Ammonolysis catalyst as well as preparation method and application thereof

Abstract

The invention discloses an ammonolysis catalyst and a preparation method and application thereof, and relates to the technical field of catalysts, the catalyst comprises a carrier and an active component loaded on the carrier; the active component comprises a main active component and an auxiliary agent; the main active component is Ni; the auxiliary agent is at least one of IIIB group elements, VIB group elements, VIIB group elements and IIIA group elements; based on the weight percentage of the catalyst, the content of the main active component is 20-45wt%; and the content of the auxiliary agent is 0.5-4.0 wt%. According to the method, secondary amine and ammonia gas are subjected to ammonolysis reaction through an ammonolysis catalyst bed layer in the presence of hydrogen, so that primary amine can be generated with higher selectivity.

Description

Technical Field

[0001] The present invention relates to the technical field of catalysts, and more particularly to an ammonolysis catalyst and a preparation method and application thereof. Background Art

[0002] Amines refer to products produced when one or more hydrogen atoms in an ammonia molecule are replaced by hydrocarbon groups. Amines can be divided into primary amines, secondary amines, and tertiary amines according to the number of hydrogen atoms replaced in the amine molecule. Amines are widely present in the biological world and have extremely important physiological and biological activities. For example, proteins, nucleic acids, many hormones, antibiotics, and alkaloids are all derivatives of amines. Most of the drugs used clinically are also amines or amine derivatives.

[0003] The properties of amines are very similar to those of ammonia. Low-order aliphatic amines are gases or volatile liquids with an unpleasant odor; high-order amines are solids; aromatic amines are high-boiling-point liquids or low-melting-point solids with a special odor, insoluble in water, and soluble in organic solvents. Like ammonia, amines are polar compounds. The boiling point of amines is higher than that of hydrocarbons with similar relative molecular mass, but lower than that of alcohols or carboxylic acids with similar relative molecular mass. Tertiary amines have no hydrogen atoms on their nitrogen atoms and cannot form hydrogen bonds between molecules, so their boiling points are lower than those of their primary and secondary isomers. Primary, secondary, and tertiary amines can all form hydrogen bonds with water molecules, so low-order amines are easily soluble in water, but amines with 6 carbon atoms are insoluble in water. In addition, amines are generally soluble in organic solvents such as ether, alcohol, and benzene.

[0004] Secondary amine is a type of amine, also known as secondary amine, with the general formula R2NH. It reacts with primary amine (RNH2), tertiary amine (R3N), quaternary ammonium salt (R4N + X - ) together constitute the four major categories of organic amines. Generally speaking, alcohols, ketones or aldehydes are usually used to react with ammonia or amines to prepare the corresponding amines. However, in the process of amination or amination, primary amines, secondary amines and even tertiary amines are generally reacted at the same time. In the consumer market, primary amines are mostly the most demanded varieties, such as monoisopropylamine, monoethylamine, ethylenediamine, hexamethylenediamine and other primary amine products.

[0005] Monoethylamine, also known as ethylamine, aminoethane, is a colorless liquid, flammable, volatile and has an ammonia smell. It is miscible with water, alcohol and ether, and is used to make dyes, rubber accelerators, surfactants, and also used to make pesticides such as simazine and atrazine. Chinese patent CN112691677 discloses a catalyst for preparing ethylamine by hydrogenation of ethanol and its application. It can be seen from the data of Example 14 that the product contains monoethylamine, diethylamine and triethylamine, and the proportion of diethylamine is as high as more than 50%, while the proportion of monoethylamine is only 16-17%. Chinese patent CN114315593 discloses a method for producing ethylamine with an adjustable product ratio, wherein the diethylamine produced in the product is further reacted with ethanol, ammonia, etc. to prepare triethylamine, thereby achieving an adjustable product ratio of ethylamine.

[0006] Ethylenediamine, also known as 1,2-diaminoethane, is a colorless, transparent, viscous liquid that is easily soluble in water and miscible with ethanol. It has the characteristics of alkalinity and surface activity. It is an important chemical raw material and fine chemical intermediate. It is widely used in epoxy resin curing agent, pesticide, medicine, low molecular weight polyamide resin, chelating agent and other fields, involving many industries. Chinese patent CN110201671 discloses a catalyst for preparing monoethanolamine and liquid ammonia reduction amination synthesis of ethyleneamine using an ammonia complex and its preparation and use method, which effectively improves the selectivity of ethanolamine reduction amination synthesis of ethylenediamine under hydrogen conditions, up to 69%, and the rest are by-products such as diethylenetriamine. Chinese patent CN109908900A discloses a supported catalyst for preparing ethyleneamines by the ethanolamine process. The main active component of the catalyst is Ni, Co or Cu, and the auxiliary agent is at least one of metals or oxides such as Fe, Cr, Re, Ru, B, Mg, Ba, etc.; the carrier is alumina, silica, alumina-silica, H-ZSM-5 or H-β molecular sieve. The main products of the catalyst are ethylenediamine and piperazine, and diethylenetriamine (DETA), hydroxyethylpiperazine (HEP), N-aminoethylpiperazine (AEP) and hydroxyethylethylenediamine (AEEA) are produced as by-products. The selectivity of diethylenetriamine in the embodiment is 6.9-18.3%.

