large power consumption, serious electrode corrosion, large sewage discharge, being not beneficial to large-scale production and the like in the actual production. The biological fermentation method is a method for producing succinic acid by using bacteria or other microorganisms to ferment and taking starch, sugar or other wastes which can be utilized by the microorganisms as raw materials, and is considered to be the succinic acid production method with the most development potential. But the production efficiency is low, the production cost is high, a large amount of waste water is generated, and simultaneously, a large amount of starchiness grain raw materials are consumed, so that the national food supply and demand contradiction is increased. Therefore, the production of succinic acid by using grain raw materials is not a long-term measure, and the domestic application of succinic acid is only in the initial stage. The catalytic hydrogenation method has the advantages of high conversion rate, high product purity, no obvious side reaction and the like, and is the most widely applied succinic acid synthesis method in the industry at present.

Zhaoyuanxiang (CN103570650B, CN107597159A) of Shanxi university dissolves maleic anhydride with one or more mixed organic solvents of arene, alkane, alcohol, ketone and ether, and produces succinic anhydride and succinic acid as side product with supported Ni/Cu as catalyst. Adopts a one-section fixed bed and a two-section trickle bed process. The existing problems are: (1) the raw material is maleic anhydride, and the price is higher. Benzene oxidation is absorbed by water to obtain maleic acid aqueous solution, 70 percent of water is evaporated by rectification and dehydration reaction is carried out to obtain maleic anhydride, the process is complex, and the cost is high; (2) the use of organic solvents has problems such as high cost. Aromatic hydrocarbon solvents are strong carcinogens and pollute the environment. The product is easy to react with raw materials or products to generate byproducts, organic alcohol, ether and ester can generate esterification reaction with organic acid, and the solubility of alkane to dibasic acid is low; (3) one section adopts a fixed bed, and the temperature is difficult to control effectively. The fixed bed is an adiabatic reactor, and the reaction with higher concentration and larger reaction heat is difficult to effectively transfer heat no matter the fixed bed is in an upflow type or a downflow type; (4) the Ni/Cu catalyst has poor corrosion resistance, and serious loss in long-term operation, which causes the problems of catalyst inactivation, overproof Ni metal content in the product and the like.

Chilean Cecilia C.Torres et al studied the hydrogenation of maleic anhydride to succinic anhydride at 5 wt% Ni/TiO₂The catalyst is a high-pressure autoclave, the solvent is THF, the reaction temperature is 50-120 ℃, the reaction pressure is 4MPa, the catalyst has good activity and selectivity, the catalyst is repeatedly used for 5 times, and the performance of the catalyst is basically unchanged.

US patent 5952514 discloses a process for the direct liquid phase hydrogenation of maleic anhydride to succinic anhydride. The method adopts VIII metal element as active component of the catalyst, and the VIII metal element is mixed with IV group and V group elements or forms alloy to enhance the mechanical strength of the catalyst. However, the product is also subjected to vacuum rectification, so that the product has high chroma and high production energy consumption, and strong acid waste is discharged in the refining process of succinic anhydride, which causes adverse effects on the environment.

European patent EP0691335 discloses a process for the preparation of succinic anhydride by the one-step hydrogenation of maleic anhydride in the presence of a solvent. The catalyst used is noble metal Pd, the mass fraction of the noble metal is as high as 2-10%, and the cost of the catalyst is high. By adopting the catalyst, under the condition that the reaction pressure is 4-6MPa, the yield of the succinic anhydride is 90-95%, and the reaction pressure is higher.

US2245404(a) discloses a method of controlling the temperature rise of a catalyst bed by using an internal heat exchange tube to remove the heat of the maleic anhydride hydrogenation reaction. The method is suitable for removing the reaction heat of a small reaction device, and if the reaction device is enlarged, the heat removal pipe cannot uniformly remove the reaction heat and can influence the distribution of reaction liquid in the reactor, so that the reaction performance of the catalyst is reduced.

Liuna et al studied a one-pot method for aqueous-phase synthesis of succinic acid with maleic anhydride, and prepared a supported nano Pd/AC catalyst by a colloidal solution method, and maleic anhydride was subjected to two-step reaction of hydrolysis and hydrogenation to generate fumaric acid and malic acid as byproducts. The catalyst can be recycled for 10 times, and still can maintain higher activity and selectivity.

