Catalyst with catalytic ammonolysis function, preparation method and application thereof

Abstract

This invention relates to the field of catalysis, and discloses a catalyst with catalytic ammonolysis function, its preparation method, and its application. The catalyst comprises a support and a main metal element Ni, secondary metal elements La and In supported on the support, with Ni accounting for 10-40 wt% of the total catalyst weight. When using this catalyst to catalyze the ammonolysis reaction of bis(hexamethylene)triamine, hexamethylenediamine and cycloheximine can be generated simultaneously, and the reaction exhibits high conversion rate, high selectivity, good stability, relatively mild reaction conditions, and a wide operating window, making it more suitable for industrial production.

Description

Technical Field

[0001] This invention relates to the field of catalysis, specifically to a catalyst with catalytic ammonolysis function, its preparation method, and its application. Background Technology

[0002] The rapid development of my country's automotive, textile, coating, electronics, and construction industries has greatly boosted the market demand for hexamethylenediamine. Growth has been particularly rapid in the automotive and coating sectors, and the popularization and promotion of lightweight vehicles and new energy vehicles will further stimulate the consumption demand for Nylon 66 (polyhexamethylenediamine, a downstream product of hexamethylenediamine).

[0003] The key to hexamethylenediamine technology lies in the preparation of adiponitrile. Currently, the main technologies for the synthesis of adiponitrile include butadiene cyanation, acrylonitrile dimerization, and adipic acid ammoniation and dehydration.

[0004] The butadiene cyanation process involves the reaction of butadiene with hydrogen cyanide. The cyanation process is relatively complex, and the catalyst and reaction conditions determine the complexity of the reaction products. US1112539 developed the butadiene cyanation process into a direct hydrocyanation method, using zero-valent nickel complexes and alkali metal borohydrides or quaternary ammonium borohydrides. The reaction of butadiene with hydrogen cyanide was achieved under mild conditions of 120°C and atmospheric pressure, resulting in a low polymer yield. Then, under acidic conditions, 3-pentenonitrile was isomerized to 4-pentenonitrile, followed by hydrocyanation to produce adiponitrile. CN105148999A introduced sulfur into nickel metal to form sulfur-containing nickel metal particles, enabling nickel metal sources that are not normally prone to forming nickel-ligand complexes to easily and efficiently form nickel-ligand complexes, thus improving the catalyst system.

[0005] US3649511 developed a diaphragm-free electrolysis process using an electrolyte consisting of an emulsion of acrylonitrile and 10–15% sodium dihydrogen phosphate. The aqueous phase contains a low concentration of quaternary ammonium salt (0.4%) and a saturated concentration of 7% acrylonitrile. The quaternary ammonium salt is hexamethylene diethyl dibutylammonium phosphate. The generated adiponitrile is extracted into the organic phase, resulting in a high yield. Furthermore, the quaternary ammonium salt used is more easily extracted from the organic phase with water than simpler quaternary ammonium salts.

[0006] Besides the hydrogenation of adiponitrile, other methods for preparing hexamethylenediamine include the amination and dehydration of caprolactam to prepare 6-aminohexanonitrile followed by hydrogenation, and the direct amination of hexanediol. CN107739318A describes a liquid-phase method for preparing 6-aminohexanonitrile using caprolactam as a raw material, employing phosphoric acid or a phosphate catalyst in a reactor. The temperature is raised to 200-250°C in the presence of an organic solvent, and ammonia gas is introduced at a mass ratio of ammonia to caprolactam of 5-20:1. The reaction is then carried out at 260-280°C for 0.5-2 hours, achieving a caprolactam conversion of 65% and a 6-aminohexanonitrile selectivity of 98.2%.

[0007] Cycloheximine (HMI) is an important chemical intermediate and a high-tech fine organic chemical. It can be used not only as a pharmaceutical and pesticide intermediate but also in the production of soda ash, developing agents, and waste treatment, among many other fields. Due to the difficulty in selecting the catalyst for its synthesis, only a few countries in the world are capable of producing it. US3830800 discloses a 90% yield of hexamethyleneimine achieved by catalyzing hexamethylenediamine on an inert support at a reaction temperature of 225–250 °C. However, due to unresolved intermolecular condensation issues, this route has not yet been industrially applied, and research using caprolactam as a raw material has attracted widespread attention.

[0008] However, current processes for producing hexamethylenediamine and cyclohexylimine generally suffer from poor catalyst performance, low reactant conversion rates, low selectivity for target products, and relatively harsh reaction conditions. There is still a need to develop better processes for producing hexamethylenediamine and cyclohexylimine. Summary of the Invention

[0009] The purpose of this invention is to overcome the aforementioned problems in the prior art and provide a catalyst with catalytic ammonolysis function, its preparation method and application. When using this catalyst to catalyze the ammonolysis reaction of bis(hexamethylene)triamine, hexamethylenediamine and cycloheximine can be generated simultaneously. Moreover, the reaction has high conversion rate, high selectivity, good stability, relatively mild reaction conditions, and a wide operating window, making it more suitable for industrial production.