[0007] 1,6-Hexanediamine, also known as 1,6-diaminohexane and hexamethylenediamine, has a chemical formula of C6H 16N2 is an important chemical intermediate, mainly used in organic synthesis and polymer production, and can also be used as epoxy resin curing agent and chemical reagent. Chinese patent CN116272969 discloses a catalyst for synthesizing hexamethylenediamine, the catalyst comprising a carrier and ruthenium loaded on the carrier, the carrier being obtained by calcining a phenanthroline compound and a carrier matrix. The catalyst was used for the reaction of hexanediol reductive amination to synthesize hexanediamine. The conversion rate of hexanediol was 100%, the selectivity of hexanediamine was about 50%, and other by-products were: cyclohexylimine, 6-aminolyzed-1-hexanol, hexylamine, hexanol, dimer (N-(6-aminohexyl)-1,6-hexanediamine and N-(6-aminohexyl)cyclohexylimine. The literature Science China Chemsitry 2017, 60, 920-926. reported a metal ruthenium-based catalyst for the reductive amination of hexanediol to prepare hexanediamine. The data in the article showed that the conversion rate of hexanediol was 100%, the selectivity of hexanediamine was only 38.4%, and there were many by-products.

[0008] It is known from the literature that when alcohols, ketones or aldehydes are used to react with ammonia or amines to prepare corresponding amines, not only primary amines are generated, but secondary amines or even tertiary amines are generally generated in the reaction. In order to increase the yield of primary amines to a greater extent, it is often necessary to return the generated secondary amines or tertiary amines to the reaction inlet and then carry out an amination reaction together with fresh raw materials. This method will cause a large amount of materials to circulate back and forth continuously, which consumes a lot of energy and energy, and will also produce a large amount of secondary amines or even tertiary amines. Therefore, it is of great economic and practical significance to develop an ammonialysis catalyst to prepare primary amines by ammonialysis of secondary amines. Summary of the invention

[0009] In order to solve the problems existing in the prior art, the present invention provides an ammonolysis catalyst and a preparation method and application thereof. In the present invention, secondary amine and ammonia are subjected to an ammonolysis reaction in the presence of hydrogen through an ammonolysis catalyst bed, thereby generating primary amines with higher selectivity.

[0010] One of the objects of the present invention is to provide an ammonolysis catalyst.

[0011] The ammonolysis catalyst of the present invention comprises a carrier and an active component supported on the carrier;

[0012] The active components include main active components and auxiliary agents;

[0013] The main active component is Ni;

[0014] The auxiliary agent is at least one of the elements of Group IIIB, Group VIB, Group VIIB and Group IIIA;

[0015] In order to balance the different catalytic properties of ammonolysis catalysts, such as dehydrogenation, ammonolysis and adsorption and desorption capabilities,

[0016] Taking the total weight of the catalyst as 100%:

[0017] The content of the main active component is 20-45wt%;

[0018] The content of the auxiliary agent is 0.5-4.0wt%.

[0019] Preferably,

[0020] Taking the total weight of the catalyst as 100%:

[0021] The content of the main active component is 24-42wt%;

[0022] The content of the auxiliary agent is 0.75-3.75wt%.

[0023] Preferably,

[0024] In order to further reduce side reactions and improve primary amine selectivity in the ammonolysis reaction process, the auxiliary agent is at least one of La, Mn and Re, preferably Re; and / or,

[0025] The carrier is a modified zirconium dioxide carrier; preferably, the modified zirconium dioxide carrier is zirconium dioxide modified by mordenite; more preferably, the content of zirconium dioxide is 50-80wt% of the total weight of the carrier, preferably 60-75wt%.

[0026] Preferably,

[0027] The modified zirconium dioxide carrier is prepared by fully stirring a zirconium source and mordenite, adding an extrusion aid solution, extruding and molding, and drying and calcining.

[0028] The zirconium dioxide carrier itself has certain acidic and basic sites, and its specific properties vary with the production method, calcination and processing of the carrier raw materials. The inventors have found that it can also be artificially added with some other substances to change it. After research, the inventors found that adding an appropriate amount of mordenite helps to improve the pore structure and surface physical and chemical properties of the carrier, thereby increasing the yield of primary amines.

[0029] In the technical solution of the present invention, the carrier can also be treated with fluorine-containing compounds, phosphorus-containing compounds, sulfur-containing compounds or selenium-containing compounds, and the above compounds can be added for modification during the carrier molding process or the catalyst molding process. In addition, these compounds or other forms of corresponding elements can also be introduced when producing the carrier raw materials.

[0030] Preferably,

[0031] The zirconium source is at least one of zirconium oxychloride, zirconium acetate, zirconium sulfate, zirconyl nitrate and zirconyl sulfate; and / or,

[0032] The mordenite has a silicon-to-aluminum ratio of 10-20, and / or a grain size of 0.5-1.0 μm, and / or a sodium content of ≤0.1 wt%; and / or,

[0033] In order to enable the catalyst carrier to be extruded, the extrusion aid is at least one of citric acid, acetic acid and nitric acid; and / or,

[0034] The solvent of the extrusion aid solution is water. Preferably, the concentration of the extrusion aid solution is 3-10 vol%. The extrusion aid solution mainly promotes the extrusion molding of the zirconium source and the mordenite. The amount of the extrusion aid solution is not particularly limited, and those skilled in the art can adjust it adaptively according to the molding effect of the zirconium source and the mordenite.

[0035] Preferably,

[0036] The drying temperature is 70-150° C., and / or the drying time is 5-10 hours; and / or,

[0037] The calcination temperature is 800-1100° C., and / or the calcination time is 2-8 hours.

[0038] Since the catalyst is a porous material, it is filled with micro-channels of different sizes. The pore structure has a great influence on the selectivity, life and mechanical strength of the catalyst. According to the classification of the International Union of Pure and Applied Chemistry (IUPAC), the pores of porous materials can be divided into: macropores with a pore size greater than 50nm, mesopores or medium pores with a pore size of 2-50nm, and micropores with a pore size less than 2nm. Different pore structures will cause different specific surface areas and pore size distributions of catalysts, and the diffusion, adsorption and desorption states of reactants in the pores and the surface utilization of the pores will all be different, which will in turn affect the performance of the ammonolysis reaction. The pore volume corresponding to pores of a certain pore size is different for different pore sizes, and the pore volume distribution or pore distribution of the catalyst is also very different. If the catalyst contains more capillaries, although its surface area is large at this time, it does not match the reactants and cannot diffuse into the pores, and this part of the pores cannot be fully utilized. Reasonable control of pore distribution can enable the catalyst to exert the best catalytic performance. In order to obtain a catalyst with better catalytic performance, the inventors carefully studied and screened the carrier. Preferably, the ratio of the mesopore volume of the catalyst to the total pore volume of the catalyst measured by the BET method is greater than 0.70, preferably 0.75-0.95.