Patent CN101844976B uses one or more of maleic anhydride aqueous solution, fumaric acid aqueous solution or maleic acid aqueous solution as raw material, uses one or more of Fe, Co, Ni, Pd, Pt, Ru, Rh, Ir as active component, uses one or more of silica, zirconia, activated carbon, titania or silicon carbide as carrier to prepare catalyst, obtains succinic acid aqueous solution through hydrogenation reaction, and obtains succinic acid product after cooling crystallization, filtration and drying. The method adopts water as a solvent, and has the problem that active components are easy to run off when the catalyst is operated for a long time due to the corrosivity of the aqueous solution of maleic acid. Meanwhile, the technology is not reported in industrial application because metal ions corroded by equipment can be accumulated on the catalyst to cause rapid deactivation of the catalyst.

Patent CN102417445B uses an aqueous solution of maleate as a raw material, and obtains an aqueous solution of succinate by hydrogenation, and obtains succinic acid by acidifying and separating the obtained succinate. The method reduces the corrosion of the strong acid reaction solution to the catalyst. But the subsequent acidification step is added, and the reaction process step is complicated.

Patent CN106861702A discloses a catalyst for directly synthesizing succinic acid by maleic anhydride aqueous phase hydrogenation, and a preparation method and application thereof, wherein the catalyst takes maleic anhydride aqueous solution as a raw material, the concentration of the raw material is 8-30 wt%, and carbon-coated nickel-copper CuNi/Al is adopted₂O₃The catalyst utilizes the hydrophobic material property of carbon to prevent the scouring of active components and Al of acidic aqueous solution₂O₃Corrosion of the carrier. However, the method is very easy to cause the corrosion of active components and carriers due to incomplete carbon coating, so that the catalyst is quickly deactivated, the content of metal ions in the product exceeds the standard, and the purity of the product is influenced.

In summary, the prior art has disadvantages such as high catalyst cost, harsh reaction conditions, loss of catalyst components, high product price, severe pollution in the production process, and special requirements for the design and material of the reactor, which seriously hinders the large-scale synthesis and application of downstream PBS. Therefore, the development of a succinic acid production technology with low cost, low energy consumption, low pollution and simple flow has important significance for promoting the development of the plastic industry to green environmental protection.

Disclosure of Invention

The invention aims to provide an acid-resistant catalyst, a preparation method thereof and application thereof in producing succinic acid by aqueous phase hydrogenation.

The invention provides an acid-resistant hydrogenation catalyst, which consists of two parts of an active component and an acid-resistant carrier, wherein the active component consists of at least two of Ni, Cu, Co, Mo, W, Cr, Ru, Rh, Pd, Pt, Au, Ag, B, Al, Ga, P and Bi, and has good hydrogenation performance, the acid-resistant carrier is one of active carbon, α alumina, silicon oxide or silicon carbide, the mass percentage of the active component is 0.3-30 percent calculated by oxide, and the rest part is the carrierSolid solution, in order to improve the corrosion resistance of the catalyst. Meanwhile, the formed active phase has high hydrogenation activity, and the use amount of the catalyst can be effectively reduced. 2) The catalyst has good hydrophilicity, the contact angle between the catalyst and water is less than 60 degrees, the reaction is carried out in water, and the good hydrophilicity enables the catalyst and a reaction substrate to be well adsorbed, diffused and desorbed, so that the reactivity is improved. 3) The acid content of the catalyst is 0.01-2.0mmol NH₃The proper amount of acid is beneficial to improving the selectivity of the catalyst and avoiding generating byproducts. 4) The ratio of pore volume of the catalyst with the pore diameter of less than 1nm to the total pore volume is less than 50 percent, and the pore diameter of the catalyst is too small to be beneficial to the diffusion of reaction substrates and products. It is necessary to select a suitable carrier and to subject it to an appropriate pretreatment.