[0010] To achieve the above objectives, the first aspect of the present invention provides a catalyst with catalytic ammonolysis function, the catalyst comprising a support and a main metal element Ni, a secondary metal element La and In supported on the support, wherein the content of Ni accounts for 10-40 wt% of the total weight of the catalyst.

[0011] The carrier includes alumina, silicon dioxide and calcium oxide, and the weight ratio of alumina, silicon dioxide and calcium oxide is (7-25):(0.8-5):1.

[0012] The second aspect of the present invention provides a method for preparing a catalyst with catalytic ammonolysis function. The method includes: loading a primary metal element Ni, a secondary metal element La and In onto a support, such that the loading amount of Ni accounts for 10-40 wt% of the total weight of the catalyst. The support includes alumina, silica and calcium oxide, and the weight ratio of alumina, silica and calcium oxide is (7-25):(0.8-5):1.

[0013] A third aspect of the present invention provides a catalyst having catalytic ammonolysis function prepared by the method described above.

[0014] The fourth aspect of the present invention provides the application of a catalyst having catalytic ammonolysis function as described in the first or third aspect in the catalytic ammonolysis of bis(hexamethylene)triamine.

[0015] The fifth aspect of the present invention provides a method for preparing hexamethylenediamine and cyclohexylimine by ammonolysis of bis(hexamethylene)triamine, the method comprising: subjecting bis(hexamethylene)triamine to an ammonolysis reaction under ammonolysis conditions and in the presence of a catalyst having the function of catalyzing ammonolysis as described in the first or third aspect.

[0016] The catalyst provided by this invention can catalyze the ammonolysis reaction of bis(hexamethylene)triamine to produce hexamethylenediamine and cyclohexylimine, and the reaction exhibits high selectivity and conversion rate, relatively mild reaction conditions, and a wide operating window (catalytic reaction can be carried out within a wide range of operating conditions). Furthermore, the catalyst has good stability; long-term use does not significantly change the selectivity and conversion rate of the catalytic reaction, making it more suitable for practical applications. Detailed Implementation

[0017] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0018] In a first aspect, the present invention provides a catalyst with catalytic ammonolysis function, the catalyst comprising a support and a main metal element Ni, a secondary metal element La and In supported on the support, wherein the content of Ni accounts for 10-40 wt% of the total weight of the catalyst.

[0019] The carrier includes alumina, silicon dioxide and calcium oxide, and the weight ratio of alumina, silicon dioxide and calcium oxide is (7-25):(0.8-5):1.

[0020] The aforementioned metallic elements can exist on the catalyst in the form of elemental substances or oxides. Before use, they can be activated to ensure that at least some Ni exists on the catalyst in a reduced state (such as elemental substance) for application in the catalytic reaction.

[0021] The inventors of this invention discovered that when the aforementioned metal elements are loaded onto the support, the resulting product exhibits a balance of acidity, alkalinity, and ammonolysis capability, efficiently catalyzing the ammonolysis of bis(hexamethylene)triamine to generate hexamethylenediamine and cyclohexylimine. The reaction demonstrates high selectivity and conversion rate, while minimizing the formation of byproducts. Furthermore, the catalytic reaction can proceed under mild conditions and over a wide range of operating conditions. In addition, the catalyst exhibits good stability, with no significant change in selectivity and conversion rate over long-term use.

[0022] According to the present invention, preferably, the weight ratio of aluminum oxide, silicon dioxide and calcium oxide is (9-23):(1-4):1.

[0023] The inventors of this invention have further discovered that when a carrier having the above composition and satisfying the above range is used, such a composite carrier can better cooperate with the metal loaded on it, further ensuring that the reaction has a high conversion rate and selectivity.

[0024] According to the present invention, preferably, the Ni content accounts for 11.5-30 wt% of the total weight of the catalyst.

[0025] According to the present invention, preferably, the weight of La accounts for 1-15 wt% of the total weight of the catalyst, more preferably 3-10 wt%.

[0026] According to the present invention, preferably, the weight of In accounts for 0.1-5 wt% of the total weight of the catalyst, more preferably 0.5-2.5 wt%.

[0027] According to the present invention, preferably, the weight ratio of Ni, La and In is (10-35):(1.5-10):1. Wherein, all components except the active component can be carriers.

[0028] When the above range is met, the conversion rate of the reaction and the selectivity of hexamethylenediamine and cycloheximine can be further improved.

