N-butyraldehyde liquid phase hydrogenation catalyst as well as preparation method and application thereof

Abstract

The invention provides an n-butyraldehyde liquid phase hydrogenation catalyst as well as a preparation method and application thereof, and relates to the technical field of catalysts. The catalyst provided by the invention is an assistant-modified supported metal nickel catalyst, and is prepared from 20-80% of an active component Ni, 2-20% of an assistant and a carrier through a coprecipitation method. The catalyst provided by the invention is used for a two-stage hydrogenation process of n-butyraldehyde. The method is simple in process, low in cost, high in catalyst stability, moderate in surface acidity and alkalinity, capable of preparing the n-butyl alcohol with the high conversion rate of the n-butyraldehyde, capable of remarkably inhibiting generation of by-products and capable of improving the yield of the n-butyl alcohol, suitable for industrial application and capable of providing an excellent scheme for efficient preparation of the n-butyl alcohol.

Description

Technical Field

[0001] The present invention relates to the technical field of catalysts, and in particular to a liquid-phase hydrogenation catalyst for n-butyraldehyde, a preparation method thereof, and an application thereof. Background Art

[0002] n-Butanol is an important basic chemical raw material, which is widely used in the fields of chemicals, pharmaceuticals, food, and energy. It is mainly used for the production of chemicals such as plasticizer dibutyl phthalate, butyl acetate, butyl acrylate, and butyl methacrylate, and is also commonly used as a special solvent and an organic synthesis intermediate.

[0003] Industrial production methods of n-butanol include the acetaldehyde condensation method, the fermentation method, and the propylene hydroformylation method. Among them, the propylene hydroformylation method has become the mainstream process because of the cheap and easily available raw materials, mild reaction conditions, few side reactions, and high efficiency. This method uses propylene, carbon monoxide, and hydrogen as raw materials, generates n-butyraldehyde through carbonylation, and then obtains n-butanol through catalytic hydrogenation. The hydrogenation of n-butyraldehyde is one of the key steps in the propylene hydroformylation method.

[0004] Since the gas-phase hydrogenation method has high energy consumption, the liquid-phase hydrogenation method has gradually attracted attention. However, n-butyraldehyde is chemically active and prone to side reactions such as disproportionation and condensation under high-temperature liquid-phase conditions, resulting in low reaction selectivity, many by-products, and ultimately low yield and purity of n-butanol. Summary of the Invention

[0005] In view of this, the present invention provides a liquid-phase hydrogenation catalyst for n-butyraldehyde, a preparation method thereof, and an application thereof. The present invention uses a supported metal nickel modified with an auxiliary agent as a catalyst, combined with a specific two-stage hydrogenation process, which can ensure a high conversion rate of n-butyraldehyde, effectively inhibit the generation of by-products, and improve the yield of n-butanol during the preparation of n-butanol by liquid-phase hydrogenation of n-butyraldehyde, and is suitable for industrial application.

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

[0007] 20% - 80% of active components, 2% - 20% of auxiliary agents, and the balance is a carrier;

[0008] The active component is Ni; the auxiliary agents are MgO, ZnO, ZrO 2 , Cr 2 O 3 , Ga 2 O 3 , Y 2 O 3 , La 2 O 3 , CeO 2 , Al 2 O 3at least one of; the carrier is SiO 2 、Al 2 O 3 、activated carbon or at least one of them.

[0009] The present invention provides a method for preparing a liquid-phase hydrogenation catalyst for n-butyraldehyde, which specifically includes the following steps:

[0010] Dissolve nickel salt and promoter salt in deionized water to obtain a mixed salt solution; disperse the carrier in deionized water for heat treatment, and obtain a carrier suspension after the heat treatment is completed; add the mixed salt solution and the precipitant to the carrier suspension together, precipitate and age; wash, dry and calcine the precipitate to obtain the liquid-phase hydrogenation catalyst for n-butyraldehyde.

[0011] Preferably, the nickel salt is at least one of Ni(NO 3 ) 2 ·6H 2 O, NiSO 4 ·6H 2 O, NiCl 2 , Ni(CH 3 COO) 2 .