[0039] A second object of the present invention is to provide a method for preparing an ammonolysis catalyst.

[0040] The preparation method of the ammonolysis catalyst of the present invention comprises:

[0041] The catalyst is prepared by heating a precursor solution of a main active component and a precursor solution of an auxiliary agent, spraying the solution onto a carrier, drying, calcining and reducing the solution.

[0042] Preferably,

[0043] There is no particular limitation on the precursor of the active component nickel, and it can be a water-soluble salt of the main active component, preferably at least one of sulfate, nitrate, and acetate, that is, at least one of nickel sulfate, nickel nitrate, and nickel acetate; and / or,

[0044] The concentration of the main active component precursor solution is not particularly limited. Those skilled in the art can adjust the amount of solvent water according to the amount of the main active component precursor to ensure that the main active component precursor is fully dissolved; and / or,

[0045] The auxiliary agent precursor is a water-soluble salt of the auxiliary agent, preferably an ammonium salt, such as ammonium perrhenate; and / or,

[0046] There is no special limitation on the concentration of the auxiliary agent precursor solution. Those skilled in the art can adjust the amount of solvent water according to the amount of the auxiliary agent precursor to ensure that the auxiliary agent precursor is fully dissolved.

[0047] Preferably,

[0048] The heating temperature is 70-90° C.; and / or,

[0049] The number of spraying is 1 or more, and the amount of the mixed solution sprayed each time is adaptively adjusted according to the water absorption rate of the carrier. The main active component precursor solution and the auxiliary agent precursor solution can be impregnated into the carrier in any desired order, or the mixed solution containing the main active component precursor and the auxiliary agent precursor can be used for continuous impregnation, and the appropriate solution concentration is selected to load the active component on the carrier; when spraying multiple times, it is best to dry and roast after each spraying; and / or,

[0050] The drying temperature is 80-150° C., preferably 100-150° C., and / or the drying time is 4-8 hours; in actual operation, the required drying time can be set according to the temperature, material amount and equipment performance, and the water content in the dried carrier does not affect the subsequent roasting; and / or,

[0051] The dried catalyst precursor needs to be calcined at a certain temperature to remove the crystal water in the salt, or to decompose the salt of the active component into oxides. The calcination temperature is 150-500°C, preferably 300-500°C, and / or the calcination time is 3-8h, preferably 4-6h; and / or,

[0052] The finally obtained oxidized catalyst needs to be reduced to have catalytic activity. During the reduction, the reduction temperature can be gradually increased, and the temperature increase should not be too fast. The reduction temperature is 400-550°C, and / or the reduction time is 2-10h, preferably 3-8h, and / or the temperature increase rate of the reduction process does not exceed 20°C / hour; in the actual operation process, other methods can also be selected to reduce the catalyst, such as radiation in-situ reduction and infrared in-situ reduction; and / or,

[0053] The gas used for reduction can be pure hydrogen or a mixed gas, such as a mixed gas of hydrogen and nitrogen. The gas used in the reduction process is hydrogen or nitrogen, preferably hydrogen.

[0054] The following solutions can be adopted:

[0055] (1) weighing a zirconium source and mordenite in proportion, mixing the two, adding them into a kneader and stirring them thoroughly, adding an appropriate amount of an extrusion aid solution and extruding them, drying them at 70-150° C. for 5-10 hours, and then calcining them in a muffle furnace at 800-1100° C. for 2-8 hours, and then cooling them to obtain the modified zirconium dioxide carrier;

[0056] (2) Weighing a certain amount of the modified zirconium dioxide carrier obtained in step (1), weighing a water-soluble salt of nickel and a water-soluble salt of an auxiliary agent according to the loading amount and preparing an aqueous solution, heating the aqueous solution to 70-90° C., spraying the aqueous solution on the carrier in equal volumes according to the water absorption rate of the carrier, drying at 80-150° C. for 4-8 hours, and then calcining and decomposing the aqueous solution in a muffle furnace at 150-500° C. to obtain a catalyst precursor; the above-mentioned spraying step can be performed multiple times according to the amount of the aqueous solution;

[0057] (3) reducing the catalyst precursor obtained in step (2) at a reduction temperature of 400-550° C., cooling it to 40° C. and directly placing it in water for sealing or passivating it before unloading to obtain the ammonolysis catalyst.

[0058] The shape and size of the ammonolysis catalyst of the present invention can be customized arbitrarily, such as spherical, strip, columnar, ring, etc., and the size is mostly between 0.3 and 6 mm, more preferably between 0.5 and 4 mm. This size requirement is mainly based on the design of the fixed bed reactor to facilitate installation, reduce bed pressure and other requirements.

[0059] The ammonolysis catalyst of the present invention can also be prepared by a variety of methods, such as precipitation method, impregnation method, etc., and technicians in this field can make adaptive selections according to actual conditions.

[0060] The third object of the present invention is to provide an application of an ammonolysis catalyst in the reaction of preparing primary amines by ammonolysis of secondary amines.

[0061] Since the application of ammonolysis catalysts requires the use of appropriate ammonolysis processes to exert their performance:

[0062] Preferably,

[0063] The secondary amine is at least one of diisopropylamine, diethylamine, di-n-propylamine, diethylenetriamine, dipropylenetriamine and dihexylenetriamine.