[0029] Secondly, the present invention provides a method for preparing a catalyst with catalytic ammonolysis function. The method includes: loading a primary metal element Ni, a secondary metal element La and In onto a support, such that the loading amount of Ni accounts for 10-40 wt% of the total weight of the catalyst. The support includes alumina, silica and calcium oxide, and the weight ratio of alumina, silica and calcium oxide is (7-25):(0.8-5):1.

[0030] According to the present invention, preferably, the weight ratio of aluminum oxide, silicon dioxide and calcium oxide is (9-23):(1-4):1.

[0031] According to the present invention, the carrier can be obtained by conventional methods in the art. However, preferably, the method for preparing the carrier includes: kneading, extruding, first drying and first calcination of an aluminum source, a silicon source and a calcium source in sequence, wherein the weight amounts of the aluminum source, silicon source and calcium source are such that the weight ratio of alumina, silicon dioxide and calcium oxide in the carrier is (7-25):(0.8-5):1.

[0032] The mixing and kneading can be carried out in a kneading machine.

[0033] In this process, the silicon source and calcium source can be mixed with water to form a solution, and then mixed with the aluminum source.

[0034] According to the present invention, preferably, extrusion is carried out in the presence of a propellant selected from at least one of citric acid, acetic acid, nitric acid, and phosphoric acid. Using the above-mentioned propellant further ensures that the strength and pore structure of the prepared catalyst better meet the application requirements. More preferably, the above-mentioned propellant is used in the form of an aqueous solution, wherein the concentration of the propellant in the aqueous solution can be 3-15 wt%. The amount of propellant used is not particularly limited and can be a conventional choice in the art; for example, the amount of propellant used relative to 100 g of aluminum source can be 3-12 g. The aluminum source, silicon source, and calcium source can be thoroughly mixed before adding the propellant.

[0035] According to the present invention, preferably, the aluminum source is selected from at least one of boehmite, alumina powder, boehmite and aluminum hydroxide.

[0036] According to the present invention, preferably, the silicon source is selected from at least one of silica sol, water glass, tetraethyl orthosilicate, tetraethyl orthosilicate, and methyltrimethoxysilane.

[0037] According to the present invention, preferably, the calcium source is selected from at least one of calcium nitrate tetrahydrate, calcium bicarbonate, calcium acetate, calcium bisulfate, calcium bisulfite, calcium dihydrogen phosphate, calcium permanganate, and calcium gluconate.

[0038] The shape and size of the extrusion can be conventionally selected in the field, such as (toothed) spherical, strip, clover-shaped, cylindrical and annular, etc., and the size can be 0.3-10mm, especially between 0.5-5mm. This size is more suitable for fixed bed reactors, such as facilitating installation and reducing bed pressure.

[0039] The conditions for the first drying and the first calcination are not particularly limited. However, it is preferred that the temperature for the first drying is 70-150°C, more preferably 100-120°C, and the time is 5-10 hours, more preferably 6-8 hours.

[0040] Preferably, the temperature of the first roasting is 700-1000℃, more preferably 750-950℃.

[0041] Preferably, the first roasting time is 2-8 hours, more preferably 4-6 hours. The first roasting can be carried out in a muffle furnace.

[0042] The method of loading Ni, La and In onto the support is not particularly limited and can be a conventional method in the art. However, the preferred method of loading Ni, La and In onto the support includes: mixing the support with Ni salt, La salt and In salt, performing hydrothermal crystallization, and performing a second drying and a second calcination.

[0043] According to the present invention, preferably, the Ni salt is selected from at least one of nickel nitrate, nickel sulfate and nickel acetate.

[0044] According to the present invention, preferably, the La salt is selected from at least one of lanthanum nitrate, lanthanum acetate, lanthanum sulfate, and lanthanum chloride.

[0045] According to the present invention, preferably, the indium salt is selected from indium nitrate and / or indium sulfate.

[0046] It is understood that the aforementioned metal salts can be in the form of their respective hydrated salts. According to a particularly preferred embodiment of the invention, the aluminum source is boehmite; the silicon source is selected from silica sol and / or methyltrimethoxysilane; the calcium source is selected from calcium nitrate tetrahydrate and / or calcium acetate; the nickel salt is selected from nickel sulfate hexahydrate and / or nickel acetate tetrahydrate; the lanthanum salt is lanthanum acetate monohydrate; and the indium salt is indium nitrate pentahydrate.

[0047] According to the present invention, preferably, the hydrothermal crystallization is performed in multiple stages. Multiple hydrothermal crystallization stages can further improve the uniformity of metal dispersion on the support and further enhance catalytic performance.

[0048] It is understandable that, regardless of whether multiple hydrothermal crystallizations are performed or only one hydrothermal crystallization is carried out, the total amount of support and Ni salt, La salt and In salt used all meet the above range.