The catalyst is prepared by adopting an impregnation method or a spraying method, and the preparation method comprises the following specific steps:

1) carrying out hydrophilic pretreatment on the carrier;

2) preparing a mixed solution from the soluble precursor of the active component, heating to ensure that the temperature of the mixed solution is between 15 and 80 ℃, and adjusting the pH value to be between 0.5 and 7.0 by using a pH regulator;

3) loading the solution obtained in the step 2) on the carrier obtained in the step 1) in a dipping or spraying mode, controlling the dipping and spraying time to be between 2 and 24 hours, continuously stirring the solution during the dipping and spraying time to enable active components to be uniformly loaded on the carrier, and then curing the obtained sample at room temperature for 6 to 36 hours;

4) roasting the sample obtained in the step 3) in sections, raising the temperature to 150 ℃ at the heating rate of 10-20 ℃/h, and keeping the temperature constant for 2-12 h; then the temperature is raised to 900 ℃ at the heating rate of 10-20 ℃/h, and the temperature is kept constant for 2-12h, thus obtaining the required catalyst.

The hydrophilic pretreatment in the step 1) is oxidation treatment by ozone, nitric acid, hypochlorous acid (salt) and the like, or alkali washing by alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia water and the like, or surface treatment by a silane coupling agent and tetraethoxysilane.

And 2) the soluble precursor of the active component is nitrate, phosphate, acetate, sulfate, chloride, carbonate and ammonia complex. The pH regulator is one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, citric acid, ammonia water and ethylenediamine.

If the carrier is activated carbon, the step 4) is carried out in an inert atmosphere, wherein the inert atmosphere is nitrogen, helium, argon or water vapor, and the oxygen content in the inert atmosphere is strictly controlled to be below 0.01 percent by volume.

The invention also discloses the using conditions of the catalyst: the reaction temperature is 20-300 ℃, preferably 50-200 ℃; the pressure is 1-10MPa, preferably 2-5 MPa; the volume ratio of the hydrogen to the oil is 100-1000, preferably 200-500. The reaction mode may be a batch type or a continuous type, and a continuous type is preferred. The raw material is maleic acid aqueous solution obtained by benzene oxidation or butane oxidation, wherein the mass percentage of the maleic acid is 10-50 wt%.

Drawings

FIG. 1 example 12 catalyst contact angle with water is 50;

FIG. 2 TEM image of example 12 shows a transmission electron micrograph of the catalyst, wherein a is an HRTEM image and b is an EDS image.

Detailed Description

The invention is further illustrated, but not limited, by the following examples.

Example 1:

weighing 10g of activated carbon, soaking the activated carbon in nitric acid with the mass percentage of 15% for 24 hours, filtering out the activated carbon, washing the activated carbon with water until the pH value is 7.0, and drying the activated carbon for 24 hours at 150 ℃ for later use. 5.6g of nickel nitrate and 6.7g of copper nitrate are weighed, 12.5ml of water is added to prepare a mixed solution, the mixed solution is heated to 80 ℃, and the pH value is adjusted to 7.0 by using 10 mass percent of ammonia water. And pouring the treated activated carbon into the solution for equal volume impregnation, continuously stirring the solution to uniformly load the active components on the carrier, impregnating for 24 hours, curing the obtained sample at room temperature for 6 hours, and roasting the obtained sample in a nitrogen gas stage by stage, wherein the volume percentage of oxygen in the nitrogen gas is lower than 0.01 percent. Heating to 100 ℃ at a heating rate of 10 ℃/h, and keeping the temperature constant for 12 h; then the temperature is raised to 200 ℃ at the heating rate of 10 ℃/h, and the temperature is kept constant for 12h, thus obtaining the required catalyst (the composition and the property of the catalyst are detailed in Table 1). The obtained catalyst is evaluated in a fixed bed, the reaction temperature is 300 ℃, the pressure is 1MPa, and the volume space velocity is 0.2h^-1The volume ratio of hydrogen to oil is 100. The maleic acid content of the used raw materials was 20% by mass, and the obtained results are shown in table 1.