[0064] Preferably,

[0065] The reaction conditions of the secondary amine ammonolysis are: reaction temperature 150-250°C, and / or reaction pressure 0.1-25.0 MPa, and / or feed liquid phase volume hourly space velocity 0.05-1.0 m / s. 3 / (m 3 ·h), and / or, the molar ratio of hydrogen: liquid ammonia: secondary amine is (0.1-10):(1-100):1.

[0066] Preferably,

[0067] The secondary amine can be fed alone or in a mixed solution with a solvent of a certain concentration. Preferably, the solvent is at least one of water, 1.4-dioxane, tetrahydrofuran, and phenyl ether. More preferably, the weight percentage of the secondary amine in the mixed solution is 20-100wt%. Studies have shown that using an appropriate amount of solvent can improve the secondary amine conversion rate and primary amine selectivity, reduce the generation of by-products and thus reduce coking, and extend the service life of the ammonolysis catalyst.

[0068] The present invention uses zirconium dioxide modified by mordenite: 1. The alkalinity and amount of alkalinity on its surface are reduced, which is more suitable for ammonolysis reaction; 2. The overall pore structure of the carrier is adjusted, and the reactants and reaction products are more easily adsorbed and desorbed on the surface of the ammonolysis catalyst, which promotes diffusion in the pores; 3. The stability of the ammonolysis catalyst is greatly improved. The present invention deeply studies the existing ammoniation reaction technology and proposes an ammonolysis catalyst for the reaction system, which can effectively improve the activity and selectivity of generating primary amines. DETAILED DESCRIPTION

[0069] The present invention is described in detail below in conjunction with specific embodiments. It is necessary to point out that the following embodiments are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made to the present invention by those skilled in the art based on the contents of the present invention still fall within the scope of protection of the present invention.

[0070] The raw materials used in the examples and comparative examples of the present invention are all commercially available products.

[0071] Example 1

[0072] 292.59 g of zirconium oxynitrate and 44 g of commercially available mordenite (Si / Al ratio of 10-20, grain size of 0.5-1.0 μm, sodium content of 0.05 wt%) powders were added into a kneader and mixed thoroughly. The mixture was kneaded and extruded using a dilute acid solution containing 5 vol% nitric acid. The mixture was dried at 120°C for 6 h and then calcined at 880°C for 6 h to prepare the desired modified zirconium dioxide carrier.

[0073] 238.42g of nickel nitrate hexahydrate (industrial grade, purity 98%) and 3.25g of ammonium perrhenate were dissolved in water to form 106mL of solution, and the solution was heated to 80°C and loaded on the obtained 100g of the modified zirconium dioxide carrier by spraying twice, and dried at 100°C for 8h after each spraying, and then calcined at 380°C for 6h; finally, the temperature was gradually increased with hydrogen for reduction at a heating rate of 20°C / h, and the reduction was performed at 420°C for 5h to obtain an ammonolysis catalyst, and the specific composition is shown in Table 1. The ratio of its mesopore volume to the total pore volume of the ammonolysis catalyst was 0.85 as determined by the BET method.

[0074] Example 2

[0075] 262.58 g of zirconium oxynitrate and 60 g of commercially available mordenite (Si / Al ratio of 10-20, grain size of 0.5-1.0 μm, sodium content of 0.05 wt%) powders were added into a kneader and mixed thoroughly. The mixture was kneaded and extruded using a dilute acid solution containing 5 vol% nitric acid. The mixture was dried at 130°C for 5 h and then calcined at 960°C for 3 h to prepare the desired modified zirconium dioxide carrier.

[0076] 379.73g nickel nitrate hexahydrate (industrial grade, purity 98%) and 8.41g ammonium perrhenate were dissolved in water to form 168mL solution, the solution was heated to 85°C and loaded on the obtained 100g modified zirconium dioxide carrier by spraying method three times, and dried at 120°C for 6h after each spraying, and then calcined at 350°C for 4h; finally, the temperature was gradually increased with hydrogen for reduction, the temperature increase rate was 15°C / h, and the reduction was performed at 460°C for 4h to obtain an ammonolysis catalyst, the specific composition of which is shown in Table 1. The ratio of its mesopore volume to the total pore volume of the ammonolysis catalyst was 0.82 as determined by the BET method.

[0077] Example 3

[0078] 247.58 g of zirconium oxynitrate and 68 g of commercially available mordenite (Si / Al ratio of 10-20, grain size of 0.5-1.0 μm, sodium content of 0.05 wt%) powders were added into a kneader and mixed thoroughly. The mixture was kneaded and extruded using a dilute acid solution containing 8 vol% nitric acid. The mixture was dried at 100°C for 8 h and then calcined at 1030°C for 2 h to prepare the desired modified zirconium dioxide carrier.

[0079] 166.93g nickel nitrate hexahydrate (industrial grade, purity 98%) and 1.55g ammonium perrhenate were dissolved in water to form 121mL solution, the solution was heated to 90°C and loaded on the obtained 100g modified zirconium dioxide carrier by spraying twice, and dried at 110°C for 7h after each spraying, and then calcined at 330°C for 6h; finally, the temperature was gradually increased with hydrogen for reduction, the temperature increase rate was 15°C / h, and the reduction was carried out at 450°C for 4h to obtain an ammonolysis catalyst, the specific composition of which is shown in Table 1. The ratio of its mesopore volume to the total pore volume of the ammonolysis catalyst was 0.88 as determined by the BET method.

[0080] Example 4

[0081] 225.07g of zirconium oxynitrate and 80g of commercially available mordenite (Si / Al ratio of 10-20, grain size of 0.5-1.0μm, sodium content of 0.05wt%) powders were added into a kneader and mixed thoroughly. The mixture was kneaded and extruded using a dilute acid solution containing 3vol% nitric acid. The mixture was dried at 140°C for 6h and then calcined at 970°C for 4h to prepare the desired modified zirconium dioxide carrier.

