Slurry bed maleic anhydride hydrogenation supported nickel-based catalyst as well as preparation method and application thereof

Abstract

The invention provides a slurry reactor maleic anhydride hydrogenation supported nickel-based catalyst and a preparation method and application thereof.In the catalyst, the content of nickel is 0.2-2 wt%, the content of a coupling agent is 0.1-10 wt%, the content of copper is 0.01-1 wt%, the content of a carrier is 90-99.8 wt%, the particle size of the catalyst is 80-150 [mu] m, the coupling agent can promote the catalyst to form a skeleton structure, and the coupling agent can promote the catalyst to form a non-skeleton structure. Therefore, interaction of metal is improved, and loss is reduced. The catalyst provided by the invention can perform selective hydrogenation reaction under a liquid-phase pressurization condition, and compared with gas-phase hydrogenation, the process condition is more beneficial to industrial production; meanwhile, the catalyst provided by the invention can realize selective hydrogenation of maleic anhydride C = C double bonds, the selectivity of hydrogenolysis byproducts of C = O hydrogenation groups is low, and the selectivity of the target product succinic anhydride is remarkably improved.

Description

Technical Field

[0001] The present invention belongs to the chemical engineering field, and relates to a catalyst for preparing succinic anhydride by maleic anhydride hydrogenation, specifically to a supported nickel-based catalyst for maleic anhydride hydrogenation in a slurry bed, and its preparation method and application. Background Art

[0002] Succinic anhydride, also known as amber anhydride, abbreviated as SA, is an important chemical intermediate, which is widely used in food additives as a flavoring agent for soy sauce, sake, beverages, etc., and also used as raw materials for pharmaceuticals, pesticides, dyes, etc. Succinic anhydride and its hydrolyzed product succinic acid can be polycondensed with butanediol to prepare polybutylene succinate (PBS), a biodegradable plastic with excellent properties. The PBS structural unit contains easily hydrolyzable ester groups, which can be easily decomposed and metabolized by various microorganisms in nature or enzymes in animals and plants under conditions such as composting and contacting specific microorganisms, and finally form CO2 and H2O, thus avoiding environmental pollution.

[0003] With the gradual improvement of people's environmental awareness, PBS biodegradable plastic products with excellent performance and rich raw material sources are favored by people. The production of succinic anhydride by direct hydrogenation of maleic anhydride is considered to be the best process route to meet the future demand for key monomers of degradable plastics, and has broad market prospects. However, at present, the high-energy-consuming electrolysis method of maleic anhydride is used to produce succinic acid (anhydride), with complex process, low production capacity and high production cost.

[0004] Since maleic anhydride and succinic anhydride have relatively high melting points and are solids at room temperature, in order to avoid clogging of the reactor pipeline, most of the currently developed processes for catalytic hydrogenation of maleic anhydride to produce succinic anhydride use the liquid-phase solvent method, that is: maleic anhydride is dissolved in an organic solvent, and then hydrogenation-separation is carried out to obtain succinic anhydride.

[0005] Chinese Patent CN1453066A uses a nickel-based catalyst and directly hydrogenates with THF, toluene and 1,4-dioxane as solvents to produce succinic anhydride. This patent uses a nickel-based catalyst and can achieve a maleic anhydride conversion rate greater than 99.7% and a succinic anhydride selectivity greater than 99%. However, the selection of solvents such as THF, toluene and 1,4-dioxane greatly increases the production cost.

[0006] Chinese Patent CN102311332A uses γ-butyrolactone as a solvent and 5wt% Pd-2wt% Fe / C as a catalyst. Under the conditions of 70°C and 1.5 MPa hydrogen pressure, continuous reaction is carried out in a fixed-bed reactor for 300 h. The maleic anhydride conversion rate is 100% and the succinic anhydride selectivity is 99.2%. This patent uses an Fe / C catalyst to achieve efficient conversion of maleic anhydride, but still uses γ-butyrolactone as a solvent, with a relatively low reaction temperature, difficult control of reaction heat dissipation, and high cost of the noble metal catalyst used.