[0049] According to the present invention, the preferred conditions for hydrothermal crystallization include: performing the crystallization under ultrasound, with an ultrasound power of 0.1-2.0 kW, an ultrasound frequency of 35-130 kHz, and a temperature of 100-200°C, preferably 120-160°C; the total hydrothermal crystallization time is 10-48 h. By employing the above-described method of hydrothermal crystallization under ultrasound conditions, the interaction between the active metal component and the carrier can be further enhanced, promoting a highly uniform dispersion of the active metal component.

[0050] According to the present invention, after each hydrothermal crystallization, the material is subjected to a second drying and a second calcination.

[0051] According to the present invention, preferably, hydrothermal crystallization is performed in two separate processes, each lasting 6-22 hours. The duration of each hydrothermal crystallization process may be the same or different.

[0052] According to the present invention, preferably, hydrothermal crystallization is carried out in the presence of a structure-directing agent selected from ethylenediamine and / or hexamethylenediamine, wherein the ratio of the total mass of the structure-directing agent to the mass of the carrier is (0.001-0.1):1.

[0053] For example, a portion of Ni, La, and In salts is prepared into an aqueous solution, and then subjected to a first hydrothermal crystallization in a hydrothermal crystallization vessel together with a support and a structure directing agent, followed by a second drying and a second calcination. The remaining Ni, La, and In salts are prepared into an aqueous solution, and then subjected to a second hydrothermal crystallization together with the material after the first hydrothermal crystallization and the remaining structure directing agent, followed by a second drying and a second calcination. In the two hydrothermal crystallizations, the amount of Ni salt used in the first process can be 51wt%-80wt% of the total required Ni salt, and the same applies to La, In, and the structure directing agent. This ensures a more uniform distribution of the active metal components within the pores of the support.

[0054] The conditions for the second drying and the second calcination are not particularly limited. However, preferably, the temperature for each second drying is independently 100-150°C, and the time is independently 4-8 hours. The temperature and time for each second drying can be consistent or inconsistent.

[0055] Preferably, the temperature for each second roasting is independently 300-500℃, more preferably 350-450℃, and the time is independently 4-12 hours, more preferably 6-8 hours. The second roasting can be carried out in a muffle furnace. The second roasting can decompose the metal salts (Ni salts, La salts, and In salts) into their corresponding oxides. The temperature and time of each second roasting can be consistent or inconsistent.

[0056] According to the present invention, preferably, the product after the final second calcination is reduced. This reduction ensures that at least a portion of the Ni exists in a reduced state on the catalyst.

[0057] According to the present invention, preferably, the reduction method includes: using a nitrogen-hydrogen mixture as the reducing gas, wherein the hydrogen volume percentage in the reducing gas is 1-50% by volume, heating the material to 300-600°C at a heating rate of 10-100°C / h, and maintaining the temperature at a constant temperature for 3-10h.

[0058] More preferably, the reduction method includes: using a nitrogen-hydrogen mixture as the reducing gas, wherein the hydrogen volume percentage in the reducing gas is 15-30%, heating the material to 400-500℃ at a heating rate of 40-80℃ / h, and maintaining the temperature at a constant temperature for 4-8h.

[0059] By using the above-mentioned temperature-increasing procedure, the active metal components in the catalyst precursor can be further reduced to metal.

[0060] Thirdly, the present invention provides a catalyst with catalytic ammonolysis function prepared by the method described above.

[0061] Fourthly, the present invention provides the application of a catalyst having catalytic ammonolysis function as described in the first or third aspect in the catalytic ammonolysis of bis(hexamethylene)triamine.

[0062] Fifthly, the present invention provides a method for preparing hexamethylenediamine and cyclohexylimine by ammonolysis of bis(hexamethylene)triamine, the method comprising: subjecting bis(hexamethylene)triamine to an ammonolysis reaction under ammonolysis conditions and in the presence of a catalyst having the function of catalyzing ammonolysis as described in the first or third aspect.

[0063] According to the present invention, preferred ammonolysis conditions include: a temperature of 150-250°C, more preferably 170-230°C (e.g., values ​​within the range of 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, and any two of the above values); a pressure of 10-25 MPa, more preferably 15-22 MPa (e.g., values ​​within the range of 15 MPa, 16 MPa, 17 MPa, 18 MPa, 19 MPa, 20 MPa, 21 MPa, 22 MPa, and any two of the above values); and a feed liquid hourly space velocity (LHSV) of 0.01-1 m³ / s. 3 / (m 3 ·h), more preferably 0.1-0.8m 3 / (m 3 (e.g., 0.1m) 3 / (m 3 ·h), 0.2m 3 / (m 3 ·h), 0.3m 3 / (m 3 ·h), 0.4m 3 / (m 3 ·h), 0.5m 3 / (m 3 ·h), 0.6m 3 / (m 3 ·h), 0.7m 3 / (m 3·h), 0.8m 3 / (m 3 •h) and values ​​within the range formed by any two of the above values; carried out in the presence of hydrogen and ammonia, wherein the molar ratio of hydrogen, ammonia and bis(hexamethylene)triamine is (1-15):(50-150):1, more preferably (2-10):(80-120):1.