[0082] 225.21g nickel nitrate hexahydrate (industrial grade, purity 98%) and 8.73g ammonium perrhenate were dissolved in water to form 130mL solution, the solution was heated to 85°C and loaded on the obtained 100g modified zirconium dioxide carrier by spraying twice, and dried at 130°C for 5h after each spraying, and then calcined at 420°C for 4h; finally, the temperature was gradually increased with hydrogen for reduction at a heating rate of 20°C / h, and the reduction was performed at 480°C for 3h to obtain an ammonolysis catalyst, the specific composition of which is shown in Table 1. The ratio of its mesopore volume to the total pore volume of the ammonolysis catalyst was 0.76 as determined by the BET method.

[0083] Example 5

[0084] 247.58 g of zirconium oxynitrate and 68 g of commercially available mordenite (Si / Al ratio of 10-20, grain size of 0.5-1.0 μm, sodium content of 0.05 wt%) powders were added into a kneader and mixed thoroughly. The mixture was kneaded and extruded using a dilute acid solution containing 8 vol% acetic acid. The mixture was dried at 120°C for 6 h and then calcined at 920°C for 5 h to prepare the desired modified zirconium dioxide carrier.

[0085] 344.67g of nickel nitrate hexahydrate (industrial grade, purity 98%) and 6.26g of ammonium perrhenate were dissolved in water to form 175mL of solution, and the solution was heated to 90°C and loaded on the obtained 100g of the modified zirconium dioxide carrier by spraying method three times, and dried at 150°C for 5h after each spraying, and then calcined at 400°C for 4h; finally, the temperature was gradually increased with hydrogen for reduction, the temperature increase rate was 10°C / h, and the reduction was performed at 450°C for 4h to obtain an ammonolysis catalyst, and the specific composition is shown in Table 1. The ratio of its mesopore volume to the total pore volume of the ammonolysis catalyst was 0.9 as determined by the BET method.

[0086] Example 6

[0087] 270.08g of zirconium oxynitrate and 56.0g of commercially available mordenite (Si / Al ratio of 10-20, grain size of 0.5-1.0μm, sodium content of 0.05wt%) powders were added into a kneader and mixed thoroughly. The mixture was kneaded and extruded using a dilute acid solution containing 10vol% nitric acid. The mixture was dried at 130°C for 6h and then calcined at 900°C for 5h to prepare the desired modified zirconium dioxide carrier.

[0088] 232.23g of nickel acetate tetrahydrate (industrial grade, purity 98%) and 2.48g of ammonium perrhenate were dissolved in water to form 110mL of solution, and the solution was heated to 85°C and loaded on the obtained 100g of the modified zirconium dioxide carrier by spraying twice, and dried at 140°C for 4h after each spraying, and then calcined at 360°C for 6h; finally, the temperature was gradually increased with hydrogen for reduction at a heating rate of 10°C / h, and the reduction was performed at 440°C for 6h to obtain an ammonolysis catalyst, and the specific composition is shown in Table 1. The ratio of its mesopore volume to the total pore volume of the ammonolysis catalyst was 0.84 as determined by the BET method.

[0089] Example 7

[0090] 202.56 g of zirconium oxynitrate and 92.0 g of commercially available silk zeolite (Si / Al ratio of 10-20, grain size of 0.5-1.0 μm, sodium content of 0.05 wt%) powders were added into a kneader and mixed thoroughly. The mixture was kneaded and extruded using a dilute acid solution containing 3 vol% citric acid solution and 4 vol% nitric acid. The mixture was dried at 100°C for 8 h and then calcined at 1000°C for 4 h to prepare the desired modified zirconium dioxide carrier.

[0091] 223.85g nickel nitrate hexahydrate (industrial grade, purity 98%) and 7.81g ammonium perrhenate were dissolved in water to form 136mL solution, the solution was heated to 85°C and loaded on the obtained 100g modified zirconium dioxide carrier by spraying twice, and dried at 120°C for 6h after each spraying, and then calcined at 380°C for 4h; finally, the temperature was gradually increased with hydrogen for reduction at a heating rate of 15°C / h, and the reduction was performed at 500°C for 4h to obtain an ammonolysis catalyst, the specific composition of which is shown in Table 1. The ratio of its mesopore volume to the total pore volume of the ammonolysis catalyst was 0.82 as determined by the BET method.

[0092] Example 8

[0093] 275.92 g of zirconium sulfate and 80.0 g of commercially available mordenite (Si / Al ratio of 10-20, grain size of 0.5-1.0 μm, sodium content of 0.05 wt%) powder were added into a kneader and mixed thoroughly. The mixture was kneaded and extruded using a dilute acid solution containing 6 vol% nitric acid. The mixture was dried at 150°C for 5 h and then calcined at 860°C for 8 h to prepare the desired modified zirconium dioxide carrier.

[0094] 185.69g of nickel acetate tetrahydrate (industrial grade, purity 98%) and 3.15g of ammonium perrhenate were dissolved in water to form 132mL of solution, and the solution was heated to 90°C and loaded on the obtained 100g of the modified zirconium dioxide carrier by spraying twice, and dried at 120°C for 8h after each spraying, and then calcined at 400°C for 5h; finally, the temperature was gradually increased with hydrogen for reduction at a heating rate of 18°C / h, and the reduction was performed at 460°C for 7h to obtain an ammonolysis catalyst, and the specific composition is shown in Table 1. The ratio of its mesopore volume to the total pore volume of the ammonolysis catalyst was 0.77 as determined by the BET method.

[0095] Example 9

[0096] 312.8 g of zirconium sulfate tetrahydrate and 60 g of commercially available mordenite (Si / Al ratio of 10-20, grain size of 0.5-1.0 μm, sodium content of 0.05 wt%) powder were added into a kneader and mixed thoroughly. The mixture was kneaded and extruded using a dilute acid solution containing 5 vol% nitric acid. The mixture was dried at 110°C for 8 h and then calcined at 980°C for 4 h to prepare the desired modified zirconium dioxide carrier.