[0012] Preferably, the promoter salt is at least one of Mg(NO 3 ) 2 ·6H 2 O, Zn(NO 3 ) 2 ·6H 2 O, ZrOCl 2 ·8H 2 O, Cr(NO 3 ) 3 ·9H 2 O, Ga(NO 3 ) 3 , Y(NO 3 ) 3 ·6H 2 O, La(NO 3 ) 3 ·6H 2 O, Ce(NO 3 ) 3 ·6H 2 O, Al(NO 3 ) 3 .

[0013] Preferably, the precipitant is NH 3 ·H 2 O, (NH 4 ) 2 CO 3, NaOH, Na 2 CO 3 At least one of the solutions.

[0014] Preferably, the heat treatment temperature is 50°C to 100°C, and the heat treatment time is 1 to 5 h.

[0015] Preferably, the calcination temperature is 400°C to 800°C, and the calcination time is 2 to 8 h.

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

[0017] The present invention also provides an application of a n-butyraldehyde liquid-phase hydrogenation catalyst in the liquid-phase hydrogenation of n-butyraldehyde to n-butanol.

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

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

[0020] Preferably, during the entire hydrogenation process, the hydrogen pressure is 0.5 to 5 MPa

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

[0022] The present invention uses a supported metal nickel modified with a promoter as a catalyst. The strong interaction between the promoter, the active center nickel, and the carrier improves the stability of the catalyst. At the same time, the present invention regulates the interaction among the active component, the promoter, and the carrier by controlling the composition and ratio among the three, so that the catalyst has moderate surface acidity and basicity, which not only ensures the catalytic efficiency but also reduces the generation amount of by-products, making the catalyst exhibit excellent comprehensive performance during the two-stage liquid-phase hydrogenation of n-butyraldehyde to n-butanol.

[0023] The present invention prepares the catalyst by a simple co-precipitation method. The process is simple, the production cost is low, and it is easy to realize industrial production. At the same time, the present invention increases the number of active groups on the carrier surface by appropriately heat-treating the carrier, enhances the interaction between the carrier and the nickel and promoter salts, inhibits the sintering and agglomeration of the active component, improves the dispersion and stability, provides more active sites for the n-butyraldehyde liquid phase, and increases the hydrogenation catalytic activity.

[0024] The present invention adopts a two-stage hydrogenation process. In the first-stage hydrogenation reaction, most of the n-butyraldehyde can be converted into stable products and intermediates at low temperature, while in the second-stage hydrogenation reaction, the remaining small amount of n-butyraldehyde and intermediates can be hydrogenated into n-butanol. Thus, while ensuring a high conversion rate, the formation of by-products can be effectively inhibited, and the yield of n-butanol can be increased. Detailed implementation manners

[0025] Next, in combination with the embodiments of the present invention, the technical solutions of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0026] The present invention provides a liquid-phase hydrogenation catalyst for n-butyraldehyde, which, calculated by mass percentage, includes:

[0027] 20% - 80% of active components, 2% - 20% of promoters, and the balance is a carrier;

[0028] The active component is Ni; the promoters are at least one of MgO, ZnO, ZrO 2 , Cr 2 O 3 , Ga 2 O 3 , Y 2 O 3 , La 2 O 3 , CeO 2 , Al 2 O 3 ; and the carrier is at least one of SiO 2 , Al 2 O 3 , activated carbon.

[0029] In some specific embodiments of the present invention, the liquid-phase hydrogenation catalyst for n-butyraldehyde, calculated by mass percentage, includes: 30 - 60% of active components; 5 - 10% of promoters, and the balance is a carrier.

[0030] In some specific embodiments of the present invention, the nickel salt is at least one of Ni(NO 3 ) 2 ·6H 2 O, NiSO 4 ·6H 2 O, NiCl 2 , Ni(CH 3 COO) 2 ; and the promoter salt is Mg(NO 3 )2 ·6H 2 O, Zn(NO 3 ) 2 ·6H 2 O, ZrOCl 2 ·8H 2 O, Cr(NO 3 ) 3 ·9H 2 O, Ga(NO 3 ) 3 , Y(NO 3 ) 3 ·6H 2 O, La(NO 3 ) 3 ·6H 2 O, Ce(NO 3 ) 3 ·6H 2 O, Al(NO 3 ) 3 at least one of

[0031] The present invention provides a method for preparing a liquid-phase hydrogenation catalyst for n-butyraldehyde, which specifically includes the following steps:

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

[0033] Dissolving the active component (nickel salt) and the promoter salt uniformly can ensure the 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 avoid the formation of too large or too dense precipitate particles due to too high concentration, thereby reducing the dispersion of active sites;

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

[0035] The present invention improves the surface activity of the carrier through heat treatment of the carrier, enhances its interaction with the active component and the promoter, and at the same time increases the porosity to provide more active sites for the catalyst. Controlling the heat treatment temperature and treatment time can balance the generation of active sites and the integrity of the carrier structure, preventing structure collapse or phase transformation;

[0036] Carrier concentration 20 - 80 g / L: Ensure the dispersion of the carrier in the liquid phase and avoid deposition or being too dilute from affecting the uniformity of the precipitation reaction.