[0064] According to the present invention, the preferred conditions for ammonolysis include: a temperature of 150-250°C, more preferably 170-230°C; a pressure of 10-25 MPa, more preferably 15-22 MPa; and a feed liquid hourly space velocity of 0.01-1 h⁻¹ for bis(hexamethylene)triamine. -1 Preferably 0.1-0.8h -1 The process is carried out in the presence of hydrogen and ammonia, with the molar ratio of hydrogen, ammonia and bis(hexamethylene)triamine being (1-15):(50-150):1, preferably (2-10):(80-120):1.

[0065] Under the above conditions, the catalyst can exhibit better catalytic activity, conversion rate, and selectivity.

[0066] The present invention will be described in detail below through examples. In the following examples, the dry basis (Al2O3) content of the pseudoboehmite powder is about 70% by weight; the silica sol was purchased from Qingdao Marine Chemical Plant, model JN-40.

[0067] Example 1

[0068] This invention is used to illustrate the catalyst and its preparation method provided by the present invention.

[0069] (1) Weigh 110.87g of boehmite, 38.0g of silica sol (JN-40), and 34.95g of calcium nitrate tetrahydrate. Place the boehmite in a kneader, add the weighed silica sol and calcium nitrate tetrahydrate to 44.62g of water to make a solution, and add the solution to the boehmite in the kneader and stir thoroughly. Then add 54.54g of an aqueous solution containing 3.33g of citric acid, knead and extrude into a clover shape, dry it at 100℃ for 8h, and then calcine it in a muffle furnace at 850℃ for 5h. After cooling, the composite carrier is obtained.

[0070] (2) Weigh 71g of the composite carrier prepared in (1), weigh 61.58g of nickel sulfate hexahydrate, 3.75g of lanthanum acetate monohydrate, and 1.87g of indium nitrate pentahydrate, add them to 65.32g of water to prepare a solution, add both to a hydrothermal crystallization kettle, and add 0.98g of ethylenediamine at the same time. Seal the kettle and place it in an ultrasonic water bath at 120℃ for 20h. The ultrasonic power is 1.0kW and the ultrasonic frequency is 100kHz. Then dry it at 120℃ for 5h, and then calcine it in a muffle furnace at 400℃ to obtain Semi-finished product; Weigh 50.38g of nickel sulfate hexahydrate, 3.03g of lanthanum acetate monohydrate and 1.53g of indium nitrate pentahydrate again and add them to 65.32g of water to make a solution. Add the above decomposed semi-finished product and the aqueous solution together to a hydrothermal crystallization kettle, and add 0.80g of ethylenediamine at the same time. Seal the kettle and place it in an ultrasonic water bath at 120℃ for 20h. The ultrasonic power is 1.0kW and the ultrasonic frequency is 100kHz. Then dry it at 120℃ for 4h. Then calcine it in a muffle furnace at 400℃ to decompose it and obtain the catalyst precursor.

[0071] (3) The catalyst precursor in (2) is reduced by a programmed temperature rise method. The heating rate is 40℃ / h, the maximum reduction temperature is 400℃, and the temperature is kept constant for 6h. The reducing gas is a nitrogen-hydrogen mixture, in which the hydrogen volume percentage is 25%. Catalyst product A-1 is obtained.

[0072] Example 2

[0073] (1) Weigh 124.64 g of boehmite, 21.25 g of silica sol (JN-40), and 23.16 g of calcium nitrate tetrahydrate. Place the boehmite in a kneader, add the weighed silica sol and calcium nitrate tetrahydrate to water to prepare a 50.35 g solution, add it to the boehmite in the kneader and stir thoroughly. Then add 61.54 g of an aqueous solution containing 6.23 g of acetic acid, knead and extrude into a cylindrical shape, dry it at 120 °C for 7 h, and then calcine it in a muffle furnace at 800 °C for 6 h. After cooling, the composite carrier is obtained.

[0074] (2) Weigh 72g of the composite carrier prepared in (1), weigh 49.26g of nickel sulfate hexahydrate, 7.51g of lanthanum acetate monohydrate, and 3.74g of indium nitrate pentahydrate, add them to 66.24g of water to prepare a solution, add both to a hydrothermal crystallization kettle, and add 1.13g of ethylenediamine at the same time. Seal the kettle and place it in an ultrasonic water bath at 130℃ for 22h. The ultrasonic power is 1.5kW and the ultrasonic frequency is 80kHz. Then dry it at 130℃ for 6h, and then calcine it in a muffle furnace at 420℃ to obtain Semi-finished product; Weigh 40.31g of nickel sulfate hexahydrate, 6.14g of lanthanum acetate monohydrate and 3.06g of indium nitrate pentahydrate again and add them to 66.24g of water to make a solution. Add the above decomposed semi-finished product and the aqueous solution together to a hydrothermal crystallization kettle, and add 0.93g of ethylenediamine at the same time. Seal the kettle and place it in an ultrasonic water bath at 130℃ for 22h. The ultrasonic power is 1.5kW and the ultrasonic frequency is 80kHz. Then dry it at 130℃ for 8h. Then calcine it in a muffle furnace at 420℃ to obtain the catalyst precursor.