[0097] 180.17g nickel nitrate hexahydrate (industrial grade, purity 98%) and 3.50g ammonium perrhenate were dissolved in water to form 114mL solution, the solution was heated to 85°C and loaded on the obtained 100g modified zirconium dioxide carrier by spraying twice, and dried at 130°C for 6h after each spraying, and then calcined at 350°C for 6h; finally, the temperature was gradually increased with hydrogen for reduction at a heating rate of 15°C / h, and the reduction was performed at 450°C for 6h to obtain an ammonolysis catalyst, the specific composition of which is shown in Table 1. The ratio of its mesopore volume to the total pore volume of the ammonolysis catalyst was 0.91 as determined by the BET method.

[0098] Comparative Example 1

[0099] 225.07g of zirconium oxynitrate and 80g of commercially available mordenite (Si / Al ratio of 10-20, grain size of 0.5-1.0μm, sodium content of 0.05wt%) powders were added into a kneader and mixed thoroughly. The mixture was kneaded and extruded using a dilute acid solution containing 10vol% nitric acid. The mixture was dried at 110°C for 6h and then calcined at 940°C for 4h to prepare the desired modified zirconium dioxide carrier.

[0100] 501.48g of nickel nitrate hexahydrate (industrial grade, purity 98%) and 1.75g ​​of ammonium perrhenate were dissolved in water to form 195mL of solution, and the solution was heated to 90°C and loaded on the obtained 100g of the modified zirconium dioxide carrier by spraying method three times, and dried at 120°C for 8h after each spraying, and then calcined at 370°C for 4h; finally, the temperature was gradually increased with hydrogen for reduction, the temperature increase rate was 20°C / h, and the reduction was carried out at 420°C for 6h to obtain an ammonolysis catalyst, and the specific composition is shown in Table 1. The ratio of its mesopore volume to the total pore volume of the ammonolysis catalyst was 0.78 as determined by the BET method.

[0101] Comparative Example 2

[0102] 262.58 g of zirconium oxynitrate and 60 g of commercially available mordenite (Si / Al ratio of 10-20, grain size of 0.5-1.0 μm, sodium content of 0.05 wt%) powders were added into a kneader and mixed thoroughly. The mixture was kneaded and extruded using a dilute acid solution containing 5 vol% nitric acid. The mixture was dried at 150°C for 5 h and then calcined at 1000°C for 6 h to prepare the desired modified zirconium dioxide carrier.

[0103] 110.37g nickel nitrate hexahydrate (industrial grade, purity 98%) and 2.14g ammonium perrhenate were dissolved in water to form 116mL solution, the solution was heated to 85°C and loaded on the obtained 100g modified zirconium dioxide carrier by spraying twice, and dried at 110°C for 8h after each spraying, and then calcined at 390°C for 4h; finally, the temperature was gradually increased with hydrogen for reduction at a heating rate of 15°C / h, and the reduction was performed at 490°C for 3h to obtain an ammonolysis catalyst, the specific composition of which is shown in Table 1. The ratio of its mesopore volume to the total pore volume of the ammonolysis catalyst was 0.86 as determined by the BET method.

[0104] Comparative Example 3

[0105] 337.60g of zirconium oxynitrate and 20.0g of commercially available mordenite (Si / Al ratio of 10-20, grain size of 0.5-1.0μm, sodium content of 0.05wt%) powders were added into a kneader and mixed thoroughly. The mixture was kneaded and extruded using a dilute acid solution containing 5vol% nitric acid. The mixture was dried at 120°C for 6h and then calcined at 860°C for 8h to prepare the desired modified zirconium dioxide carrier.

[0106] 273.52g of nickel nitrate hexahydrate (industrial grade, purity 98%) and 3.64g of ammonium perrhenate were dissolved in water to form 151mL of solution, and the solution was heated to 85°C and loaded on the obtained 100g modified zirconium dioxide carrier by spraying twice, and dried at 130°C for 5h after each spraying, and then calcined at 450°C for 4h; finally, the temperature was gradually increased with hydrogen for reduction, the temperature increase rate was 20°C / h, and the reduction was performed at 460°C for 5h to obtain an ammonolysis catalyst, and the specific composition is shown in Table 1. The ratio of its mesopore volume to the total pore volume of the ammonolysis catalyst was 0.69 as determined by the BET method.

[0107] Comparative Example 4

[0108] 168.8 g of zirconium oxynitrate and 110.0 g of commercially available mordenite (Si / Al ratio of 10-20, grain size of 0.5-1.0 μm, sodium content of 0.05 wt%) powders were added into a kneader and mixed thoroughly. The mixture was kneaded and extruded using a dilute acid solution containing 5 vol% nitric acid. The mixture was dried at 140°C for 5 h and then calcined at 980°C for 6 h to prepare the desired modified zirconium dioxide carrier.

[0109] 219.23g nickel nitrate hexahydrate (industrial grade, purity 98%) and 4.67g ammonium perrhenate were dissolved in water to form 136mL solution, the solution was heated to 80°C and loaded on the obtained 100g modified zirconium dioxide carrier by spraying twice, and dried at 150°C for 4h after each spraying, and then calcined at 420°C for 4h; finally, the temperature was gradually increased with hydrogen for reduction at a heating rate of 15°C / h, and the reduction was performed at 480°C for 5h to obtain an ammonolysis catalyst, the specific composition of which is shown in Table 1. The ratio of its mesopore volume to the total pore volume of the ammonolysis catalyst was 0.89 as determined by the BET method.

