A catalyst for liquid phase hydrogenation of n-butyraldehyde, a preparation method and application thereof

Abstract

The application provides a normal butyl aldehyde liquid-phase hydrogenation catalyst and a preparation method and application thereof, and relates to the technical field of catalysts. The catalyst is an auxiliary agent modified supported metal nickel catalyst, which is prepared by a coprecipitation method and is composed of 20-80% active components Ni, 2-20% auxiliary agents and a carrier. The catalyst is used in a two-stage hydrogenation process of normal butyl aldehyde. The process is simple and low in cost, the catalyst is high in stability, the surface acid and alkali are moderate, the normal butyl aldehyde can be prepared at a high conversion rate, the generation of by-products is obviously inhibited, the yield of normal butyl alcohol is improved, the catalyst is suitable for industrial application, and an excellent scheme for efficiently preparing normal butyl alcohol is provided.

Description

Technical Field

[0001] This invention relates to the field of catalyst technology, and in particular to a liquid-phase hydrogenation catalyst for n-butyraldehyde, its preparation method, and its application. Background Technology

[0002] n-Butanol is an important basic chemical raw material, widely used in the chemical, pharmaceutical, food and energy fields. It is mainly used to produce plasticizers such as dibutyl phthalate, butyl acetate, butyl acrylate, and butyl methacrylate. It is also commonly used as a special solvent and organic synthesis intermediate.

[0003] Industrial production methods for n-butanol include acetaldehyde condensation, fermentation, and propylene carbonyl synthesis. Among these, propylene carbonyl synthesis has become the mainstream process due to its inexpensive and readily available raw materials, mild reaction conditions, few side reactions, and high efficiency. This method uses propylene, carbon monoxide, and hydrogen as raw materials, which are carbonylated to produce n-butyraldehyde, and then catalytically hydrogenated to obtain n-butanol. The hydrogenation of n-butyraldehyde is one of the key steps in the propylene carbonyl synthesis method.

[0004] Because gas-phase hydrogenation consumes a lot of energy, liquid-phase hydrogenation has gradually gained attention. However, n-butyraldehyde is chemically reactive and is prone to side reactions such as disproportionation and condensation under high-temperature liquid-phase conditions, which ultimately leads to low reaction selectivity, many by-products, and problems such as low n-butanol yield and low purity. Summary of the Invention

[0005] In view of this, the present invention provides a liquid-phase hydrogenation catalyst for n-butyraldehyde, its preparation method and application. The present invention uses a supported metallic nickel modified with an auxiliary agent as a catalyst, combined with a specific two-stage hydrogenation process, to ensure a high conversion rate of n-butyraldehyde in the process of preparing n-butanol by liquid-phase hydrogenation of n-butyraldehyde, while effectively suppressing the formation of by-products and improving the yield of n-butanol, which is suitable for industrial application.

[0006] The n-butyraldehyde liquid-phase hydrogenation catalyst of the present invention comprises, by mass percentage:

[0007] The active ingredient comprises 20%–80%, the auxiliary agent comprises 2%–20%, and the remainder is a carrier;

[0008] The active component is Ni; the auxiliary agent is at least one of MgO, ZnO, ZrO2, Cr2O3, Ga2O3, Y2O3, La2O3, CeO2, and Al2O3; and the support is at least one of SiO2, Al2O3, and activated carbon.

[0009] This invention provides a method for preparing a liquid-phase hydrogenation catalyst for n-butyraldehyde, specifically comprising the following steps:

[0010] Nickel salt and auxiliary salt are dissolved in deionized water to obtain a mixed salt solution; the support is dispersed in deionized water and heat-treated to obtain a support suspension; the mixed salt solution and precipitant are added to the support suspension to precipitate and age; the precipitate is washed, dried and calcined to obtain the n-butyraldehyde liquid-phase hydrogenation catalyst.

[0011] Preferably, the nickel salt is at least one of Ni(NO3)2·6H2O, NiSO4·6H2O, NiCl2, and Ni(CH3COO)2.

[0012] Preferably, the auxiliary salt is at least one selected from Mg(NO3)2·6H2O, Zn(NO3)2·6H2O, ZrOCl2·8H2O, Cr(NO3)3·9H2O, Ga(NO3)3, Y(NO3)3·6H2O, La(NO3)3·6H2O, Ce(NO3)3·6H2O, and Al(NO3)3.

[0013] Preferably, the precipitant is at least one of NH3·H2O, (NH4)2CO3, NaOH, and Na2CO3 solution.

[0014] Preferably, the heat treatment temperature is 50℃~100℃, and the heat treatment time is 1~5h.

[0015] Preferably, the calcination temperature is 400℃~800℃ and the calcination time is 2~8h.

[0016] Preferably, the calcination is carried out in an air or nitrogen atmosphere.