[0075] (3) The catalyst precursor in (2) is reduced by a programmed temperature rise method. The heating rate is 60℃ / h, the maximum reduction temperature is 490℃, and the temperature is kept constant for 4h. The reducing gas is a nitrogen-hydrogen mixture, in which the hydrogen volume percentage is 25%. Catalyst product A-2 is obtained.

[0076] Example 3

[0077] (1) Weigh 114.93g of boehmite, 33.75g of silica sol (JN-40), and 30.32g of calcium nitrate tetrahydrate. Place the boehmite in a kneader, add the weighed silica sol and calcium nitrate tetrahydrate to 47.78g of water to make a solution, and add the solution to the boehmite in the kneader and stir thoroughly. Then add 58.39g of an aqueous solution containing 4.61g of dilute nitric acid, knead and extrude into a clover shape, dry it at 110℃ for 6h, and then calcine it in a muffle furnace at 820℃ for 6h. After cooling, the composite carrier is obtained.

[0078] (2) Weigh 75.5g of the composite carrier prepared in (1), weigh 36.95g of nickel sulfate hexahydrate, 10.01g of lanthanum acetate monohydrate, and 2.81g of indium nitrate pentahydrate, add them to 69.46g of water to prepare a solution, add both to a hydrothermal crystallization kettle, and add 1.38g of ethylenediamine at the same time. Seal the kettle and place it in an ultrasonic water bath at 150℃ for 15h. The ultrasonic power is 0.7kW and the ultrasonic frequency is 120kHz. Then dry it at 120℃ for 8h, and then calcine it in a muffle furnace at 370℃ to decompose it, obtaining The semi-finished product was obtained; 30.23g of nickel sulfate hexahydrate, 8.19g of lanthanum acetate monohydrate and 2.30g of indium nitrate pentahydrate were weighed again and added to 69.46g of water to prepare a solution. The semi-finished product and the aqueous solution were added together to the hydrothermal crystallization kettle, and 1.13g of ethylenediamine was added at the same time. The kettle was sealed and placed in an ultrasonic water bath at 150℃ for 15h. The ultrasonic power was 0.7kW and the ultrasonic frequency was 120kHz. Then it was dried at 120℃ for 8h. Finally, it was calcined in a muffle furnace at 370℃ to decompose and obtain the catalyst precursor.

[0079] (3) The catalyst precursor in (2) is reduced by a programmed temperature rise method. The heating rate is 80℃ / h, the maximum reduction temperature is 420℃, and the temperature is kept constant for 5h. The reducing gas is a nitrogen-hydrogen mixture, in which the hydrogen volume percentage is 25%. Catalyst product A-3 is obtained.

[0080] Example 4

[0081] (1) Weigh 96.67g of boehmite, 66.5g of silica sol (JN-40) and 28.21g of calcium nitrate tetrahydrate. Place the boehmite in a kneader, add the weighed silica sol and calcium nitrate tetrahydrate to 29.90g of water to make a solution, add the solution to the boehmite in the kneader and stir thoroughly, then add 36.54g of an aqueous solution containing 1.93g of phosphoric acid and knead and extrude into toothed spheres, dry them at 120℃ for 6h, then calcine them in a muffle furnace at 870℃ for 4h, and obtain the composite carrier after cooling.

[0082] (2) Weigh 67.8g of the composite carrier prepared in (1), weigh 64.13g of nickel acetate tetrahydrate, 4.38g of lanthanum acetate monohydrate, and 2.25g of indium nitrate pentahydrate, add them to 62.38g of water to prepare a solution, add both to a hydrothermal crystallization kettle, and add 1.86g of ethylenediamine at the same time. Seal the kettle and place it in an ultrasonic water bath at 160℃ for 8h. The ultrasonic power is 1.2kW and the ultrasonic frequency is 100kHz. Then dry it at 140℃ for 4h, and then calcine it in a muffle furnace at 390℃ to decompose it, obtaining The semi-finished product was obtained; 52.47g of lanthanum acetate tetrahydrate, 3.58g of lanthanum acetate monohydrate and 1.84g of indium nitrate pentahydrate were weighed again and added to 62.38g of water to prepare a solution. The semi-finished product and the aqueous solution were added together to the hydrothermal crystallization kettle, and 1.53g of ethylenediamine was added at the same time. The kettle was sealed and placed in an ultrasonic water bath at 160℃ for 8h. The ultrasonic power was 1.2kW and the ultrasonic frequency was 100kHz. Then it was dried at 140℃ for 4h. Finally, it was calcined in a muffle furnace at 390℃ to decompose and obtain the catalyst precursor.