Example 2:

weighing 10g of α -alumina, treating the alumina with 20 volume percent of ozone for 24 hours, filtering out α -alumina, washing the alumina with water until the pH value is 7.0, drying the alumina for 24 hours at 150 ℃ for later use, weighing 2.5g of cobalt acetate and 0.8g of phosphoric acid, adding 20ml of water to prepare a mixed solution, heating the mixed solution to 80 ℃, adjusting the pH value to 7.0 by using a 5 mass percent ethylenediamine aqueous solution, pouring the treated carrier into the solution for supersaturation and impregnation, continuously stirring the mixed solution to uniformly load active components on the carrier, impregnating for 2 hours, curing the obtained sample at room temperature for 36 hours, roasting the obtained sample in air in sections, increasing the temperature to 150 ℃ at a rate of 20 ℃/h, keeping the temperature constant for 2 hours, increasing the temperature to 900 ℃ at a rate of 20 ℃/h, keeping the temperature constant for 2 hours, and obtaining the required catalyst (the composition and the property of the catalyst are detailed in Table 1)^-1The volume ratio of hydrogen to oil was 300. The maleic acid content of the used raw materials was 30% by mass, and the obtained results are shown in table 1.

Example 3:

weighing 10g of silicon carbide, soaking the silicon carbide in 30 mass percent hypochlorous acid for 5 hours, filtering and washing the silicon carbide until the pH value is 6.5, and drying the silicon carbide at 120 ℃ for 12 hours for later use. Weighing 2.4g of ammonium heptamolybdate, 0.0458g of chloroplatinic acid, 3.7g of sodium borate and 0.35g of bismuth trichloride, adding 20ml of water to prepare a mixed solution, and adjusting the pH to 5.0 by using 20 mass percent hydrochloric acid at the temperature of 15 ℃. And pouring the treated silicon carbide into the solution for supersaturated impregnation, continuously stirring during the supersaturated impregnation to enable active components to be uniformly loaded on a carrier, impregnating for 12 hours, then curing the obtained sample at room temperature for 18 hours, and roasting the obtained sample in a nitrogen gas sectional manner, wherein the volume percentage of oxygen in the nitrogen gas is lower than 0.01%. Heating to 120 ℃ at a heating rate of 15 ℃/h, and keeping the temperature constant for 10 h; then the temperature is raised to 500 ℃ at the heating rate of 15 ℃/h and is kept constant for 9h, thus obtaining the required catalyst (the composition and the property of the catalyst are detailed in table 1). The obtained catalyst is evaluated in a fixed bed, the reaction temperature is 150 ℃, the pressure is 2.5MPa, and the volume space velocity is 1.2h^-1The volume ratio of hydrogen to oil was 500. The maleic acid content of the raw materials used was 15% by mass, and the results are shown in table 1.

Example 4:

weighing 10g of silicon dioxide, soaking the silicon dioxide in 3 mass percent of sodium carbonate for 5 hours, filtering the silicon dioxide, washing the silicon dioxide with water until the pH value is 7.0, and drying the silicon dioxide for 24 hours at 100 ℃ for later use. 0.0146g of palladium chloride, 0.95g of ammonium metatungstate and 0.53g of gallium sulfate are weighed, 3ml of water is added to prepare a mixed solution, the mixed solution is heated to 60 ℃, and the pH value is adjusted to 4.0 by using 10 mass percent of acetic acid. And spraying the obtained solution on silicon dioxide, continuously stirring the solution during the spraying process to enable the active components to be uniformly loaded on the carrier, curing the obtained sample for 8 hours at room temperature after the spraying process is carried out for 2 hours, and roasting the obtained sample in air in a segmented manner. Heating to 110 ℃ at the heating rate of 12 ℃/h, and keeping the temperature constant for 3 h; then the temperature is raised to 300 ℃ at the heating rate of 12 ℃/h and is kept constant for 3h, thus obtaining the required catalyst (the composition and the property of the catalyst are detailed in table 1). The obtained catalyst is evaluated in a fixed bed, the reaction temperature is 120 ℃, the pressure is 3MPa, and the volume space velocity is 0.6h^-1The volume ratio of hydrogen to oil was 400. The maleic acid content of the used raw materials was 25% by mass, and the obtained results are shown in table 1.