[0007] Chinese patents CN105597742A and CN105801536A respectively provide a catalyst for the liquid-phase hydrogenation of maleic anhydride to succinic anhydride and a method for the two-stage low-temperature and low-pressure liquid-phase hydrogenation of maleic anhydride to prepare succinic anhydride. In this patent, two hydrogenation reactors are used in series. Maleic anhydride, solvent and hydrogen are fed into the first-stage reactor for partial hydrogenation at 40°C and 0.2 - 2.0 MPa, and then enter the second-stage reactor for complete hydrogenation at 60 - 120°C and 0.2 - 2.0 MPa. Both stages of the reaction use a supported Pd catalyst, and the solvents used are dimethyl succinate, diethyl succinate, ethyl acetate, butyl acetate, γ-butyrolactone. This patent uses a Pd catalyst that can selectively hydrogenate the double bond of maleic anhydride, but a large amount of dimethyl succinate, diethyl succinate, ethyl acetate, butyl acetate, γ-lactone, etc. are used as solvents, resulting in a high cost.

[0008] Chinese patent CN101735182A provides a process for the continuous production of succinic anhydride by the hydrogenation of maleic anhydride. A supported nickel catalyst is used, the concentration of the maleic anhydride solution is 0.04 - 0.08 g / mL, and the solvent is any one of tetrahydrofuran, acetone, 1,4-dioxane, benzene, toluene, γ-butyrolactone, propyl ether, isopropyl ether, butyl ether, isobutyl ether, ethyl acetate, isopropyl acetate, isopentyl acetate, diethyl succinate, dimethyl succinate, etc. The yield of succinic anhydride is higher than 97.5%. This patent uses a nickel-based catalyst that can effectively improve the conversion rate of maleic anhydride and the selectivity of succinic anhydride, but it does not solve the problem of high cost brought about by the use of solvents.

[0009] Chinese patent CN113332999A discloses a catalyst for the hydrogenation of maleic anhydride to prepare succinic anhydride. The catalyst contains a carrier and a metal component supported on the carrier. The metal component includes a first active center component, a second active center component, a first promoter and a second promoter. The first active center component is one or any combination of Pd, Ru, Pt or Au, the second active center component is one or any combination of Cu, Ni, Co and Cr, the first promoter is one or any combination of Zn, Mo, W, Fe, and the second promoter is one or two of La or Ce; the carrier is one or any combination of activated carbon, aluminum trioxide, silicon dioxide, titanium dioxide or silica molecular sieve. However, the catalyst of this patent requires the use of a variety of precious metal promoters, and the cost is extremely high in actual use; on the other hand, when the reaction temperature rises (for example, when the reaction temperature is above 200°C), the selectivity of the catalyst of this patent for succinic anhydride decreases significantly, and it cannot specifically improve the selectivity of succinic anhydride. Instead, the selectivity of 1,4-butanediol increases. In actual industrial applications, it is impossible to effectively control the temperature rise caused by the reaction heat release, which further reduces the selectivity of succinic anhydride and increases the production cost.

[0010] In summary, in the prior art, there are generally problems of high catalyst cost, poor selectivity, and high production cost. For the problems existing in the above prior art, it is urgent to develop a corresponding key and efficient catalyst for the directional hydrogenation of maleic anhydride in slurry bed to produce succinic anhydride, further improve the selectivity of succinic anhydride, and reduce the production cost. Summary of the Invention

[0011] The purpose of the present invention is to solve the above technical problems and deficiencies, and provide a supported nickel-based catalyst for maleic anhydride hydrogenation in slurry bed, its preparation method and application.

[0012] In the first aspect, the present invention provides a supported nickel-based catalyst for maleic anhydride hydrogenation in slurry bed, wherein the content of nickel in the catalyst is 0.2-2 wt%, the content of coupling agent is 0.1-10 wt%, the content of copper is 0.01-1 wt%, and the content of carrier is 90-99.8 wt%.

[0013] Preferably, the content of nickel is 0.3-0.8 wt%; and / or the content of coupling agent is 1-5 wt%; and / or the content of copper is 0.1-0.5 wt%; and / or the content of carrier is 93.7-99.7 wt%.

[0014] Preferably, the coupling agent is an amino silane coupling agent and / or a mercapto silane coupling agent.

[0015] Preferably, the amino silane coupling agent is one or any combination of KH-550 (3-aminopropyltriethoxysilane), KH-540 (3-aminopropyltrimethoxysilane), KH-791 ((N-(2-aminoethyl)-3-aminopropyl) tris-(2-ethoxy) silane), KH-792 (N-β-aminoethyl-γ-aminopropyltrimethoxysilane), KH-902 (γ-aminopropylmethyldiethoxysilane).

[0016] Preferably, the mercapto silane coupling agent is one or any combination of KH-590 (3-mercaptopropyltrimethoxysilane), KH-580 (3-mercaptopropyltriethoxysilane), KH-970 (3-mercaptopropylmethyldimethoxysilane).