[0037] S3. Add the mixed salt solution of S1 and the precipitant to the carrier suspension of S2, and age at 50 °C to 100 °C for 4 to 10 h;

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

[0039] S4. Wash the precipitate, dry it at 90°C to 120°C for 8 to 12 hours, and then calcine it at 400°C to 800°C for 2 to 8 hours. After cooling, the liquid-phase hydrogenation catalyst for n-butyraldehyde 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 NH 3 ·H 2 O, (NH 4 ) 2 CO 3 , NaOH, Na 2 CO 3 solution. The concentration of the precipitant solution is 10% to 40%, and the molar ratio of the precipitant to the nickel salt and the promoter salt is 1:1.2.

[0042] The present invention also provides an application of the liquid-phase hydrogenation catalyst for n-butyraldehyde in the liquid-phase hydrogenation of n-butyraldehyde to n-butanol.

[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, and the hydrogenation process is a two-stage continuous process. The specific steps are as follows:

[0044] n-Butyraldehyde enters the first hydrogenation reactor and undergoes primary hydrogenation under the condition that the molar ratio of hydrogen to n-butyraldehyde is (5 to 20):1. The mass space velocity of the first hydrogenation reactor is 0.1 to 2 h -1 , and the primary hydrogenation product enters the second hydrogenation reactor as reaction material for deep hydrogenation. The mass space velocity of the second hydrogenation reactor is 0.5 to 5 h -1 . After the deep hydrogenation reaction, n-butanol is obtained. The hydrogen pressure during the primary hydrogenation and the deep hydrogenation is 0.5 to 5 MPa, and the reaction temperature is 60°C to 120°C.

[0045] Next, the technical solutions in the embodiments of the present application will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present application, not all of them. Based on the embodiments in the present application, other embodiments obtained by those of ordinary skill in the art without creative efforts all belong to the scope of protection of the invention. In the following embodiments, all raw materials are commercially available.

[0046] Except as otherwise specified, all experiments were repeated three times, and the results were expressed as the average value. A significant difference was indicated when P < 0.05.

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

[0048] In a fixed-bed continuous-flow reactor, under the conditions of a hydrogen pressure of 3.0 MPa and a molar ratio of hydrogen to n-butyraldehyde of 10:1, the reaction temperature of the first hydrogenation reactor was 70 °C and the mass space velocity was 1.0 h -1 ; the reaction temperature of the second hydrogenation reactor was 90 °C and the mass space velocity was 3.0 h -1 , n-butyraldehyde was contacted with the hydrogenation catalyst in the two-stage reactor respectively to obtain the n-butanol product.

[0049] Among them, the catalyst in the first hydrogenation reactor was Ni-ZrO 2 / SiO 2 n-butyraldehyde liquid-phase hydrogenation catalyst; the catalyst in the second hydrogenation reactor was Ni-Al 2 O 3 / SiO 2 n-butyraldehyde liquid-phase hydrogenation catalyst.

[0050] The Ni-ZrO 2 / SiO 2 n-butyraldehyde liquid-phase hydrogenation catalyst, including by mass percentage: Ni 40%, promoter ZrO 2 8%, and the balance was SiO 2 carrier;

[0051] The preparation method of this catalyst is as follows:

[0052] S1. Dissolve Ni(NO 3 ) 2 ·6H 2 O and ZrOCl 2 ·8H 2 O in deionized water to obtain a 0.5 M mixed salt solution;

[0053] S2. Under vigorous stirring, disperse SiO 2 powder in deionized water and heat-treat it at 80 °C for 3 h. After the heat treatment, a carrier suspension with a carrier concentration of 50 g / L was obtained;

[0054] S3. Add the mixed salt solution of S1 and 20% Na 2 CO 3 to the carrier suspension of S2, where the molar amount of Na 2 CO 3 was 1.2 times that of the mixed salt. After precipitation, it was aged at 80 °C for 6 h;

[0055] S4. Wash the precipitate, dry it at 100 °C for 10 h, then calcine it at 600 °C in an air atmosphere for 4 h. After cooling, the Ni-ZrO 2 / SiO 2 n-butanal liquid-phase hydrogenation catalyst is obtained.