Example 5:

weighing 10g of silicon carbide, soaking the silicon carbide in a silane coupling agent with the mass percentage of 15% and the model of KH550 for 6 hours, and drying the silicon carbide for later use at 130 ℃ for 24 hours. 10g of nickel nitrate and 0.8g of chromium nitrate are weighed, 8ml of water is added to prepare a mixed solution, the mixed solution is heated to 50 ℃, and the pH value is adjusted to 4.0 by using mixed alkali (the mass percentage of ammonia water is 2 percent, and the mass percentage of ethylenediamine is 8 percent). And pouring the treated silicon carbide into the solution to be supersaturated and impregnated, continuously stirring the solution during the supersaturated and impregnated process to enable active components to be uniformly loaded on a carrier, after the impregnation process is carried out for 4 hours, then curing the obtained sample at room temperature for 10 hours, and roasting the obtained sample in a segmented manner under nitrogen, wherein the volume percentage of oxygen in the nitrogen is lower than 0.01%. Heating to 180 ℃ at a heating rate of 14 ℃/h, and keeping the temperature constant for 8 h; then the temperature is raised to 250 ℃ at the heating rate of 14 ℃/h and is kept constant for 15h, thus obtaining the required catalyst (the composition and the property of the catalyst are detailed in Table 1). The obtained catalyst is evaluated in a fixed bed, the reaction temperature is 100 ℃, the pressure is 8MPa, and the volume space velocity is 0.8h^-1The volume ratio of hydrogen to oil was 600. The maleic acid content of the raw materials was 10% by mass, and the results are shown in table 1.

Example 6:

weighing 10g of α -alumina, soaking the alumina in 15 percent nitric acid for 24 hours, filtering out α -alumina, washing the alumina with water until the pH value is 7.0, drying the alumina for 24 hours at 150 ℃ for later use, weighing 0.0458g of chloroplatinic acid and 0.0145g of palladium chloride, adding 20ml of water to prepare a mixed solution, heating the mixed solution to 50 ℃, adjusting the pH value to 5.0 by 10 percent potassium hydroxide, pouring the treated α -alumina into the solution to be supersaturated and impregnated, continuously stirring the mixed solution to uniformly load active components on a carrier, impregnating the carrier for 6 hours, curing the obtained sample for 8 hours at room temperature, sectionally roasting the obtained sample in air, increasing the temperature to 120 ℃ at a rate of 10 ℃/h, keeping the temperature constant for 12 hours, increasing the temperature to 600 ℃ at a rate of 10 ℃/h, keeping the temperature constant for 12 hours, and obtaining the required catalyst (the composition and the property of the catalyst are detailed in table 1)^-1The volume ratio of hydrogen to oil was 700. The maleic acid content of the used raw materials was 20% by mass, and the obtained results are shown in table 1.

Example 7:

weighing 10g of silicon carbide, soaking the silicon carbide in 15 mass percent ethyl orthosilicate ethanol solution for 21 hours, filtering out the silicon carbide, and drying the silicon carbide at the temperature of 140 ℃ for 20 hours for later use. 0.115g of chloroplatinic acid and 0.031g of ruthenium trichloride are weighed, 10ml of water is added to prepare a mixed solution, the mixed solution is heated to 70 ℃, and the pH value is adjusted to 0.5 by using 10 mass percent of citric acid. Pouring the treated silicon carbide into the solution for equal volume impregnation, continuously stirring the solution during the impregnation to uniformly load the active components on the carrier, impregnating for 20 hours, then curing the obtained sample at room temperature for 10 hours, and roasting the obtained sample in air in a segmented manner. Heating to 140 ℃ at the heating rate of 18 ℃/h, and keeping the temperature constant for 7 h; then the temperature is raised to 350 ℃ at the heating rate of 13 ℃/h, and the temperature is kept constant for 21h, thus obtaining the required catalyst (the composition and the property of the catalyst are detailed in Table 1). The obtained catalyst is evaluated in a fixed bed, the reaction temperature is 80 ℃, the pressure is 2MPa, and the volume space velocity is 1.5h^-1The volume ratio of hydrogen to oil was 650. Use ofThe mass percentage of maleic acid in the raw material was 15%, and the obtained results are shown in table 1.