[0017] Preferably, the particle size of the carrier is 80-150 μm.

[0018] Preferably, the carrier is one or any combination of alumina, silica, titanium oxide, zinc oxide, magnesium oxide, activated carbon, and silica-alumina molecular sieve.

[0019] Preferably, the alumina is α-Al2O3 and / or γ-Al2O3.

[0020] Second aspect, the present invention provides a method for preparing the above-mentioned supported nickel-based catalyst, and the preparation method includes the following steps:

[0021] (1) Add the carrier into the coupling agent solution, mix evenly, transfer it into a closed container for impregnation treatment and then dry to obtain a catalyst precursor;

[0022] (2) Add the catalyst precursor obtained in step (1) into the mixed solution of a soluble nickel salt solution and a soluble copper salt solution, mix evenly, and obtain the supported nickel-based catalyst after impregnation, drying and reduction.

[0023] Preferably, in step (1), the mass ratio of the carrier to the coupling agent solution is (1-2):(1-3); the solvent of the coupling agent solution is ethanol or water; the concentration of the coupling agent solution is 1-10 wt%; the impregnation conditions: normal temperature, normal pressure, and the time is 12-24 h; the drying conditions: the temperature is 60-80 °C and the time is 8-24 h.

[0024] Preferably, in step (2), the mass ratio of the catalyst precursor to the mixed solution of the soluble nickel salt solution and the soluble copper salt solution is (1-3):(1-5); the mass ratio of the soluble nickel salt solution to the soluble copper salt solution is (2-5):1; the concentration of the soluble nickel salt solution is 0.2-1 moL / L; the concentration of the soluble copper salt solution is 0.01-1 mol / L.

[0025] Preferably, in step (2), the soluble nickel salt is one or any several of nickel nitrate, nickel chloride, nickel sulfate, nickel formate, nickel acetate, nickel oxalate, nickel citrate; the soluble copper salt is one or any several of copper nitrate, copper chloride, copper sulfate, basic copper carbonate, copper acetate.

[0026] Preferably, in step (2), the impregnation conditions: normal temperature, normal pressure, and the time is 12-24 h; the drying conditions: the temperature is 80-120 °C and the time is 8-24 h; the reduction conditions: reduction with pure H2, the temperature is 300-600 °C and the time is 3-12 h.

[0027] Third aspect, the present invention provides an application of the above-mentioned supported nickel-based catalyst, which is used for maleic anhydride hydrogenation in a slurry bed, and the specific application method includes the following steps:

[0028] Load the above catalyst into a slurry bed reactor, set the reaction temperature to 120 - 180 °C, the reaction pressure to 2 - 3 MPa, and the hydrogen gas flow rate to 600 - 1000 mL / min; after the hydrogenation reaction starts, input maleic anhydride into the slurry bed reactor at a flow rate of 0.04 - 1 mL / min. When the reaction is in operation, the maleic anhydride flow rate enters the reactor, and the reaction runs for 24 - 72 h to complete the liquid-phase hydrogenation of maleic anhydride.

[0029] The present invention has the following beneficial effects:

[0030] (1) The supported nickel-based catalyst developed in the present invention can achieve selective hydrogenation of the C = C double bond of maleic anhydride, improve the selectivity of succinic anhydride, and greatly reduce the selectivity of hydrogenolysis by-products of the C = O group hydrogenation. The selectivity of the target product succinic anhydride has been significantly improved.

[0031] (2) The supported nickel-based catalyst developed in the present invention is prepared by the homogeneous-impregnation method. The obtained supported nickel-based catalyst includes hydrogenation nickel, a carrier, a coupling agent, and a hydrogenation promoter copper. The coupling agent can form a coordination structure between nickel and copper, enabling the supported nickel-based catalyst to form a framework structure, which is beneficial to the formation of interactions between metals, avoiding metal loss, and significantly improving the activity and selectivity of the catalyst for catalytic hydrogenation.

[0032] (3) The supported nickel-based catalyst developed in the present invention has high activity and can carry out selective hydrogenation reactions under the conditions of slurry bed pressurization and liquid phase; due to the catalyst of the present invention being more suitable for slurry bed pressurization reactions, a solvent-free feeding method is adopted, and maleic anhydride is hydrogenated to produce succinic anhydride under the conditions of a temperature of 120 - 180 °C and liquid phase. Compared with fixed-bed gas-phase hydrogenation, the slurry bed has a greater output, is easier to remove the excess heat generated during the reaction, is beneficial to improving the selectivity of succinic anhydride, reducing the generation of by-products, and the process conditions are more conducive to industrial production. Specific embodiments

[0033] The following provides a detailed description of the specific embodiments of the present invention. The specific embodiments described herein are only used to illustrate and explain the present invention, but not to limit the present invention.