[0017] This invention also provides the application of a n-butyraldehyde liquid-phase hydrogenation catalyst in the production of n-butanol from n-butyraldehyde via liquid-phase hydrogenation.

[0018] Preferably, the liquid-phase hydrogenation of n-butyraldehyde to n-butanol is a two-stage continuous process, specifically: n-butyraldehyde raw material first enters the first hydrogenation reactor for hydrogenation reaction, and then the product of the first hydrogenation reactor is used as reactant to directly enter the second hydrogenation reactor for deep hydrogenation reaction to obtain n-butanol.

[0019] Preferably, the mass hourly space velocity (MSV) of the first hydrogenation reactor is 0.1–2 h⁻¹. -1 The molar ratio of hydrogen to n-butyraldehyde is (5–20):1, and the mass hourly space velocity (HHSV) of the second hydrogenation reactor is 0.5–5 h⁻¹. -1 .

[0020] Preferably, the hydrogen pressure is 0.5–5 MPa throughout the hydrogenation process.

[0021] Preferably, the reaction temperature of the hydrogenation reactor is 60°C to 120°C.

[0022] This invention uses supported metallic nickel modified with an additive as a catalyst. The strong interaction between the additive, the active nickel center, and the support improves the catalyst's stability. Simultaneously, this invention regulates the interaction among the active component, additive, and support by adjusting their composition and ratio, resulting in a catalyst with moderate surface acidity / basicity. This ensures catalytic efficiency while reducing the amount of byproducts generated, leading to excellent overall performance of the catalyst in the two-stage liquid-phase hydrogenation of n-butyraldehyde to n-butanol.

[0023] This invention employs a simple co-precipitation method to prepare the catalyst, which is simple in process, low in production cost, and easy to implement for industrial production. Simultaneously, by appropriately heat-treating the support, this invention increases the number of active groups on the support surface, enhances the interaction between the support and nickel and auxiliary salts, inhibits the sintering and agglomeration of active components, improves dispersion and stability, provides more active sites for the n-butyraldehyde liquid phase, and increases the hydrogenation catalytic activity.

[0024] This invention employs a two-stage hydrogenation process. The first stage hydrogenation reaction can convert most of the n-butyraldehyde into stable products and intermediates at low temperatures, while the second stage hydrogenation reaction can hydrogenate the remaining small amount of n-butyraldehyde and intermediates into n-butanol. This effectively suppresses the formation of by-products and increases the yield of n-butanol while ensuring a high conversion rate. Detailed Implementation

[0025] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0026] This invention provides a liquid-phase hydrogenation catalyst for n-butyraldehyde, wherein the catalyst comprises, by mass percentage:

[0027] The active ingredient comprises 20%–80%, the auxiliary agent comprises 2%–20%, and the remainder is a carrier;

[0028] The active component is Ni; the auxiliary agent is at least one of MgO, ZnO, ZrO2, Cr2O3, Ga2O3, Y2O3, La2O3, CeO2, and Al2O3; and the support is at least one of SiO2, Al2O3, and activated carbon.

[0029] In some specific embodiments of the present invention, the n-butyraldehyde liquid-phase hydrogenation catalyst comprises, by mass percentage: 30-60% active component; 5-10% auxiliary agent; and the balance being a support.

[0030] In some specific embodiments of the present invention, the nickel salt is at least one of Ni(NO3)2·6H2O, NiSO4·6H2O, NiCl2, and Ni(CH3COO)2; the auxiliary salt is at least one of Mg(NO3)2·6H2O, Zn(NO3)2·6H2O, ZrOCl2·8H2O, Cr(NO3)3·9H2O, Ga(NO3)3, Y(NO3)3·6H2O, La(NO3)3·6H2O, Ce(NO3)3·6H2O, and Al(NO3)3.

[0031] This invention provides a method for preparing a liquid-phase hydrogenation catalyst for n-butyraldehyde, specifically comprising the following steps:

[0032] S1. Dissolve the nickel salt and auxiliary salt in deionized water to obtain a 0.5M mixed salt solution;

[0033] Uniformly dissolving the active component (nickel salt) and the auxiliary salt ensures a uniform distribution of metal ions in the subsequent reaction, thereby improving the uniformity and performance of the catalyst. Controlling the concentration of the mixed salt solution can prevent the precipitate particles from becoming too large or too dense due to excessive concentration, thus reducing the dispersibility of the active sites.

[0034] S2. Disperse the carrier in deionized water and heat-treat at 50℃~100℃ for 1~5h. After heat treatment, a carrier suspension with a carrier concentration of 20~80g / L is obtained.

[0035] This invention improves the surface activity of the support through heat treatment, enhances its interaction with active components and additives, and increases porosity to provide more active sites for the catalyst. Controlling the temperature and time of heat treatment can balance the generation of active sites and the integrity of the support structure, preventing structural collapse or crystal phase transformation.