[0110] Comparative Example 5

[0111] 275.13 g of zirconium oxynitrate powder was added into a kneader and mixed thoroughly. The mixture was kneaded and extruded using a dilute acid solution containing 4 vol% nitric acid. The mixture was dried at 150°C for 4 h and then calcined at 990°C for 5 h to prepare the desired zirconium dioxide carrier.

[0112] 225.54g of nickel nitrate hexahydrate (industrial grade, purity 98%) and 1.91g of ammonium perrhenate were dissolved in water to form 122mL of solution, and the solution was heated to 80°C and loaded on the obtained 100g of the above-mentioned zirconium dioxide carrier by spraying twice, and dried at 140°C for 5h after each spraying, and then calcined at 440°C for 5h; finally, the temperature was gradually increased with hydrogen for reduction at a heating rate of 20°C / h, and the reduction was performed at 460°C for 8h to obtain an ammonolysis catalyst, and the specific composition is shown in Table 1. The ratio of its mesopore volume to the total pore volume of the ammonolysis catalyst was 0.75 as determined by the BET method.

[0113] Table 1

[0114]

[0115] Experimental Example 1

[0116] 100 ml of the ammonolysis catalyst prepared in the embodiment and the comparative example were respectively taken and loaded into a fixed bed reactor, activated with hydrogen at 240° C. for 3 h, then cooled to 190° C., the system pressure was increased to 15.5 MPa with hydrogen, and then ammonia was metered into the reactor after being preheated and mixed with hydrogen with a metering pump, and a mixed solution of 30 wt% of dihexyltriamine and 70 wt% of tetrahydrofuran was sent into the reactor with a metering pump, and the three reacted through the catalyst bed, under the condition that the molar ratio of hydrogen: ammonia: dihexyltriamine was 2:65:1; the liquid phase volume space velocity of dihexyltriamine was 0.3 h -1 After the reaction stabilized, samples were taken for analysis. The reaction results are shown in Table 2.

[0117] Table 2

[0118]

[0119] It can be seen from the comparative evaluation data of different catalysts in Table 2 that, compared with other catalysts, the ammonolysis catalyst prepared in the embodiment of the present invention has a better catalytic effect.

[0120] Experimental Example 2

[0121] 100 ml of the ammonolysis catalyst prepared in Example 8 was placed in a fixed bed reactor and activated with hydrogen at 250°C for 2h. The rest was the same as in Experimental Example 1, except that only the experimental conditions, such as temperature, pressure, molar ratio of hydrogen: ammonia: dihexyltriamine, liquid phase volume space velocity of dihexyltriamine, etc., were changed. The effects of different reaction conditions on the performance of the ammonolysis catalyst were investigated. The reaction conditions and results are shown in Table 3.

[0122] Table 3

[0123]

[0124] It can be seen from the evaluation data in Table 3 that within the range of different process conditions, the ammonolysis catalyst prepared by the present invention has a good ammonolysis reaction effect.

[0125] Experimental Example 3

[0126] 100 ml of the ammonolysis catalyst prepared in Example 3 was taken and placed in a fixed bed reactor, activated with hydrogen at 240° C. for 3 h, then cooled to 190° C., the system pressure was increased to 5.5 MPa, and then ammonia was metered by a metering pump and mixed with hydrogen after preheating and entering the reactor. Diisopropylamine was sent into the reactor by a metering pump, and the three reacted through the catalyst bed. The molar ratio of hydrogen: ammonia: diisopropylamine was 3:40:1, and the liquid phase volume space velocity of diisopropylamine was 0.5 h -1 After the reaction stabilized, samples were taken for analysis. The conversion rate of diisopropylamine was calculated to be 50.8%, and the selectivity of monoisopropylamine was 95.9%.

[0127] Experimental Example 4

[0128] 100 ml of the ammonolysis catalyst prepared in Example 3 was taken and placed in a fixed bed reactor, activated with hydrogen at 240°C for 3 h, then cooled to 200°C, the system pressure was increased to 8.0 MPa, and then ammonia was metered by a metering pump and mixed with hydrogen after preheating and entering the reactor, and diethylamine was sent into the reactor by a metering pump. The three reacted through the catalyst bed, the molar ratio of hydrogen: ammonia: diethylamine was 5:46:1, and the liquid phase volume space velocity of diethylamine was 0.3 h -1 After the reaction stabilized, samples were taken for analysis. The conversion rate of diethylamine was calculated to be 58.4%, and the selectivity of monoethylamine was 90.7%.

[0129] Experimental Example 5

[0130] 100 ml of the ammonolysis catalyst prepared in Example 3 was taken and placed in a fixed bed reactor, activated with hydrogen at 240° C. for 3 h, then cooled to 210° C., the system pressure was increased to 7.0 MPa, and then ammonia was metered into the reactor after being preheated and mixed with hydrogen using a metering pump, and diisopropylamine was sent into the reactor using a metering pump. The three reacted through the catalyst bed, the molar ratio of hydrogen: ammonia: di-n-propylamine was 3:45:1, and the liquid phase volume space velocity of di-n-propylamine was 0.3 h -1 After the reaction stabilized, samples were taken for analysis. The conversion rate of di-n-propylamine was calculated to be 60.3%, and the selectivity of mono-n-propylamine was 91.5%.

[0131] Experimental Example 6

[0132] 100 ml of the ammonolysis catalyst prepared in Example 3 was taken and placed in a fixed bed reactor, activated with hydrogen at 240°C for 3h, then cooled to 200°C, the system pressure was increased to 15.5MPa, and then ammonia was metered by a metering pump and mixed with hydrogen after preheating and entering the reactor. A mixed solution of 25wt% diethylenetriamine and 75wt% tetrahydrofuran was sent into the reactor by a metering pump. The three reacted through the catalyst bed, the molar ratio of hydrogen: ammonia: diethylenetriamine was 2:37:1, and the liquid phase volume space velocity of diethylenetriamine was 0.3h -1 After the reaction stabilized, samples were taken for analysis. The conversion rate of diethylenetriamine was calculated to be 94.8%, and the selectivity of ethylenediamine was 20.6%.