[0083] (3) The catalyst precursor in (2) is reduced by a programmed temperature rise method. The heating rate is 50℃ / h, the maximum reduction temperature is 440℃, and the temperature is kept constant for 5h. The reducing gas is a nitrogen-hydrogen mixture, in which the hydrogen volume percentage is 25%. Catalyst product A-4 is obtained.

[0084] Example 5

[0085] (1) Weigh 103.91g of boehmite, 50.56g of methyltrimethoxysilane, and 16.92g of calcium acetate. Place the boehmite in a kneader, add the weighed methyltrimethoxysilane and calcium acetate to 42.08g of water to make a solution, and add the solution to the boehmite in the kneader and stir thoroughly. Then add 51.44g of an aqueous solution containing 3.12g of citric acid, knead and extrude into a cylindrical shape, dry it at 110℃ for 8h, and then calcine it in a muffle furnace at 890℃ for 6h. After cooling, the composite carrier is obtained.

[0086] (2) Weigh 71g of the composite carrier prepared in (1), weigh 69.96g of lanthanum acetate tetrahydrate, 6.26g of lanthanum acetate monohydrate, and 4.68g of indium nitrate pentahydrate, add them to 57.5g of water to prepare a solution, add both to a hydrothermal crystallization kettle, and add 0.69g of ethylenediamine at the same time. Seal the kettle and place it in an ultrasonic water bath at 140℃ for 16h. The ultrasonic power is 1.8kW and the ultrasonic frequency is 60kHz. Then dry it at 150℃ for 5h, and then calcine it in a muffle furnace at 380℃ to obtain Semi-finished product; weigh 57.24g of lanthanum acetate tetrahydrate, 5.12g of lanthanum acetate monohydrate and 3.83g of indium nitrate pentahydrate again and add them to 57.5g of water to make a solution. Add the above decomposed semi-finished product and the aqueous solution together to a hydrothermal crystallization kettle, and add 0.56g of ethylenediamine at the same time. Seal the kettle and place it in an ultrasonic water bath at 140℃ for 16h. The ultrasonic power is 1.8kW and the ultrasonic frequency is 60kHz. Then dry it at 150℃ for 5h. Then calcine it in a muffle furnace at 380℃ to decompose it and obtain the catalyst precursor.

[0087] (3) The catalyst precursor in (2) is reduced by a programmed temperature rise method. The heating rate is 60℃ / h, the maximum reduction temperature is 450℃, and the temperature is kept constant for 4h. The reducing gas is a nitrogen-hydrogen mixture, in which the hydrogen volume percentage is 25%. Catalyst product A-5 is obtained.

[0088] Example 6

[0089] (1) Weigh 113.04 g of boehmite, 38.54 g of methyltrimethoxysilane, and 21.05 g of calcium nitrate tetrahydrate. Place the boehmite in a kneader, add the weighed methyltrimethoxysilane and calcium nitrate tetrahydrate to 45.78 g of water to make a solution, add the solution to the boehmite in the kneader and stir thoroughly. Then add 55.96 g of an aqueous solution containing 5.65 g of acetic acid and knead and extrude into a clover shape. Dry it at 120 °C for 6 h, then calcine it in a muffle furnace at 750 °C for 6 h. After cooling, the composite carrier is obtained.

[0090] (2) Weigh 70.5g of the composite carrier prepared in (1), weigh 41.98g of lanthanum acetate tetrahydrate, 12.51g of lanthanum acetate monohydrate, and 2.81g of indium nitrate pentahydrate, add them to 64.86g of water to prepare a solution, add both to a hydrothermal crystallization kettle, and add 1.55g of ethylenediamine at the same time. Seal the kettle and place it in an ultrasonic water bath at 130℃ for 18h. The ultrasonic power is 1.4kW and the ultrasonic frequency is 130kHz. Then dry it at 120℃ for 6h, and then calcine it in a muffle furnace at 450℃ to decompose it, obtaining To obtain the semi-finished product; weigh out 34.34g of lanthanum acetate tetrahydrate, 10.24g of lanthanum acetate monohydrate and 2.30g of indium nitrate pentahydrate and add them to 64.86g of water to prepare a solution. Add the above-decomposed semi-finished product and the aqueous solution together to a hydrothermal crystallization kettle, and add 1.27g of ethylenediamine at the same time. Seal the kettle and place it in an ultrasonic water bath at 130℃ for 18h. The ultrasonic power is 1.4kW and the ultrasonic frequency is 130kHz. Then dry it at 120℃ for 6h. Then calcine it in a muffle furnace at 450℃ to obtain the catalyst precursor.