[0034] The following further illustrates the present invention through examples, but the present invention is not limited thereto.

[0035] In one embodiment, the present invention provides a supported nickel-based catalyst for slurry bed maleic anhydride hydrogenation. The content of nickel in the catalyst is 0.2 - 2 wt%, the content of the coupling agent is 0.1 - 10 wt%, the content of copper is 0.01 - 1 wt%, and the content of the carrier is 90 - 99.8 wt%.

[0036] In some preferred embodiments, the content of nickel is 0.3 - 0.8 wt%, preferably 0.4 - 0.7 wt%, more preferably 0.5 - 0.6 wt%; and / or the content of the coupling agent is 1 - 5 wt%, preferably 2 - 4 wt%, more preferably 2.5 - 3.5 wt%; and / or the content of copper is 0.1 - 0.5 wt%, preferably 0.2 - 0.4 wt%, more preferably 0.25 - 0.35 wt%; and / or the content of the carrier is 93.7 - 99.7 wt%, preferably 95.5 - 98.5 wt%, more preferably 96.5 - 97.5 wt%.

[0037] In some preferred embodiments, the coupling agent is an amino-silane coupling agent and / or a mercapto-silane coupling agent; the amino-silane coupling agent is one or any combination of KH-550, KH-540, KH-791, KH-792, KH-902, preferably KH-550; the mercapto-silane coupling agent is one or any combination of KH-590, KH-580, KH-970, preferably KH-580.

[0038] In some preferred embodiments, the particle size of the carrier is 80 - 150 μm, preferably 90 - 140 μm, more preferably 100 - 130 μm.

[0039] In some preferred embodiments, the carrier is alumina, silica, titanium oxide, zinc oxide, magnesium oxide, activated carbon, silica-aluminum; preferably alumina.

[0040] In some preferred embodiments, the alumina is α-Al2O3 and / or γ-Al2O3; preferably α-Al2O3.

[0041] In one embodiment, the present invention provides a method for preparing the above-mentioned supported nickel-based catalyst, and the preparation method includes the following steps:

[0042] (1) Add the carrier to the coupling agent solution, mix evenly, transfer it to a closed container for impregnation treatment and then dry to obtain a catalyst precursor;

[0043] (2) Add the catalyst precursor obtained in step (1) to the mixed solution of the soluble nickel salt solution and the soluble copper salt solution, mix evenly, and after impregnation, drying and reduction, obtain the supported nickel-based catalyst.

[0044] In some preferred embodiments, in step (1), the mass ratio of the carrier to the coupling agent solution is (1 - 2):(1 - 3), preferably (1 - 2):(1 - 2.5), more preferably 1:(1 - 2).

[0045] In some preferred embodiments, the solvent of the coupling agent solution in step (1) is ethanol or water, preferably ethanol; the concentration of the coupling agent solution is 1-10 wt%, preferably 1-8 wt%, more preferably 3-5 wt%.

[0046] In some preferred embodiments, the impregnation conditions in step (1) are: normal temperature and pressure, and the time is 12-24 h (preferably 14-20 h, more preferably 16-18 h); the drying conditions are: the temperature is 60-80 °C (preferably 65-75 °C, more preferably 68-72 °C), and the time is 8-24 h (preferably 10-20 h, more preferably 12-16 h).

[0047] In some preferred embodiments, the mass ratio of the catalyst precursor to the mixed solution of the soluble nickel salt solution and the soluble copper salt solution in step (2) is (1-3):(1-5), preferably (1-2):(1-4), more preferably 1:(1-1.5).

[0048] In some preferred embodiments, the mass ratio of the soluble nickel salt solution to the soluble copper salt solution in step (2) is (2-5):1, preferably (2.5-4.5):1, more preferably (3-4):1.

[0049] In some preferred embodiments, the concentration of the soluble nickel salt solution in step (2) is 0.2-1 moL / L, preferably 0.2-0.8 moL / L, more preferably 0.5-0.6 moL / L; the concentration of the soluble copper salt solution is 0.01-1 mol / L, preferably 0.1-0.8 mol / L, more preferably 0.2-0.5 mol / L.