[0133] Experimental Example 7

[0134] 100 ml of the ammonolysis catalyst prepared in Example 3 was taken and placed in a fixed bed reactor, activated with hydrogen at 250°C for 2h, then cooled to 190°C, the system pressure was increased to 10.0MPa, and then ammonia was metered by a metering pump and mixed with hydrogen after preheating into the reactor. A mixed solution of 40wt% dipropylenetriamine and 60wt% water was sent into the reactor by a metering pump. The three reacted through the catalyst bed, the molar ratio of hydrogen: ammonia: dipropylenetriamine was 1:50:1, and the liquid phase volume space velocity of dipropylenetriamine was 0.25h -1 After the reaction stabilized, samples were taken for analysis. The conversion rate of dipropylenetriamine was calculated to be 93.6%, and the selectivity of propylenediamine was 22.6%.

[0135] Experimental Example 8

[0136] 100 ml of the ammonolysis catalyst prepared in Example 4 was taken and placed in a fixed bed reactor, activated with hydrogen at 250° C. for 2 h, then cooled to 195° C., and the system pressure was raised to 16 MPa. Ammonia was then metered with a metering pump and mixed with hydrogen after preheating before entering the reactor. A mixed solution of 30 wt% dihexyltriamine and 70 wt% tetrahydrofuran was sent into the reactor with a metering pump. The molar ratio of hydrogen: ammonia: dihexyltriamine was 2:58:1, and the liquid phase volume space velocity of dihexyltriamine was 0.3 h -1 The three were reacted in a catalyst bed to investigate the stability of the ammonolysis catalyst. The specific results are shown in Table 4.

[0137] Table 4

[0138]

[0139] It can be seen from the data in Table 4 that the ammonolysis catalyst prepared by the present invention has good stability.

[0140] It is not difficult to see from the above experimental examples that the ammonolysis catalyst prepared by the present invention can enable a variety of secondary amines to efficiently prepare primary amines.

Claims

1. An ammonolysis catalyst, characterized in that The catalyst comprises a carrier and an active component supported on the carrier; The active components include main active components and auxiliary agents; The main active component is Ni; The auxiliary agent is at least one of the elements of Group IIIB, Group VIB, Group VIIB and Group IIIA; Taking the total weight of the catalyst as 100%: The content of the main active component is 20-45wt%; The content of the auxiliary agent is 0.5-4.0wt%.

2. The ammonolysis catalyst according to claim 1, characterized in that: Taking the total weight of the catalyst as 100%: The content of the main active component is 24-42wt%; The content of the auxiliary agent is 0.75-3.75wt%.

3. The ammonolysis catalyst according to claim 1, characterized in that: The auxiliary agent is at least one of La, Mn and Re, preferably Re; and / or, The carrier is a modified zirconium dioxide carrier; preferably, the modified zirconium dioxide carrier is zirconium dioxide modified by mordenite; more preferably, the content of zirconium dioxide is 50-80wt% of the total weight of the carrier, preferably 60-75wt%.

4. The ammonolysis catalyst according to claim 3, characterized in that: The modified zirconium dioxide carrier is prepared by fully stirring a zirconium source and mordenite, adding an extrusion aid solution, extruding and molding, and drying and calcining.

5. The ammonolysis catalyst according to claim 4, characterized in that: The zirconium source is at least one of zirconium oxychloride, zirconium acetate, zirconium sulfate, zirconyl nitrate and zirconyl sulfate; and / or, The mordenite has a silicon-to-aluminum ratio of 10-20, and / or a grain size of 0.5-1.0 μm, and / or a sodium content of ≤0.1 wt%; and / or, The extrusion aid is at least one of citric acid, acetic acid and nitric acid; and / or, The solvent of the extrusion aid solution is water. Preferably, the concentration of the extrusion aid solution is 3-10 vol%.

6. The ammonolysis catalyst according to claim 4, characterized in that: The drying temperature is 70-150° C., and / or the drying time is 5-10 hours; and / or, The calcination temperature is 800-1100° C., and / or the calcination time is 2-8 hours.

7. The ammonolysis catalyst according to any one of claims 1 to 6, characterized in that: The ratio of the mesopore volume of the catalyst to the total pore volume of the catalyst is greater than 0.70, preferably 0.75-0.

95.

8. A method for preparing the ammonolysis catalyst according to any one of claims 1 to 7, characterized in that The method comprises: The catalyst is prepared by heating a precursor solution of a main active component and a precursor solution of an auxiliary agent, spraying the solution onto a carrier, drying, calcining and reducing the solution.

9. The method for preparing the ammonolysis catalyst according to claim 8, characterized in that: The main active component precursor is a water-soluble salt of the main active component, preferably at least one of sulfate, nitrate and acetate; and / or, The auxiliary agent precursor is a water-soluble salt of the auxiliary agent, preferably an ammonium salt.

10. The method for preparing the ammonolysis catalyst according to claim 8, characterized in that: The heating temperature is 70-90° C.; and / or, The number of spraying times is 1 or more; and / or, The drying temperature is 80-150° C., preferably 100-150° C., and / or the drying time is 4-8 hours; and / or, The calcination temperature is 150-500° C., preferably 300-500° C., and / or the calcination time is 3-8 hours, preferably 4-6 hours; and / or, The reduction temperature is 400-550°C, and / or the reduction time is 2-10h, preferably 3-8h, and / or the heating rate of the reduction process does not exceed 20°C / hour; and / or, The gas used in the reduction process is hydrogen or nitrogen, preferably hydrogen.

11. Use of the catalyst according to any one of claims 1 to 7 or the catalyst prepared by the method according to any one of claims 8 to 10 in the preparation of primary amines by ammonolysis of secondary amines.

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