[0056] The said Ni-Al 2 O 3 / SiO 2 n-butanal liquid-phase hydrogenation catalyst comprises, by mass percentage:

[0057] Ni 50%, promoter Al 2 O 3 8%, the balance being SiO 2 support;

[0058] The preparation method of this catalyst is as follows:

[0059] S1. Dissolve NiSO 4 ·6H 2 O and Al(NO 3 ) 3 in deionized water to obtain a 0.5 M mixed salt solution;

[0060] S2. Under vigorous stirring, disperse SiO 2 powder in deionized water and heat-treat it at 80 °C for 3 h. After the heat treatment, a support suspension with a support concentration of 50 g / L is obtained;

[0061] S3. Add the mixed salt solution of S1 and 20% Na 2 CO 3 to the support suspension of S2, where the molar amount of Na 2 CO 3 is 1.2 times that of the mixed salt. After precipitation, age it at 80 °C for 6 h;

[0062] S4. Wash the precipitate, dry it at 100 °C for 10 h, then calcine it at 600 °C in an air atmosphere for 4 h. After cooling, the Ni-ZrO 2 / SiO 2 n-butanal liquid-phase hydrogenation catalyst is obtained.

[0063] After detection, the conversion rate of n-butanal > 99%, and the selectivity for n-butanol is 99.2%. Under the same conditions, the two-stage catalyst was continuously operated for 500 h, 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] After testing, the conversion rate of n-butyraldehyde > 99%, and the selectivity for n-butanol is 98.6%. Under the same conditions, the two-stage catalyst was continuously operated for 500 h, 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] After testing, the conversion rate of n-butyraldehyde > 99%, and the selectivity for n-butanol is 99.4%. Under the same conditions, the two-stage catalyst was continuously operated for 500 h, 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 space velocity is 2.0 h -1 ; In the first hydrogenation reactor, Ni-ZrO 2 / SiO 2 The liquid-phase hydrogenation catalyst for n-butyraldehyde comprises, by mass percentage: Ni 30%, promoter Al 2 O 3 5%, and the balance is SiO 2 support; In the second hydrogenation reactor, Ni-Al 2 O 3 / SiO 2 The liquid-phase hydrogenation catalyst for n-butyraldehyde comprises, by mass percentage: Ni 50%, promoter Al 2 O 3 8%, and the balance is SiO 2 support.

[0072] After testing, the conversion rate of n-butyraldehyde > 99%, and the selectivity for n-butanol is 97.9%. Under the same conditions, the two-stage catalyst was continuously operated for 500 h, 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 space velocity is 2.0 h -1 ; In the first hydrogenation reactor, Ni-ZrO 2 / SiO 2 The liquid-phase hydrogenation catalyst for n-butyraldehyde comprises, by mass percentage: Ni 60%, promoter Al 2 O 3 10%, and the balance is SiO2 Carrier

[0075] After detection, the conversion rate of n-butanal > 99%, and the selectivity for n-butanol is 99.5%. Under the same conditions, the two-stage catalyst was continuously operated for 500 h, 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 space velocity is 0.5 h -1 ; Ni-Al in the second hydrogenation reactor 2 O 3 / SiO 2 The liquid-phase hydrogenation catalyst for n-butanal comprises, by mass percentage: 60% of Ni, 10% of promoter Al 2 O 3 10%, and the balance is SiO 2 Carrier

[0078] After detection, the conversion rate of n-butanal > 99%, and the selectivity for n-butanol is 98.9%. Under the same conditions, the two-stage catalyst was continuously operated for 500 h, 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 space velocity is 5.0 h -1 ; Ni-Al in the second hydrogenation reactor 2 O 3 / SiO 2 The liquid-phase hydrogenation catalyst for n-butanal comprises, by mass percentage: 30% of Ni, 5% of promoter Al 2 O 3 5%, and the balance is SiO 2 Carrier

[0081] After detection, the conversion rate of n-butanal > 99%, and the selectivity for n-butanol is 98.1%. Under the same conditions, the two-stage catalyst was continuously operated for 500 h, and the conversion rate and selectivity did not change significantly.