[0050] In some preferred embodiments, in step (2), the soluble nickel salt is one or any several of nickel nitrate, nickel chloride, nickel sulfate, nickel formate, nickel acetate, nickel oxalate, nickel citrate, preferably one of nickel nitrate, nickel chloride, nickel sulfate, nickel acetate, more preferably nickel acetate; the soluble copper salt is one or any several of copper nitrate, copper chloride, copper sulfate, basic copper carbonate, copper acetate, preferably one of copper nitrate, copper chloride, copper acetate, more preferably copper acetate.

[0051] In some preferred embodiments, the impregnation conditions in step (2) are: normal temperature and normal pressure, and the time is 12 - 24 h (preferably 14 - 20 h, more preferably 16 - 18 h); the drying conditions are: the temperature is 80 - 120 °C (preferably 90 - 110 °C, more preferably 95 - 100 °C), and the time is 8 - 24 h (preferably 10 - 20 h, more preferably 12 - 16 h); the reduction conditions are: reduction with pure H2, the temperature is 300 - 600 °C (preferably 320 - 500 °C, more preferably 350 - 400 °C), and the time is 3 - 12 h (preferably 5 - 9 h, more preferably 6 - 8 h).

[0052] In one embodiment, the present invention provides an application of the above-mentioned supported nickel-based catalyst, which is used for maleic anhydride hydrogenation in a slurry bed. The specific application method includes the following steps:

[0053] Load the above catalyst into a slurry bed reactor, set the reaction temperature to 120 - 180 °C (preferably 130 - 160 °C, more preferably 140 - 150 °C), the reaction pressure to 2 - 3 MPa (preferably 2.5 - 3 MPa, more preferably 2.8 - 3 MPa), and the hydrogen gas flow rate to 600 - 1000 mL / min (preferably 800 - 1000 mL / min, more preferably 900 - 1000 mL / min); after the hydrogenation reaction starts, input maleic anhydride into the slurry bed reactor at a flow rate of 0.04 - 1 mL / min (preferably 0.04 - 0.08 mL / min, more preferably 0.05 - 0.06 mL / min). When the reaction is in operation, the maleic anhydride flow rate enters the reactor, and the reaction runs for 24 - 72 h (preferably 24 - 48 h, more preferably 24 - 36 h) to complete the liquid-phase hydrogenation of maleic anhydride.

[0054] Copper acetate, nickel acetate, maleic anhydride, etc. used in the following examples and comparative examples are all commercially available. For the experimental methods without specific conditions in the following examples and comparative examples, they are carried out according to conventional methods and conditions, or selected according to the product instructions.

[0055] In the following process, both the comparative examples and experimental examples are carried out in a high-pressure slurry bed reactor.

[0056] Comparative Example

[0057] A preparation method of a supported nickel-based catalyst for maleic anhydride hydrogenation in a slurry bed includes the following steps:

[0058] 100 g of alumina (α-Al2O3, particle size of 100 μm) was added to a mixed solution of 100 g of an aqueous nickel acetate solution with a concentration of 2 moL / L and 25 g of an aqueous copper acetate solution with a concentration of 1 moL / L. After mixing evenly, it was impregnated at normal temperature and pressure for 24 h, dried at 100 °C for 24 h, and reduced with pure H2 at 300 °C for 5 h to obtain a supported nickel-based catalyst with a nickel content of 15 wt%, a copper content of 2 wt%, and a carrier Al2O3 content of 83 wt%.

[0059] An application of the above catalyst in the hydrogenation of maleic anhydride to prepare succinic anhydride, and its application method includes the following steps:

[0060] 10 g of the above catalyst was loaded into a 1-L reactor, the reaction temperature was set at 120 °C, the reaction pressure was 3 MPa, and the hydrogen flow rate was 1000 mL / min; after the hydrogenation reaction started, maleic anhydride was input into the slurry bed reactor at a flow rate of 0.04 mL / min. After the reaction ran for 24 h, samples were taken from the gas-liquid separator for analysis; the reaction results are shown in Table 1.