[0036] Carrier concentration 20-80 g / L: to ensure the dispersibility of the carrier in the liquid phase and avoid deposition or excessive dilution affecting the uniformity of the precipitation reaction.

[0037] S3. Add the mixed salt solution and precipitant of S1 to the carrier suspension of S2, and after precipitation, age it at 50℃~100℃ for 4~10h.

[0038] The role of the precipitant is to enable metal ions to combine with the carrier to form a uniform precursor. Aging can further promote the interaction between the metal and the carrier and the stability of the precursor. Limiting the aging temperature and aging time can promote the crystallization and stabilization of the precipitate, avoid grain agglomeration, and ensure high dispersibility.

[0039] S4. Wash the precipitate, dry it at 90℃~120℃ for 8~12h, then calcine it at 400℃~800℃ for 2~8h, and after cooling, the n-butyraldehyde liquid-phase hydrogenation catalyst is obtained.

[0040] In some preferred embodiments of the present invention, the heat treatment temperature is 50°C to 80°C.

[0041] In some specific embodiments of the present invention, the precipitant is at least one of NH3·H2O, (NH4)2CO3, NaOH, and Na2CO3 solution, the concentration of the precipitant solution is 10% to 40%, and the molar ratio of the precipitant and nickel salt to the auxiliary salt is 1:1.2.

[0042] This invention also provides the application of a n-butyraldehyde liquid-phase hydrogenation catalyst in the production of n-butanol from n-butyraldehyde via liquid-phase hydrogenation.

[0043] In some specific embodiments of the present invention, the liquid-phase hydrogenation of n-butyraldehyde to n-butanol is carried out in a fixed-bed continuous flow reactor. The hydrogenation process is a two-stage continuous process, and the specific steps are as follows:

[0044] n-Butyraldehyde enters the first hydrogenation reactor and undergoes a single hydrogenation process under conditions where the molar ratio of hydrogen to n-butyraldehyde is (5–20):1. The mass hourly space velocity (HHSV) of the first hydrogenation reactor is 0.1–2 h⁻¹. -1 The product from the primary hydrogenation process is fed into a second hydrogenation reactor for further hydrogenation. The mass hourly space velocity (HSV) of the second hydrogenation reactor is 0.5–5 h⁻¹. -1 After deep hydrogenation, n-butanol is obtained. The hydrogen pressure is 0.5-5 MPa and the reaction temperature is 60℃-120℃ in both the primary hydrogenation and deep hydrogenation processes.

[0045] The technical solutions in the embodiments of this application will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of this application, not all of them. Other embodiments obtained by those skilled in the art based on the embodiments of this application without creative effort are all within the scope of protection of the invention. In the following embodiments, all raw materials are commercially available.

[0046] Unless otherwise specified, all experiments were repeated three times, and the results are expressed as mean values. P < 0.05 indicates a significant difference.

[0047] Example 1: A method for producing n-butanol by liquid-phase hydrogenation of n-butyraldehyde, the steps of which are as follows:

[0048] In a fixed-bed continuous flow reactor, under the conditions of a hydrogen pressure of 3.0 MPa, a hydrogen to n-butyraldehyde molar ratio of 10:1, the reaction temperature of the first hydrogenation reactor was 70 °C and the mass hourly space velocity (WHSV) was 1.0 h⁻¹. -1The reaction temperature in the second hydrogenation reactor was 90℃, and the mass hourly space velocity (H₂S) was 3.0 h⁻¹. -1 n-Butyraldehyde is reacted with hydrogenation catalysts in two separate reactors to obtain n-butanol.

[0049] The catalyst in the first hydrogenation reactor is a Ni-ZrO2 / SiO2 n-butyraldehyde liquid-phase hydrogenation catalyst; the catalyst in the second hydrogenation reactor is a Ni-Al2O3 / SiO2 n-butyraldehyde liquid-phase hydrogenation catalyst.

[0050] The Ni-ZrO2 / SiO2 n-butyraldehyde liquid-phase hydrogenation catalyst comprises, by mass percentage: 40% Ni, 8% ZrO2 as an auxiliary agent, and the balance being SiO2 support;

[0051] The catalyst is prepared as follows:

[0052] S1. Dissolve Ni(NO3)2·6H2O and ZrOCl2·8H2O in deionized water to obtain a 0.5M mixed salt solution;

[0053] S2. Under vigorous stirring, SiO2 powder is dispersed in deionized water and heat-treated at 80°C for 3 hours. After heat treatment, a carrier suspension with a carrier concentration of 50 g / L is obtained.