[0082] Comparative Example 1 A method for the liquid-phase hydrogenation of n-butanal to n-butanol, the steps are as follows:

[0083] In a fixed-bed continuous-flow reactor, at a reaction temperature of 70 °C, a hydrogen pressure of 3.0 MPa, a molar ratio of hydrogen to n-butanal of 10:1, and a mass space velocity of 1.0 h -1 Under the conditions, n-butanal is contacted with a hydrogenation catalyst to obtain an n-butanol product;

[0084] The catalyst is Ni-ZrO2 / SiO 2 The n-butanal liquid-phase hydrogenation catalyst comprises, by mass percentage: Ni 40%, ZrO 2 8%, and the balance is SiO 2 support.

[0085] After detection, the conversion rate of n-butanal > 99%, and the selectivity of n-butanol is 92.0%.

[0086] Comparative Example 2 A method for preparing n-butanol by liquid-phase hydrogenation of n-butanal, the steps are as follows:

[0087] In a fixed-bed continuous-flow reactor, at a reaction temperature of 90 °C, a hydrogen pressure of 3.0 MPa, a molar ratio of hydrogen to n-butanal of 10:1, and a mass space velocity of 3.0 h -1 Under the conditions, n-butanal is contacted with the hydrogenation catalyst to obtain n-butanol product;

[0088] The catalyst is Ni-Al 2 O 3 / SiO 2 The n-butanal liquid-phase hydrogenation catalyst comprises, by mass percentage: Ni 50%, promoter Al 2 O 3 8%, and the balance is SiO 2 support.

[0089] After detection, the conversion rate of n-butanal > 99%, and the selectivity of n-butanol is 91.5%.

[0090] Example 8 A Ni-MgO / SiO 2 The n-butanal liquid-phase hydrogenation catalyst comprises, by mass percentage: Ni 50%, promoter MgO 10%, and the balance is SiO 2 support.

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

[0092] S1. Dissolve Ni(NO 3 ) 2 ·6H 2 O and Mg(NO 3 ) 2 ·6H 2 O in deionized water to obtain a mixed salt solution with a concentration of 0.5 M;

[0093] S2. Under vigorous stirring, disperse SiO 2 powder in deionized water and treat it at 80 °C for 3 h to obtain a carrier suspension of 50 g / L;

[0094] S3. Mix the mixed salt solution with 20% Na 2 CO3 The solutions are jointly added to the carrier suspension, where the molar amount of Na 2 CO 3 is 1.2 times that of the mixed salts, aged at 80 °C for 6 h, and the precipitate is obtained by filtration;

[0095] S4. After the precipitate is washed, it is dried at 100 °C for 10 h and calcined at 600 °C for 4 h in an air atmosphere to obtain the catalyst.

[0096] Example 9 A Ni-ZnO / Al 2 O 3 n-butanal liquid-phase hydrogenation catalyst, including by mass percentage: Ni 20%, promoter ZnO 2%, and the balance is Al 2 O 3 carrier.

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

[0098] S1. NiSO 4 ·6H 2 O and Zn(NO 3 ) 2 ·6H 2 O are dissolved in deionized water to obtain a mixed salt solution with a concentration of 0.5 M;

[0099] S2. Under vigorous stirring, Al 2 O 3 powder is dispersed in deionized water and treated at 80 °C for 3 h to obtain a carrier suspension with a concentration of 80 g / L;

[0100] S3. The mixed salt solution and the Na 2 CO 3 solution with a concentration of 20% are jointly added to the carrier suspension, where the molar amount of Na 2 CO 3 is 1.2 times that of the mixed salts, aged at 80 °C for 6 h, and the precipitate is obtained by filtration;

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

[0102] Example 10 A Ni-ZrO 2 / activated carbon n-butanal liquid-phase hydrogenation catalyst, including by mass percentage: Ni 80%, promoter ZrO 2 10%, and the balance is the activated carbon carrier.