Example 8:

weighing 10g of silicon dioxide, soaking the silicon dioxide in nitric acid with the mass percentage of 15% for 24 hours, then filtering out the silicon dioxide, washing the silicon dioxide with water until the pH value is 7.0, and drying the silicon dioxide for 24 hours at 150 ℃ for later use. Weighing 2.05g of nickel nitrate and 0.035g of rhodium trichloride, adding 15ml of water to prepare a mixed solution, heating to 66 ℃, and adjusting the pH to 1.0 by using 10 mass percent of acetic acid. And pouring the treated silicon dioxide into the solution to be supersaturated and impregnated, continuously stirring the solution during the supersaturated and impregnated step to enable active components to be uniformly loaded on a carrier, after the carrier is impregnated for 8 hours, curing the obtained sample at room temperature for 9 hours, and roasting the obtained sample in a segmented manner under nitrogen, wherein the volume percentage of oxygen in the nitrogen is lower than 0.01 percent. Heating to 120 ℃ at a heating rate of 10 ℃/h, and keeping the temperature constant for 12 h; then the temperature is raised to 280 ℃ at the heating rate of 10 ℃/h and is kept constant for 12h, thus obtaining the required catalyst (the composition and the property of the catalyst are detailed in table 1). The obtained catalyst is evaluated in a fixed bed, the reaction temperature is 85 ℃, the pressure is 2.5MPa, and the volume space velocity is 5h^-1The volume ratio of hydrogen to oil is 1000. The maleic acid content of the used raw materials was 20% by mass, and the obtained results are shown in table 1.

Example 9:

weighing 10g of activated carbon, soaking the activated carbon in potassium carbonate with the mass percentage of 15% for 10 hours, filtering the activated carbon, washing the activated carbon with water until the pH value is 6.0, and drying the activated carbon for 12 hours at 150 ℃ for later use. 0.48g of copper nitrate and 0.039g of chloroauric acid are weighed, 12ml of water is added to prepare a mixed solution, the mixed solution is heated to 40 ℃, and the pH value is adjusted to 3.0 by using 10 mass percent of citric acid. And pouring the treated activated carbon into the solution to be supersaturated and impregnated, continuously stirring the solution during the supersaturated and impregnated period to enable active components to be uniformly loaded on a carrier, after the carrier is impregnated for 11 hours, curing the obtained sample at room temperature for 13 hours, and roasting the obtained sample in a nitrogen gas sectional mode, wherein the volume percentage of oxygen in the nitrogen gas is lower than 0.01%. Heating to 140 ℃ at a heating rate of 10 ℃/h, and keeping the temperature constant for 12 h; then the temperature is raised to 700 ℃ at the heating rate of 10 ℃/h and is kept constant for 6h, thus obtaining the required catalyst (the composition and the property of the catalyst are detailed in table 1). The obtained catalyst is evaluated in a fixed bed, the reaction temperature is 110 ℃, the pressure is 3.2MPa, and the volume space velocity is 3.4h^-1The volume ratio of hydrogen to oil was 800. The maleic acid content of the used raw materials was 25% by mass, and the obtained results are shown in table 1.

Example 10:

weighing 10g of activated carbon, soaking the activated carbon in nitric acid with the mass percentage of 15% for 24 hours, filtering out the activated carbon, washing the activated carbon with water until the pH value is 7.0, and drying the activated carbon for 24 hours at 150 ℃ for later use. 0.0459g of chloroplatinic acid, 0.0146g of palladium chloride and 0.044g of silver nitrate are weighed, 20ml of water is added to prepare a mixed solution, the mixed solution is heated to 60 ℃, and the pH is adjusted to 1.5 by using mixed acid (the mass percent of citric acid is 10 percent, and the mass percent of sulfuric acid is 1 percent). And pouring the treated activated carbon into the solution for equal volume impregnation, continuously stirring the solution during the impregnation to uniformly load the active components on the carrier, impregnating for 22 hours, then curing the obtained sample at room temperature for 8 hours, and roasting the obtained sample in a nitrogen gas sectional manner, wherein the volume percentage of oxygen in the nitrogen gas is lower than 0.01%. Heating to 100 ℃ at a heating rate of 10 ℃/h, and keeping the temperature constant for 12 h; then the temperature is raised to 200 ℃ at the heating rate of 10 ℃/h, and the temperature is kept constant for 12h, thus obtaining the required catalyst (the composition and the property of the catalyst are detailed in Table 1). The obtained catalyst is evaluated in a fixed bed, the reaction temperature is 20 ℃, the pressure is 10MPa, and the volume space velocity is 1.4h^-1The volume ratio of hydrogen to oil was 600. The maleic acid content of the used raw materials was 23% by mass, and the obtained results are shown in table 1.