[0054] S3. Add the mixed salt solution of S1 and Na2CO3 with a concentration of 20% to the carrier suspension of S2, wherein the molar amount of Na2CO3 is 1.2 times that of the mixed salt. After precipitation, age at 80℃ for 6 hours.

[0055] S4. Wash the precipitate, dry it at 100℃ for 10h, then calcine it at 600℃ in air for 4h, and after cooling, obtain the Ni-ZrO2 / SiO2 n-butyraldehyde liquid-phase hydrogenation catalyst.

[0056] The Ni-Al2O3 / SiO2 n-butyraldehyde liquid-phase hydrogenation catalyst comprises, by mass percentage:

[0057] Ni 50%, Al2O3 8% additive, balance SiO2 support;

[0058] The catalyst is prepared as follows:

[0059] S1. Dissolve NiSO4·6H2O and Al(NO3)3 in deionized water to obtain a 0.5M mixed salt solution;

[0060] S2. Under vigorous stirring, SiO2 powder is dispersed in deionized water and heat-treated at 80°C for 3 hours. After heat treatment, a carrier suspension with a carrier concentration of 50 g / L is obtained.

[0061] S3. Add the mixed salt solution of S1 and Na2CO3 with a concentration of 20% to the carrier suspension of S2, wherein the molar amount of Na2CO3 is 1.2 times that of the mixed salt. After precipitation, age at 80℃ for 6 hours.

[0062] S4. Wash the precipitate, dry it at 100℃ for 10h, then calcine it at 600℃ in air for 4h, and after cooling, obtain the Ni-ZrO2 / SiO2 n-butyraldehyde liquid-phase hydrogenation catalyst.

[0063] Testing showed that the conversion rate of n-butyraldehyde was >99%, and the selectivity of n-butanol was 99.2%. Under the same conditions, the two catalyst stages were run continuously for 500 hours, and the conversion rate and selectivity did not change significantly.

[0064] Example 2

[0065] Same as Example 1, except that the hydrogen pressure is 0.5 MPa and the molar ratio of hydrogen to n-butyraldehyde is 20:1.

[0066] Testing showed that the conversion rate of n-butyraldehyde was >99%, and the selectivity of n-butanol was 98.6%. Under the same conditions, the two catalyst stages were run continuously for 500 hours, and the conversion rate and selectivity did not change significantly.

[0067] Example 3

[0068] Same as Example 1, except that the hydrogen pressure is 5.0 MPa and the molar ratio of hydrogen to n-butyraldehyde is 5:1.

[0069] Testing showed that the conversion rate of n-butyraldehyde was >99%, and the selectivity of n-butanol was 99.4%. Under the same conditions, the two catalyst stages were run continuously for 500 hours, and the conversion rate and selectivity did not change significantly.

[0070] Example 4

[0071] Same as Example 1, except that: the reaction temperature of the first hydrogenation reactor is 90°C and the mass hourly space velocity is 2.0 h⁻¹. -1 The Ni-ZrO2 / SiO2 n-butyraldehyde liquid-phase hydrogenation catalyst in the first hydrogenation reactor comprises, by mass percentage: Ni 30%, Al2O3 5%, and the balance being SiO2 support; the Ni-Al2O3 / SiO2 n-butyraldehyde liquid-phase hydrogenation catalyst in the second hydrogenation reactor comprises, by mass percentage: Ni 50%, Al2O3 8%, and the balance being SiO2 support.

[0072] Testing showed that the conversion rate of n-butyraldehyde was >99%, and the selectivity of n-butanol was 97.9%. Under the same conditions, the two catalyst stages were run continuously for 500 hours, and the conversion rate and selectivity did not change significantly.

[0073] Example 5

[0074] Same as Example 1, except that the reaction temperature of the first hydrogenation reactor is 60°C and the mass hourly space velocity is 2.0 h⁻¹. -1 The Ni-ZrO2 / SiO2 n-butyraldehyde liquid-phase hydrogenation catalyst in the first hydrogenation reactor comprises, by mass percentage: Ni 60%, Al2O3 10%, and the balance being SiO2 support.

[0075] Testing showed that the conversion rate of n-butyraldehyde was >99%, and the selectivity of n-butanol was 99.5%. Under the same conditions, the two catalyst stages were run continuously for 500 hours, and the conversion rate and selectivity did not change significantly.

[0076] Example 6

[0077] Same as Example 1, except that the reaction temperature of the second hydrogenation reactor is 70°C and the mass hourly space velocity is 0.5 h⁻¹. -1 The Ni-Al2O3 / SiO2 n-butyraldehyde liquid-phase hydrogenation catalyst in the second hydrogenation reactor comprises, by mass percentage: 60% Ni, 10% Al2O3 as an auxiliary agent, and the remainder being SiO2 support.