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

[0104] S1. NiCl2 ·6H 2 O and ZrOCl 2 ·8H 2 O is dissolved in deionized water to obtain a mixed salt solution with a concentration of 0.5 M;

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

[0106] S3. The mixed salt solution and a solution of Na 2 CO 3 with a concentration of 20% are added to the carrier suspension together, where the molar amount of Na 2 CO 3 is 1.2 times that of the mixed salt, aged at 80 °C for 6 h, and the precipitate is obtained by filtration;

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

[0108] Example 11 A Ni-Cr 2 O 3 / SiO 2 n-butanal liquid-phase hydrogenation catalyst, including by mass percentage: Ni 50%, promoter Cr 2 O 3 20%, and the balance is SiO 2 carrier.

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

[0110] S1. Ni(OAc) 2 ·4H 2 O and Cr(NO 3 ) 3 ·9H 2 O are dissolved in deionized water to obtain a mixed salt solution with a concentration of 0.5 M;

[0111] S2. Under vigorous stirring, SiO 2 powder is dispersed in deionized water and treated at 80 °C for 3 h to obtain a carrier suspension with a concentration of 50 g / L;

[0112] S3. The mixed salt solution and a solution of Na 2 CO 3 with a concentration of 40% are added to the carrier suspension together, where the molar amount of Na 2 CO 3 is 1.2 times that of the mixed salt, aged at 80 °C for 6 h, and the precipitate is obtained by filtration;

[0113] S4. After the precipitate is washed, it is dried at 100 °C for 10 h and then calcined at 600 °C for 4 h in an air atmosphere to obtain the catalyst.

[0114] Example 12 A Ni-Ga 2 O 3 / SiO 2 n-butanal liquid-phase hydrogenation catalyst, including by mass percentage: Ni 50%, promoter Ga 2 O 3 10%, the balance being SiO 2 support.

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

[0116] S1. Dissolve Ni(NO 3 ) 2 ·6H 2 O and Ga(NO 3 ) 3 in deionized water to obtain a mixed salt solution with a concentration of 0.5 M;

[0117] S2. Under vigorous stirring, disperse the SiO 2 support powder in deionized water and treat it at 50 °C for 5 h to obtain a support suspension of 50 g / L;

[0118] S3. Add the mixed salt solution and 10% Na 2 CO 3 together into the support suspension, where the molar amount of Na 2 CO 3 is 1.2 times that of the mixed salt, age at 50 °C for 10 h, and filter to obtain a precipitate;

[0119] S4. After the precipitate is washed, it is dried at 100 °C for 10 h and then calcined at 800 °C for 2 h in an air atmosphere to obtain the catalyst.

[0120] Example 13 A Ni-Y 2 O 3 / SiO 2 n-butanal liquid-phase hydrogenation catalyst, including by mass percentage: Ni 50%, promoter Y 2 O 3 10%, the balance being SiO 2 support.

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

[0122] S1. Dissolve Ni(NO 3 ) 2 ·6H 2 O and Y(NO3 ) 3 ·6H 2 Dissolve Ni(NO₃)₂·6H₂O and La(NO₃)₃·6H₂O in deionized water to obtain a mixed salt solution with a concentration of 0.5 M;

[0123] S2. Under vigorous stirring, disperse the SiO₂ carrier powder in deionized water and treat it at 100 °C for 1 h to obtain a carrier suspension with a concentration of 50 g / L; 2 Dissolve Ni(NO₃)₂·6H₂O and La(NO₃)₃·6H₂O in deionized water to obtain a mixed salt solution with a concentration of 0.5 M;

[0124] S3. Add the mixed salt solution and 20% ammonium carbonate solution to the carrier suspension together, where the molar amount of Na₂CO₃ is 1.2 times that of the mixed salt, age at 100 °C for 4 h, and filter to obtain a precipitate; 2 CO 3 After the precipitate is washed, dry it at 100 °C for 10 h and calcine it at 400 °C in an air atmosphere for 8 h to obtain the catalyst.

[0125] S4. After the precipitate is washed, dry it at 100 °C for 10 h and calcine it at 400 °C in an air atmosphere for 8 h to obtain the catalyst.

[0126] Example 14 A Ni-La₂O₃ / SiO₂ liquid-phase hydrogenation catalyst for n-butanal, including by mass percentage: Ni 50%, promoter La₂O₃ 10%, and the balance is the SiO₂ carrier. 2 O 3 / SiO 2 The preparation method of the liquid-phase hydrogenation catalyst for n-butanal is as follows: 2 O 3 10%, and the balance is the SiO₂ carrier. 2 The carrier.