[0061] Example 1

[0062] A preparation method of a supported nickel-based catalyst for slurry bed hydrogenation of maleic anhydride includes the following steps:

[0063] (1) 100 g of alumina (α-Al2O3, particle size of 100 μm) was added to 100 g of a KH-550 ethanol solution with a concentration of 5 wt%. After mixing evenly, it was transferred to a sealed container and impregnated at normal temperature and pressure for 24 h, and then dried at 80 °C for 24 h to obtain a catalyst precursor;

[0064] (2) The catalyst precursor obtained in step (1) was added to a mixed solution of 100 g of an aqueous nickel acetate solution with a concentration of 0.2 moL / L and 25 g of an aqueous copper acetate solution with a concentration of 0.1 moL / L. After mixing evenly, it was impregnated at normal temperature and pressure for 24 h, dried at 100 °C for 24 h, and reduced with pure H2 at 300 °C for 5 h to obtain a supported nickel-based catalyst with a nickel content of 0.3 wt%, a copper content of 0.2 wt%, a carrier Al2O3 content of 94.5 wt%, and a KH550 content of 5 wt%.

[0065] An application of the above catalyst in the hydrogenation of maleic anhydride to prepare succinic anhydride, and its application method includes the following steps:

[0066] Load the above 10 g of catalyst into a reactor with a volume of 1 L, set the reaction temperature at 120 °C, the reaction pressure at 3 MPa, and the hydrogen flow rate at 1000 mL / min; after the hydrogenation reaction starts, input maleic anhydride into the slurry bed reactor at a flow rate of 0.04 mL / min. After the reaction runs for 24 h, take samples from the gas-liquid separator for analysis; the reaction results are shown in Table 1.

[0067] Example 2

[0068] A preparation method of a supported nickel-based catalyst for maleic anhydride hydrogenation in a slurry bed, comprising the following steps:

[0069] (1) Add 100 g of alumina (α-Al2O3, particle size of 100 μm) to 100 g of a 7 wt% KH-550 ethanol solution. After mixing evenly, transfer it to a closed container and carry out impregnation treatment at normal temperature and pressure for 24 h, then dry at 80 °C for 24 h to obtain a catalyst precursor;

[0070] (2) Add the catalyst precursor obtained in step (1) to a mixed solution of 100 g of a 0.5 moL / L nickel acetate aqueous solution and 25 g of a 0.1 moL / L copper acetate aqueous solution, mix evenly, carry out impregnation treatment at normal temperature and pressure for 24 h, dry at 100 °C for 24 h, and reduce it with pure H2 at 300 °C for 5 h to obtain a supported nickel-based catalyst with a nickel content of 0.8 wt%, a copper content of 0.2 wt%, a carrier Al2O3 content of 92.0 wt%, and a KH550 content of 7 wt%.

[0071] An application of the above catalyst in the preparation of succinic anhydride by maleic anhydride hydrogenation, and its application method comprises the following steps:

[0072] Load the above 10 g of catalyst into a reactor with a volume of 1 L, set the reaction temperature at 130 °C, the reaction pressure at 2.8 MPa, and the hydrogen flow rate at 1000 mL / min; after the hydrogenation reaction starts, input maleic anhydride into the slurry bed reactor at a flow rate of 0.04 mL / min. After the reaction runs for 24 h, take samples from the gas-liquid separator for analysis; the reaction results are shown in Table 1.

[0073] Example 3

[0074] A preparation method of a supported nickel-based catalyst for maleic anhydride hydrogenation in a slurry bed, comprising the following steps:

[0075] (1) Add 100 g of alumina (α-Al2O3, particle size of 100 μm) to 100 g of a 3 wt% KH-550 ethanol solution. After mixing evenly, transfer it to a closed container and carry out impregnation treatment at normal temperature and pressure for 24 h, then dry at 80 °C for 24 h to obtain a catalyst precursor;

[0076] (2) Add the catalyst precursor obtained in step (1) to a mixed solution of 100 g of an aqueous nickel acetate solution with a concentration of 0.8 moL / L and 25 g of an aqueous copper acetate solution with a concentration of 0.1 moL / L, mix well, impregnate at normal temperature and pressure for 24 h, dry at 100 °C for 24 h, and reduce with pure H2 at 300 °C for 5 h to obtain a supported nickel-based catalyst with a nickel content of 1.2 wt%, a copper content of 0.2 wt%, a carrier Al2O3 content of 95.6 wt%, and a KH550 content of 3 wt%.

[0077] An application of the above catalyst in the hydrogenation of maleic anhydride to prepare succinic anhydride, and the application method includes the following steps:

[0078] Load 10 g of the above catalyst into a 1-L reactor, set the reaction temperature to 130 °C, the reaction pressure to 3 MPa, and the hydrogen flow rate to 1000 mL / min; after the hydrogenation reaction starts, input maleic anhydride into the slurry bed reactor at a flow rate of 0.06 mL / min, and after the reaction runs for 24 h, take samples from the gas-liquid separator for analysis; the reaction results are shown in Table 1.