[0078] Testing showed that the conversion rate of n-butyraldehyde was >99%, and the selectivity of n-butanol was 98.9%. Under the same conditions, the two catalyst stages were run continuously for 500 hours, and the conversion rate and selectivity did not change significantly.

[0079] Example 7

[0080] Same as Example 1, except that the reaction temperature of the second hydrogenation reactor is 120°C and the mass hourly space velocity is 5.0 h⁻¹. -1 The Ni-Al2O3 / SiO2 n-butyraldehyde liquid-phase hydrogenation catalyst in the second hydrogenation reactor comprises, by mass percentage: Ni 30%, Al2O3 5%, and the balance being SiO2 support.

[0081] Testing showed that the conversion rate of n-butyraldehyde was >99%, and the selectivity of n-butanol was 98.1%. Under the same conditions, the two catalyst stages were run continuously for 500 hours, and the conversion rate and selectivity did not change significantly.

[0082] Comparative Example 1: A method for the liquid-phase hydrogenation of n-butyraldehyde to n-butanol, comprising the following steps:

[0083] In a fixed-bed continuous flow reactor, the reaction was carried out at a temperature of 70℃, a hydrogen pressure of 3.0 MPa, a hydrogen to n-butyraldehyde molar ratio of 10:1, and a mass hourly space velocity of 1.0 h⁻¹. -1 Under certain conditions, n-butyraldehyde is reacted with a hydrogenation catalyst to obtain n-butanol.

[0084] The catalyst is a Ni-ZrO2 / SiO2 n-butyraldehyde liquid-phase hydrogenation catalyst, comprising, by mass percentage: Ni 40%, ZrO2 8%, and the balance being SiO2 support.

[0085] Testing showed that the conversion rate of n-butyraldehyde was >99%, and the selectivity of n-butanol was 92.0%.

[0086] Comparative Example 2: A method for the liquid-phase hydrogenation of n-butyraldehyde to n-butanol, the steps of which are as follows:

[0087] In a fixed-bed continuous flow reactor, the reaction temperature was 90℃, the hydrogen pressure was 3.0 MPa, the hydrogen to n-butyraldehyde molar ratio was 10:1, and the mass hourly space velocity was 3.0 h⁻¹. -1 Under certain conditions, n-butyraldehyde is reacted with a hydrogenation catalyst to obtain n-butanol.

[0088] The catalyst is a Ni-Al2O3 / SiO2 n-butyraldehyde liquid-phase hydrogenation catalyst, comprising, by mass percentage: Ni 50%, Al2O3 8%, and the balance being SiO2 support.

[0089] Testing showed that the conversion rate of n-butyraldehyde was >99%, and the selectivity of n-butanol was 91.5%.

[0090] Example 8: A Ni-MgO / SiO2 n-butyraldehyde liquid-phase hydrogenation catalyst, comprising, by mass percentage: 50% Ni, 10% MgO as an auxiliary agent, and the balance being a SiO2 support.

[0091] The preparation method of the n-butyraldehyde liquid-phase hydrogenation catalyst is as follows:

[0092] S1. Dissolve Ni(NO3)2·6H2O and Mg(NO3)2·6H2O in deionized water to obtain a mixed salt solution with a concentration of 0.5M;

[0093] S2. Under vigorous stirring, SiO2 powder was dispersed in deionized water and treated at 80°C for 3 hours to obtain a carrier suspension of 50 g / L.

[0094] S3. Add the mixed salt solution and a 20% Na2CO3 solution to the carrier suspension, wherein the molar amount of Na2CO3 is 1.2 times that of the mixed salt. Aging at 80°C for 6 hours and filtering to obtain the precipitate.

[0095] S4. After washing, the precipitate is dried at 100°C for 10 hours and then calcined at 600°C in air for 4 hours to obtain the catalyst.

[0096] Example 9: A Ni-ZnO / Al2O3 n-butyraldehyde liquid-phase hydrogenation catalyst, comprising, by mass percentage: Ni 20%, ZnO 2%, and the balance being an Al2O3 support.

[0097] The preparation method of the n-butyraldehyde liquid-phase hydrogenation catalyst is as follows:

[0098] S1. Dissolve NiSO4·6H2O and Zn(NO3)2·6H2O in deionized water to obtain a mixed salt solution with a concentration of 0.5M;

[0099] S2. Under vigorous stirring, Al2O3 powder was dispersed in deionized water and treated at 80°C for 3 hours to obtain a carrier suspension of 80 g / L.

[0100] S3. Add the mixed salt solution and a 20% Na2CO3 solution to the carrier suspension, wherein the molar amount of Na2CO3 is 1.2 times that of the mixed salt. Aging at 80°C for 6 hours and filtering to obtain the precipitate.

[0101] S4. After washing, the precipitate is dried at 100°C for 10 hours and calcined at 600°C for 4 hours in an atmosphere to obtain the catalyst.