[0127] The preparation method of the liquid-phase hydrogenation catalyst for n-butanal 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 0.5 M; 3 ) 2 ·6H 2 O and La(NO₃)₃·6H₂O in deionized water to obtain a mixed salt solution with a concentration of 0.5 M; 3 ) 3 ·6H 2 Dissolve Ni(NO₃)₂·6H₂O and La(NO₃)₃·6H₂O in deionized water to obtain a mixed salt solution with a concentration of 0.5 M;

[0129] S2. Under vigorous stirring, disperse the SiO₂ carrier powder in deionized water and treat it at 80 °C for 3 h to obtain a carrier suspension with a concentration of 50 g / L; 2 Dissolve Ni(NO₃)₂·6H₂O and La(NO₃)₃·6H₂O in deionized water to obtain a mixed salt solution with a concentration of 0.5 M;

[0130] S3. Add the mixed salt solution and 20% sodium hydroxide solution to the carrier suspension together, where the molar amount of Na₂CO₃ is 1.2 times that of the mixed salt, age at 80 °C for 6 h, and filter to obtain a precipitate; 2 CO 3 After the precipitate is washed, dry it at 90 °C for 12 h and calcine it at 600 °C in an air atmosphere for 4 h to obtain the catalyst.

[0131] S4. After the precipitate is washed, dry it at 90 °C for 12 h and calcine it at 600 °C in an air atmosphere for 4 h to obtain the catalyst.

[0132] Example 15 A Ni-CeO 2 / SiO 2 n-butanal liquid-phase hydrogenation catalyst, including by mass percentage: Ni 50%, promoter CeO 2 10%, the balance being SiO 2 support.

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

[0134] S1. Dissolve Ni(NO 3 ) 2 ·6H 2 O and Ce(NO 3 ) 3 ·6H 2 O in deionized water to obtain a mixed salt solution with a concentration of 0.5 M;

[0135] S2. Under vigorous stirring, disperse the SiO 2 support powder in deionized water, and treat it at 80 °C for 3 h to obtain a support suspension with a concentration of 50 g / L;

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

[0137] S4. After washing the precipitate, dry it at 120 °C for 8 h and calcine it at 600 °C in an air atmosphere for 4 h to obtain the catalyst.

[0138] Comparative Example 3 A Ni / SiO 2 n-butanal liquid-phase hydrogenation catalyst, including by mass percentage: Ni 50%, the balance being SiO 2 support.

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

[0140] S1. Dissolve Ni(NO 3 ) 2 ·6H 2 O in deionized water to obtain a salt solution with a concentration of 0.5 M;

[0141] S2. Under vigorous stirring, disperse the SiO 2 support powder in 1000 mL of deionized water, and treat it at 80 °C for 3 h to obtain a support suspension with a concentration of 50 g / L;

[0142] S3. Add the mixed salt solution and 20% Na 2 CO 3 together to the support suspension, where Na2 CO 3 The molar amount of CO is 1.2 times that of the mixed salt, aged at 80 °C for 6 h, and the precipitate is obtained by filtration;

[0143] S4. After the precipitate is washed, it is dried at 100 °C for 10 h and calcined at 600 °C for 4 h in an air atmosphere to obtain the catalyst.

[0144] Comparative Example 4 A Ni-MgO / SiO 2 / liquid-phase hydrogenation catalyst for n-butyraldehyde, including by mass percentage: Ni 50%, promoter MgO 10%, and the balance is SiO 2 support.

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

[0146] S1. Dissolve Ni(NO 3 ) 2 ·6H 2 O and Mg(NO 3 ) 2 ·6H 2 O in deionized water to obtain a mixed salt solution with a concentration of 0.5 M;

[0147] S2. Add the SiO 2 support powder to the mixed salt solution, evaporate the water at 80 °C, dry the obtained solid at 100 °C for 10 h, and calcine it at 600 °C for 4 h in an air atmosphere to obtain the catalyst.

[0148] Example 16

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

[0150] After detection, the conversion rate of n-butyraldehyde > 99%, and the selectivity of n-butanol is 99.3%. Under the same conditions, the two-stage catalyst was continuously operated for 500 h, and the conversion rate and selectivity did not change significantly.