[0079] Example 4

[0080] A preparation method of a supported nickel-based catalyst for slurry bed hydrogenation of maleic anhydride includes the following steps:

[0081] (1) Add 100 g of alumina (α-Al2O3, particle size of 100 μm) to 100 g of a KH-550 ethanol solution with a concentration of 1 wt%, mix well, transfer to a closed container, impregnate at normal temperature and pressure for 24 h, and dry at 80 °C for 24 h to obtain a catalyst precursor;

[0082] (2) Add the catalyst precursor obtained in step (1) to a mixed solution of 100 g of an aqueous nickel acetate solution with a concentration of 0.8 moL / L and 25 g of an aqueous copper acetate solution with a concentration of 0.2 moL / L, mix well, impregnate at normal temperature and pressure for 24 h, dry at 100 °C for 24 h, and reduce with pure H2 at 300 °C for 5 h to obtain a supported nickel-based catalyst with a nickel content of 1.2 wt%, a copper content of 0.4 wt%, a carrier Al2O3 content of 97.4 wt%, and a KH550 content of 1 wt%.

[0083] An application of the above catalyst in the hydrogenation of maleic anhydride to prepare succinic anhydride, and the application method includes the following steps:

[0084] Load the above 10 g of catalyst into a 1-L reactor, set the reaction temperature at 140 °C, the reaction pressure at 3 MPa, and the hydrogen flow rate at 1000 mL / min. After the hydrogenation reaction starts, input maleic anhydride into the slurry bed reactor at a flow rate of 0.08 mL / min. After the reaction runs for 24 h, take samples from the gas-liquid separator for analysis. The reaction results are shown in Table 1.

[0085] Example 5

[0086] A preparation method of a supported nickel-based catalyst for maleic anhydride hydrogenation in a slurry bed, comprising the following steps:

[0087] (1) Add 100 g of alumina (α-Al2O3, particle size 100 μm) to 100 g of an 8 wt% KH-550 ethanol solution. After mixing evenly, transfer it to a closed container and carry out impregnation treatment at normal temperature and pressure for 24 h, then dry at 80 °C for 24 h to obtain a catalyst precursor.

[0088] (2) Add the catalyst precursor obtained in step (1) to a mixed solution of 100 g of a 0.6 moL / L nickel acetate aqueous solution and 25 g of a 0.1 moL / L copper acetate aqueous solution. Mix evenly, carry out impregnation treatment at normal temperature and pressure for 24 h, dry at 100 °C for 24 h, and reduce it with pure H2 at 300 °C for 5 h to obtain a supported nickel-based catalyst with a nickel content of 1.0 wt%, a copper content of 0.2 wt%, a carrier Al2O3 content of 90.8 wt%, and a KH550 content of 8 wt%.

[0089] An application of the above catalyst in the preparation of succinic anhydride by maleic anhydride hydrogenation, and its application method comprises the following steps:

[0090] Load the above 10 g of catalyst into a 1-L reactor, set the reaction temperature at 130 °C, the reaction pressure at 3 MPa, and the hydrogen flow rate at 1000 mL / min. After the hydrogenation reaction starts, input maleic anhydride into the slurry bed reactor at a flow rate of 0.05 mL / min. After the reaction runs for 24 h, take samples from the gas-liquid separator for analysis. The reaction results are shown in Table 1.

[0091] Testing method

[0092] The reaction liquid product is detected and analyzed using an Agilent 6890 with a test column of AB-InoWax (30 m × 0.32 mm × 0.5 μm), and each substance to be measured is quantified by the external standard method.

[0093] Reaction conversion rate (%) = (moles of converted reactants / moles of reactants in the raw material) × 100%.

[0094] Product selectivity (%) = (moles of a certain product produced / moles of reactant converted) × 100%.

[0095] Among them, others include propanol, butanol, propionic acid, butyric acid, etc.;

[0096] Table 1 Reaction results of the preparation of succinic anhydride by the directional catalytic hydrogenation of maleic anhydride

[0097]

[0098] It should be noted that the present invention has been specifically described with individual embodiments. However, without departing from the principle of the present invention, those of ordinary skill in the art can make various improvements in forms or details to the present invention, and these improvements also fall within the protection scope of the present invention.

Claims

1. A supported nickel-based catalyst for maleic anhydride hydrogenation in a slurry bed, characterized in that, The content of nickel in the catalyst is 0.2 - 2 wt%, the content of the coupling agent is 0.1 - 10 wt%, the content of copper is 0.01 - 1 wt%, and the content of the carrier is 90 - 99.8 wt%.