[0102] Example 10: A Ni-ZrO2 / activated carbon n-butyraldehyde liquid-phase hydrogenation catalyst, comprising, by mass percentage: 80% Ni, 10% ZrO2 as an auxiliary agent, and the balance being an activated carbon support.

[0103] The preparation method of the n-butyraldehyde liquid-phase hydrogenation catalyst is as follows:

[0104] S1. Dissolve NiCl2·6H2O and ZrOCl2·8H2O in deionized water to obtain a mixed salt solution with a concentration of 0.5M;

[0105] S2. Under vigorous stirring, the activated carbon powder was dispersed in deionized water and treated at 80°C for 3 hours to obtain a carrier suspension of 20 g / L.

[0106] S3. Add the mixed salt solution and a 20% Na2CO3 solution to the carrier suspension, wherein the molar amount of Na2CO3 is 1.2 times that of the mixed salt. Aging at 80°C for 6 hours and filtering to obtain the precipitate.

[0107] S4. After washing, the precipitate is dried at 100°C for 10 hours and then calcined at 600°C for 4 hours in a nitrogen atmosphere to obtain the catalyst.

[0108] Example 11: A Ni-Cr2O3 / SiO2 n-butyraldehyde liquid-phase hydrogenation catalyst, comprising, by mass percentage: Ni 50%, Cr2O3 20%, and the balance being SiO2 support.

[0109] The preparation method of the n-butyraldehyde liquid-phase hydrogenation catalyst is as follows:

[0110] S1. Dissolve Ni(OAc)2·4H2O and Cr(NO3)3·9H2O in deionized water to obtain a mixed salt solution with a concentration of 0.5M;

[0111] S2. Under vigorous stirring, SiO2 powder was dispersed in deionized water and treated at 80°C for 3 hours to obtain a carrier suspension of 50 g / L.

[0112] S3. Add the mixed salt solution and 40% Na2CO3 to the carrier suspension, wherein the molar amount of Na2CO3 is 1.2 times that of the mixed salt. Aging at 80°C for 6 hours and filtering to obtain the precipitate.

[0113] S4. After washing, the precipitate is dried at 100°C for 10 hours and then calcined at 600°C in air for 4 hours to obtain the catalyst.

[0114] Example 12: A Ni-Ga2O3 / SiO2 n-butyraldehyde liquid-phase hydrogenation catalyst, comprising, by mass percentage: Ni 50%, Ga2O3 10%, and the balance being SiO2 support.

[0115] The preparation method of the n-butyraldehyde liquid-phase hydrogenation catalyst is as follows:

[0116] S1. Dissolve Ni(NO3)2·6H2O and Ga(NO3)3 in deionized water to obtain a mixed salt solution with a concentration of 0.5M;

[0117] S2. Under vigorous stirring, the SiO2 support powder was dispersed in deionized water and treated at 50°C for 5 hours to obtain a support suspension of 50 g / L.

[0118] S3. Add the mixed salt solution and 10% Na2CO3 to the carrier suspension, wherein the molar amount of Na2CO3 is 1.2 times that of the mixed salt. Aging at 50°C for 10 hours and filtering to obtain the precipitate.

[0119] S4. After washing, the precipitate is dried at 100°C for 10 hours and then calcined at 800°C in air for 2 hours to obtain the catalyst.

[0120] Example 13: A Ni-Y2O3 / SiO2 n-butyraldehyde liquid-phase hydrogenation catalyst, comprising, by mass percentage: Ni 50%, Y2O3 10%, and the balance being SiO2 support.

[0121] The preparation method of the n-butyraldehyde liquid-phase hydrogenation catalyst is as follows:

[0122] S1. Dissolve Ni(NO3)2·6H2O and Y(NO3)3·6H2O in deionized water to obtain a mixed salt solution with a concentration of 0.5M;

[0123] S2. Under vigorous stirring, the SiO2 support powder was dispersed in deionized water and treated at 100°C for 1 hour to obtain a support suspension of 50 g / L.

[0124] S3. Add the mixed salt solution and 20% ammonium carbonate solution to the carrier suspension, wherein the molar amount of Na2CO3 is 1.2 times that of the mixed salt. Aging at 100°C for 4 hours and filtering to obtain the precipitate.

[0125] S4. After washing, the precipitate is dried at 100°C for 10 hours and then calcined at 400°C in air for 8 hours to obtain the catalyst.

[0126] Example 14: A Ni-La2O3 / SiO2 n-butyraldehyde liquid-phase hydrogenation catalyst, comprising, by mass percentage: Ni 50%, La2O3 10%, and the balance being SiO2 support.