Example 11:

weighing 10g of activated carbon, soaking the activated carbon in ammonia water with the mass percentage of 15% for 24 hours, then filtering out the activated carbon, washing the activated carbon with water until the pH value is 8.0, and drying the activated carbon for 24 hours at 150 ℃ for later use. 1.27g of copper nitrate, 0.034g of ruthenium trichloride and 1.59g of aluminum nitrate were weighed, 14ml of water was added to prepare a mixed solution, the mixed solution was heated to 30 ℃, and the pH was adjusted to 3.0 with 10% by mass of hydrochloric acid. And pouring the treated activated carbon into the solution to be supersaturated and impregnated, continuously stirring the solution during the supersaturated and impregnated period to enable active components to be uniformly loaded on a carrier, impregnating for 20 hours, then curing the obtained sample at room temperature for 9 hours, and roasting the obtained sample in a nitrogen gas sectional mode, wherein the volume percentage of oxygen in the nitrogen gas is lower than 0.01%. Heating to 100 ℃ at a heating rate of 10 ℃/h, and keeping the temperature constant for 12 h; then the temperature is raised to 800 ℃ at the heating rate of 10 ℃/h and is kept constant for 12h, thus obtaining the required catalyst (the composition and the property of the catalyst are detailed in table 1). Will be provided withThe obtained catalyst is evaluated in a fixed bed, the reaction temperature is 100 ℃, the pressure is 1.3MPa, and the volume space velocity is 4.1h^-1The volume ratio of hydrogen to oil was 200. The maleic acid content of the used raw materials was 20% by mass, and the obtained results are shown in table 1.

Example 12:

weighing 10g of activated carbon, soaking the activated carbon in nitric acid with the mass percentage of 15% for 24 hours, filtering out the activated carbon, washing the activated carbon with water until the pH value is 7.0, and drying the activated carbon for 24 hours at 150 ℃ for later use. 0.49g of ruthenium trichloride, 0.46g of aluminum nitrate, 0.1g of chromium nitrate and 0.03g of ferric nitrate are weighed, 10ml of water is added to prepare a mixed solution, the mixed solution is heated to 50 ℃, and the pH value is adjusted to 4.0 by using sulfuric acid with the mass percentage content of 10%. And pouring the treated activated carbon into the solution for equal volume impregnation, continuously stirring the solution to uniformly load the active components on the carrier, impregnating for 24 hours, curing the obtained sample at room temperature for 7 hours, and roasting the obtained sample in a nitrogen gas sectional mode, wherein the volume percentage of oxygen in the nitrogen gas is lower than 0.01%. Heating to 100 ℃ at a heating rate of 10 ℃/h, and keeping the temperature constant for 12 h; and then the temperature is raised to 200 ℃ at the heating rate of 10 ℃/h and is kept constant for 12h, thus obtaining the required catalyst (the composition and the property of the catalyst are detailed in table 1, the photo of the contact angle between the catalyst and water is shown in figure 1, and the photo of a transmission electron microscope is shown in figure 2). According to the characterization, the catalyst has better hydrophilicity, and the active components are highly dispersed on the carrier. The obtained catalyst is evaluated in a fixed bed, the reaction temperature is 30 ℃, the pressure is 1.6MPa, and the volume space velocity is 4.8h^-1The volume ratio of hydrogen to oil was 300. The maleic acid content of the used raw material was 18% by mass, and the obtained results are shown in table 1.