2. The supported nickel-based catalyst for maleic anhydride hydrogenation in slurry bed according to claim 1, characterized in that, The content of nickel is 0.3 - 0.8 wt%; and / or the content of the coupling agent is 1 - 5 wt%; and / or the content of copper is 0.1 - 0.5 wt%; and / or the content of the carrier is 93.7 - 99.7 wt%.

3. The supported nickel-based catalyst for maleic anhydride hydrogenation in slurry bed according to claim 1, characterized in that, The coupling agent is an amino silane coupling agent and / or a mercapto silane coupling agent; The amino silane coupling agent is one or any combination of KH-550, KH-540, KH-791, KH-792, KH-902; The mercapto silane coupling agent is one or any combination of KH-590, KH-580, KH-970.

4. The supported nickel-based catalyst for maleic anhydride hydrogenation in slurry bed according to claim 1, characterized in that, The particle size of the carrier is 80 - 150 μm; The carrier is one or any combination of alumina, silica, titanium oxide, zinc oxide, magnesium oxide, activated carbon, and silica-alumina molecular sieve; The alumina is α-Al2O3 and / or γ-Al2O3.

5. The preparation method of the supported nickel-based catalyst for maleic anhydride hydrogenation in slurry bed according to any one of claims 1 to 4, characterized in that, It includes the following steps: (1) Add the carrier to the coupling agent solution, mix evenly, transfer it to a closed container for impregnation treatment, and then dry to obtain a catalyst precursor; (2) Add the catalyst precursor obtained in step (1) to the mixed solution of the soluble nickel salt solution and the soluble copper salt solution, mix evenly, and after impregnation, drying, and reduction, obtain a supported nickel-based catalyst.

6. The preparation method of the supported nickel-based catalyst for maleic anhydride hydrogenation in slurry bed according to claim 5, characterized in that, In step (1), the mass ratio of the carrier to the coupling agent solution is (1 - 2):(1 - 3); the solvent of the coupling agent solution is ethanol or water; the concentration of the coupling agent solution is 1 - 10 wt%; the impregnation conditions are normal temperature and normal pressure, and the time is 12 - 24 h; the drying conditions are a temperature of 60 - 80 °C and a time of 8 - 24 h.

7. The preparation method of the supported nickel-based catalyst for maleic anhydride hydrogenation in a slurry bed according to claim 5, characterized in that, In step (2), the mass ratio of the catalyst precursor to the mixed solution of the soluble nickel salt solution and the soluble copper salt solution is (1 - 3):(1 - 5); the mass ratio of the soluble nickel salt solution to the soluble copper salt solution is (2 - 5):1; the concentration of the soluble nickel salt solution is 0.2 - 1 moL / L; the concentration of the soluble copper salt solution is 0.01 - 1 mol / L.

8. The preparation method of the supported nickel-based catalyst for maleic anhydride hydrogenation in slurry bed according to claim 7, characterized in that, The soluble nickel salt is one or any combination of nickel nitrate, nickel chloride, nickel sulfate, nickel formate, nickel acetate, nickel oxalate, nickel citrate; the soluble copper salt is one or any combination of copper nitrate, copper chloride, copper sulfate, basic copper carbonate, copper acetate.

9. The preparation method of the supported nickel-based catalyst for maleic anhydride hydrogenation in a slurry bed according to claim 5, characterized in that, In step (2), the impregnation conditions are normal temperature and normal pressure, and the time is 12 - 24 h; the drying conditions are a temperature of 80 - 120 °C and a time of 8 - 24 h; the reduction conditions are reduction with pure H2, a temperature of 300 - 600 °C, and a time of 3 - 12 h.

10. Use of the supported nickel-based catalyst for maleic anhydride hydrogenation in slurry bed according to any one of claims 1 to 4 in the production of succinic anhydride by maleic anhydride hydrogenation, characterized in that, The method of the application includes the following steps: Load the above catalyst into a slurry bed reactor, set the reaction temperature to 120 - 180 °C, the reaction pressure to 2 - 3 MPa, and the hydrogen gas flow rate to 600 - 1000 mL / min; after the hydrogenation reaction starts, input maleic anhydride into the slurry bed reactor at a flow rate of 0.04 - 1 mL / min. When the reaction is running, the maleic anhydride flow rate enters the reactor, and the reaction runs for 24 - 72 h to complete the liquid-phase hydrogenation of maleic anhydride.

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