[0127] The preparation method of the n-butyraldehyde liquid-phase hydrogenation catalyst is as follows:

[0128] S1. Dissolve Ni(NO3)2·6H2O and La(NO3)3·6H2O in deionized water to obtain a mixed salt solution with a concentration of 0.5M;

[0129] S2. Under vigorous stirring, the SiO2 support powder was dispersed in deionized water and treated at 80°C for 3 hours to obtain a support suspension of 50 g / L.

[0130] S3. Add the mixed salt solution and 20% sodium hydroxide solution to the carrier suspension, wherein the molar amount of Na2CO3 is 1.2 times that of the mixed salt, age at 80°C for 6 hours, and filter to obtain the precipitate.

[0131] S4. After washing, the precipitate is dried at 90°C for 12 hours and then calcined at 600°C in air for 4 hours to obtain the catalyst.

[0132] Example 15: A Ni-CeO2 / SiO2 n-butyraldehyde liquid-phase hydrogenation catalyst, comprising, by mass percentage: Ni 50%, CeO2 10%, and the balance being SiO2 support.

[0133] The preparation method of the n-butyraldehyde liquid-phase hydrogenation catalyst is as follows:

[0134] S1. Dissolve Ni(NO3)2·6H2O and Ce(NO3)3·6H2O in deionized water to obtain a mixed salt solution with a concentration of 0.5M;

[0135] S2. Under vigorous stirring, the SiO2 support powder was dispersed in deionized water and treated at 80°C for 3 hours to obtain a support suspension of 50 g / L.

[0136] S3. Add the mixed salt solution and 20% ammonia solution to the carrier suspension, age at 80°C for 6 hours, and filter to obtain the precipitate;

[0137] S4. After washing, the precipitate is dried at 120°C for 8 hours and then calcined at 600°C in air for 4 hours to obtain the catalyst.

[0138] Comparative Example 3: A Ni / SiO2 n-butyraldehyde liquid-phase hydrogenation catalyst, comprising, by mass percentage: 50% Ni, with the balance being a SiO2 support.

[0139] The preparation method of the n-butyraldehyde liquid-phase hydrogenation catalyst is as follows:

[0140] S1. Dissolve Ni(NO3)2·6H2O in deionized water to obtain a salt solution with a concentration of 0.5M;

[0141] S2. Under vigorous stirring, the SiO2 support powder was dispersed in 1000 mL of deionized water and treated at 80 °C for 3 h to obtain a support suspension of 50 g / L.

[0142] S3. Add the mixed salt solution and 20% Na2CO3 together to the carrier suspension, wherein the molar amount of Na2CO3 is 1.2 times that of the mixed salt, age at 80°C for 6 hours, and filter to obtain the precipitate;

[0143] S4. After washing, the precipitate is dried at 100°C for 10 hours and then calcined at 600°C in air for 4 hours to obtain the catalyst.

[0144] Comparative Example 4: A Ni-MgO / SiO2 / n-butyraldehyde liquid-phase hydrogenation catalyst, comprising, by mass percentage: 50% Ni, 10% MgO as an auxiliary agent, and the balance being a SiO2 support.

[0145] The preparation method of the n-butyraldehyde liquid-phase hydrogenation catalyst is as follows:

[0146] S1. Dissolve Ni(NO3)2·6H2O and Mg(NO3)2·6H2O in deionized water to obtain a mixed salt solution with a concentration of 0.5M;

[0147] S2. Add SiO2 support powder to a mixed salt solution, evaporate the water at 80°C, dry the resulting solid at 100°C for 10 hours, and calcine it at 600°C for 4 hours in air to obtain the catalyst.

[0148] Example 16

[0149] Same as Example 1, except that: the catalyst in the first hydrogenation reactor is the n-butyraldehyde liquid-phase hydrogenation catalyst prepared in Example 8; and the catalyst in the second hydrogenation reactor is the n-butyraldehyde liquid-phase hydrogenation catalyst prepared in Example 9.

[0150] Testing showed that the conversion rate of n-butyraldehyde was >99%, and the selectivity of n-butanol was 99.3%. Under the same conditions, the two catalyst stages were run continuously for 500 hours, and the conversion rate and selectivity did not change significantly.

[0151] Example 17

[0152] Same as Example 1, except that: the catalyst in the first hydrogenation reactor is the n-butyraldehyde liquid-phase hydrogenation catalyst prepared in Example 10; and the catalyst in the second hydrogenation reactor is the n-butyraldehyde liquid-phase hydrogenation catalyst prepared in Example 11.

[0153] Testing showed that the conversion rate of n-butyraldehyde was >99%, and the selectivity of n-butanol was 98.1%. Under the same conditions, the two catalyst stages were run continuously for 500 hours, and the conversion rate and selectivity did not change significantly.