Comparative example 1

Comparative example 1 the catalyst was prepared in the same manner as in example 2 except that the carrier was not pretreated, and the composition and physical and chemical properties of the catalyst were as shown in table 1. The reaction conditions were also the same as in example 2, since the carrier was not pretreated, the contact angle of the catalyst of comparative example 1 was 34o, and the acid amount was 2.6mmol NH₃The pore volume fraction of less than 1nm was 11%, the conversion of starting materials and the product selectivity were lower than in example 2.

Comparative example 2

Comparative example 2 catalyst except that the support was not pretreatedThe other preparation steps are the same as those of example 8, and the catalyst composition and the physicochemical properties are shown in Table 1. The reaction conditions were also the same as in example 8, since the carrier was not pretreated, the contact angle of the catalyst of comparative example 2 was 42o, and the acid amount was 2.2mmol NH₃The pore volume fraction below 1nm was 47%, the conversion of starting materials and the product selectivity were lower than in example 8.

Comparative example 3

Comparative example 3 the catalyst was prepared in the same manner as in example 12 except that the carrier was not pretreated, and the composition and physical and chemical properties of the catalyst were as shown in table 1. The reaction conditions were also the same as in example 12, since the carrier was not pretreated, the contact angle of the catalyst of comparative example 3 was 90 degrees, and the acid amount was 0.4mmol NH₃The pore volume fraction of less than 1nm was 52%, the conversion of starting materials and the product selectivity were lower than in example 12.

TABLE 1 catalyst composition, physicochemical Properties, reaction conditions, and evaluation results

Claims

1. The acid-resistant hydrogenation catalyst consists of two parts, namely an active component and an acid-resistant carrier, wherein the active component consists of at least two of Ni, Cu, Co, Mo, W, Cr, Ru, Rh, Pd, Pt, Au, Ag, B, Al, Ga, P and Bi, and the acid-resistant carrier is one of active carbon, α alumina, silicon oxide or silicon carbide, and is characterized in that the catalyst simultaneously has the following technical characteristics:

the active component is uniformly dispersed on the carrier in the form of alloy or solid solution;

the catalyst has hydrophilicity, and the contact angle of the catalyst with water is less than 60 degrees;

the acid content of the catalyst is 0.01-2.0mmol NH₃/g；

The ratio of the pore volume of the catalyst with a pore diameter of less than 1nm to the total pore volume is less than 50%.

2. The catalyst according to claim 1, wherein the active component is 0.3-30% by mass of the oxide, and the balance is a carrier.

3. A preparation method of a catalyst for producing succinic acid by aqueous phase hydrogenation is characterized in that the catalyst is prepared by adopting an impregnation method or a spraying method, and the preparation method specifically comprises the following steps:

1) carrying out hydrophilic pretreatment on the carrier;

4. The method for preparing the catalyst according to claim 3, wherein the hydrophilic pretreatment in step 1) is an oxidation treatment with ozone, nitric acid, hypochlorous acid (salt), or the like, or an alkali washing with an alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, or ammonia water, or a surface treatment with a silane coupling agent or ethyl orthosilicate.

5. The method for preparing the catalyst according to any one of claims 3 to 4, wherein the active component soluble precursor in the step 2) is nitrate, phosphate, acetate, sulfate, chloride, carbonate and ammonia complex.

6. The method for preparing the catalyst according to any one of claims 3 to 5, wherein the pH regulator in step 2) is one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, citric acid, ammonia water and ethylenediamine.

7. The method for preparing a catalyst according to any one of claims 3 to 6, wherein if the support is activated carbon, the step 4) is performed under an inert atmosphere in which the oxygen content by volume is controlled to be less than 0.01%.

8. Use of a catalyst according to any one of claims 1-2 or a catalyst prepared by a process according to any one of claims 3-7 in the aqueous hydrogenation of succinic acid, wherein the catalyst is used under the following conditions: the reaction temperature is 20-300 ℃, preferably 50-200 ℃; the pressure is 1-10MPa, preferably 2-5 MPa; the volume space velocity is 0.2-5h^-1Preferably 0.5-2h^-1(ii) a The volume ratio of the hydrogen to the oil is 100-1000, preferably 200-500.

9. Use according to claim 8, wherein the reaction is carried out batchwise or continuously, preferably continuously.