[0151] Example 17

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

[0153] After detection, the conversion rate of n-butyraldehyde > 99%, and the selectivity of n-butanol is 98.1%. Under the same conditions, the two-stage catalyst was continuously operated for 500 h, 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-butanal liquid-phase hydrogenation catalyst prepared in Example 12; the catalyst in the second hydrogenation reactor is the n-butanal liquid-phase hydrogenation catalyst prepared in Example 13.

[0156] After detection, the conversion rate of n-butanal > 99%, and the selectivity of n-butanol is 99.1%. Under the same conditions, the two-stage catalyst was continuously operated for 500 h, 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-butanal liquid-phase hydrogenation catalyst prepared in Example 14; the catalyst in the second hydrogenation reactor is the n-butanal liquid-phase hydrogenation catalyst prepared in Example 15.

[0159] After detection, the conversion rate of n-butanal > 99%, and the selectivity of n-butanol is 99.0%. Under the same conditions, the two-stage catalyst was continuously operated for 500 h, 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-butanal liquid-phase hydrogenation catalyst prepared in Comparative Example 4.

[0162] After detection, the conversion rate of n-butanal is 95.5%, and the selectivity of n-butanol is 92.8%.

[0163] Comparative Example 6

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

[0165] After detection, the conversion rate of n-butanal is 93.8%, and the selectivity of n-butanol is 90.1%.

[0166] The above-described embodiments merely represent several implementation manners of the present invention. The description is relatively specific and detailed, but it should not be construed as a limitation on the scope of the invention patent. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several deformations and improvements can still be made, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the present invention patent shall be subject to the appended claims.

Claims

1. A liquid phase hydrogenation catalyst for n-butyraldehyde, characterized in that In terms of mass percentage, it includes: Active ingredient 20% to 80%, auxiliary agent 2% to 20%, and the balance is carrier; 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 carrier is at least one of SiO2, Al2O3, and activated carbon.

2. The method for preparing the liquid phase hydrogenation catalyst of n-butyraldehyde according to claim 1, characterized in that: The following steps are involved: Dissolving nickel salt and auxiliary salt in deionized water to obtain a mixed salt solution; The carrier is dispersed in deionized water and subjected to heat treatment, and a carrier suspension is obtained after the heat treatment is completed; adding the mixed salt solution and the precipitant into the carrier suspension to precipitate and age; The precipitate is washed, dried and calcined to obtain the n-butyraldehyde liquid phase hydrogenation catalyst.

3. The preparation method according to claim 2, characterized in that: The nickel salt is at least one of Ni(NO3)2·6H2O, NiSO4·6H2O, NiCl2, and Ni(CH3COO)2.

4. The preparation method according to claim 2, 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.

5. The preparation method according to claim 2, characterized in that: The precipitant is at least one of NH3·H2O, (NH4)2CO3, NaOH and Na2CO3 solution.

6. The preparation method according to claim 2, characterized in that: The heat treatment temperature is 50° C. to 100° C., and the heat treatment time is 1 to 5 hours.

7. Use of a n-butyraldehyde liquid phase hydrogenation catalyst in the preparation of n-butanol by liquid phase hydrogenation of n-butyraldehyde, characterized in that: The n-butyraldehyde liquid phase hydrogenation catalyst is the n-butyraldehyde liquid phase hydrogenation catalyst according to claim 1 or the n-butyraldehyde liquid phase hydrogenation catalyst prepared by the method according to any one of claims 2 to 8.

8. The use according to claim 7, characterized in that: The liquid phase hydrogenation of n-butyraldehyde to n-butanol is a two-stage continuous process, specifically: the 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 the reaction material and directly enters the second hydrogenation reactor for deep hydrogenation reaction to obtain n-butanol.

9. The use according to claim 8, characterized in that: The liquid phase hydrogenation of n-butyraldehyde to n-butanol is a two-stage continuous process, and the mass space velocity of the first hydrogenation reactor is 0.1 to 2 h -1 The molar ratio of hydrogen to n-butyraldehyde is (5-20):1, and the mass space velocity of the second hydrogenation reactor is 0.5-5h -1 More preferably, the mass space velocity of the first hydrogenation reactor is 0.1 to 1 h -1 , the molar ratio of hydrogen to n-butyraldehyde is (5-15):

1.

10. The use according to claim 8, characterized in that: The reaction temperature of the hydrogenation reactor is 60° C. to 120° C., and the hydrogen pressure is 0.5 to 5.0 MPa.