[0154] Example 18

[0155] Same as Example 1, except that: the catalyst in the first hydrogenation reactor is the n-butyraldehyde liquid-phase hydrogenation catalyst prepared in Example 12; and the catalyst in the second hydrogenation reactor is the n-butyraldehyde liquid-phase hydrogenation catalyst prepared in Example 13.

[0156] Testing showed that the conversion rate of n-butyraldehyde was >99%, and the selectivity of n-butanol was 99.1%. Under the same conditions, the two catalyst stages were run continuously for 500 hours, and the conversion rate and selectivity did not change significantly.

[0157] Example 19

[0158] Same as Example 1, except that: the catalyst in the first hydrogenation reactor is the n-butyraldehyde liquid-phase hydrogenation catalyst prepared in Example 14; and the catalyst in the second hydrogenation reactor is the n-butyraldehyde liquid-phase hydrogenation catalyst prepared in Example 15.

[0159] Testing showed that the conversion rate of n-butyraldehyde was >99%, and the selectivity of n-butanol was 99.0%. Under the same conditions, the two catalyst stages were run continuously for 500 hours, and the conversion rate and selectivity did not change significantly.

[0160] Comparative Example 5

[0161] Same as Example 16, except that the catalyst in the first hydrogenation reactor is the n-butyraldehyde liquid-phase hydrogenation catalyst prepared in Comparative Example 4.

[0162] The test results showed that the conversion rate of n-butyraldehyde was 95.5%, and the selectivity of n-butanol was 92.8%.

[0163] Comparative Example 6

[0164] Same as Example 16, except that the catalyst in the first hydrogenation reactor is the n-butyraldehyde liquid-phase hydrogenation catalyst prepared in Comparative Example 5.

[0165] The test results showed that the conversion rate of n-butyraldehyde was 93.8%, and the selectivity of n-butanol was 90.1%.

[0166] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. The application of a n-butyraldehyde liquid-phase hydrogenation catalyst in the production of n-butanol from n-butyraldehyde by liquid-phase hydrogenation, characterized in that, The liquid-phase hydrogenation of n-butyraldehyde to n-butanol is a two-stage continuous process. Specifically, n-butyraldehyde raw material first enters the first hydrogenation reactor for hydrogenation reaction, and then the product of the first hydrogenation reactor is used as reactant to directly enter the second hydrogenation reactor for deep hydrogenation reaction to obtain n-butanol. The n-butyraldehyde liquid-phase hydrogenation catalyst comprises, by mass percentage: The active ingredient comprises 20%–80%, the auxiliary agent comprises 2%–20%, and the remainder is a carrier. The active component is Ni; the auxiliary agent is at least one selected from MgO, ZnO, ZrO2, Cr2O3, Ga2O3, Y2O3, La2O3, CeO2, and Al2O3; the support is at least one selected from SiO2, Al2O3, and activated carbon. The preparation method of the n-butyraldehyde liquid-phase hydrogenation catalyst includes the following steps: Nickel salt and auxiliary salt are dissolved in deionized water to obtain a mixed salt solution; the support is dispersed in deionized water and heat-treated to obtain a support suspension; the mixed salt solution and precipitant are added to the support suspension to precipitate and age; the precipitate is washed, dried and calcined to obtain the n-butyraldehyde liquid-phase hydrogenation catalyst. The heat treatment temperature is 50℃~100℃, and the heat treatment time is 1~5 h.

2. The application according to claim 1, characterized in that, The nickel salt is at least one of Ni(NO3)2•6H2O, NiSO4•6H2O, NiCl2, and Ni(CH3COO)2.

3. The application according to claim 1, characterized in that, The auxiliary salt is at least one of Mg(NO3)2•6H2O, Zn(NO3)2•6H2O, ZrOCl2•8H2O, Cr(NO3)3•9H2O, Ga(NO3)3, Y(NO3)3•6H2O, La(NO3)3•6H2O, Ce(NO3)3•6H2O, and Al(NO3)3.

4. The application according to claim 1, characterized in that, The precipitant is at least one of NH3·H2O, (NH4)2CO3, NaOH, and Na2CO3 solution.

5. The application according to claim 1, characterized in that, The mass hourly space velocity (MSV) of the first hydrogenation reactor is 0.1–2 h⁻¹. -1 The molar ratio of hydrogen to n-butyraldehyde is (5~20):1, and the mass hourly space velocity (HHSV) of the second hydrogenation reactor is 0.5~5 h⁻¹. -1 .

6. The application according to claim 5, characterized in that, The mass hourly space velocity (MSV) of the first hydrogenation reactor is 0.1 to 1 h⁻¹. -1 The molar ratio of hydrogen to n-butyraldehyde is (5~15):

1.

7. The application according to claim 1, characterized in that, The reaction temperature of the hydrogenation reactor is 60℃~120℃ and the hydrogen pressure is 0.5~5.0 MPa.