[0091] (3) The catalyst precursor in (2) is reduced by a programmed temperature rise method. The heating rate is 70℃ / h, the maximum reduction temperature is 410℃, and the temperature is kept constant for 5h. The reducing gas is a nitrogen-hydrogen mixture, in which the hydrogen volume percentage is 25%. Catalyst product A-6 is obtained.

[0092] Example 7

[0093] (1) Weigh 121.16g of boehmite, 24.49g of methyltrimethoxysilane, and 15.79g of calcium acetate. Place the boehmite in a kneader, add the weighed methyltrimethoxysilane and calcium acetate to 49.07g of water to make a solution, and add the solution to the boehmite in the kneader and stir thoroughly. Then add 59.97g of an aqueous solution containing 4.85g of dilute nitric acid and knead and extrude into toothed spheres. Dry them at 110℃ for 8h, and then calcine them in a muffle furnace at 910℃ for 4h. After cooling, the composite carrier is obtained.

[0094] (2) Weigh 67.0g of the composite carrier prepared in (1), weigh 55.97g of lanthanum acetate tetrahydrate, 8.76g of lanthanum acetate monohydrate, and 3.74g of indium nitrate pentahydrate, add them to 65.32g of water to prepare a solution, add both to a hydrothermal crystallization kettle, and add 0.82g of ethylenediamine at the same time. Seal the kettle and place it in an ultrasonic water bath at 145℃ for 12h. The ultrasonic power is 2.0kW and the ultrasonic frequency is 80kHz. Then dry it at 130℃ for 5h, and then calcine it in a muffle furnace at 420℃ to decompose it, obtaining To obtain the semi-finished product; weigh out 45.79g of lanthanum acetate tetrahydrate, 7.17g of lanthanum acetate monohydrate and 3.06g of indium nitrate pentahydrate and add them to 65.32g of water to prepare a solution. Add the above-decomposed semi-finished product and the aqueous solution together to a hydrothermal crystallization kettle, and add 0.67g of ethylenediamine at the same time. Seal the kettle and place it in an ultrasonic water bath at 145℃ for 12h. The ultrasonic power is 2.0kW and the ultrasonic frequency is 80kHz. Then dry it at 130℃ for 4h. Then calcine it in a muffle furnace at 420℃ to obtain the catalyst precursor.

[0095] (3) The catalyst precursor in (2) is reduced by a programmed temperature rise method. The heating rate is 40℃ / h, the maximum reduction temperature is 490℃, and the temperature is kept constant for 4h. The reducing gas is a nitrogen-hydrogen mixture, in which the hydrogen volume percentage is 25%. Catalyst product A-7 is obtained.

[0096] Example 8

[0097] (1) Weigh 99.28g of boehmite, 60.01g of silica sol (JN-40), and 31.58g of calcium nitrate tetrahydrate. Place the boehmite in a kneader, add the weighed silica sol and calcium nitrate tetrahydrate to 32.94g of water to make a solution, and add the solution to the boehmite in the kneader and stir thoroughly. Then add 40.26g of an aqueous solution containing 1.90g of phosphoric acid, knead and extrude into a clover shape, dry it at 100℃ for 8h, and then calcine it in a muffle furnace at 950℃ for 4h. After cooling, the composite carrier is obtained.

[0098] (2) Weigh 74.0g of the composite carrier prepared in (1), weigh 51.30g of lanthanum acetate tetrahydrate, 3.75g of lanthanum acetate monohydrate, and 1.87g of indium nitrate pentahydrate, add them to 68.08g of water to prepare a solution, add both to a hydrothermal crystallization kettle, and add 2.04g of ethylenediamine at the same time. Seal the kettle and place it in an ultrasonic water bath at 135℃ for 10h. The ultrasonic power is 0.4kW and the ultrasonic frequency is 110kHz. Then dry it at 140℃ for 4h, and then calcine it in a muffle furnace at 400℃ to decompose it, obtaining To obtain the semi-finished product; weigh out 41.98g of lanthanum acetate tetrahydrate, 3.07g of lanthanum acetate monohydrate and 1.53g of indium nitrate pentahydrate and add them to 68.08g of water to prepare a solution. Add the above-decomposed semi-finished product and the aqueous solution together to a hydrothermal crystallization kettle, and add 1.67g of ethylenediamine at the same time. Seal the kettle and place it in an ultrasonic water bath at 135℃ for 10h. The ultrasonic power is 0.4kW and the ultrasonic frequency is 110kHz. Then dry it at 140℃ for 4h. Then calcine it in a muffle furnace at 400℃ to obtain the catalyst precursor.

[0099] (3) The catalyst precursor in (2) is reduced by a programmed temperature rise method. The heating rate is 80℃ / h, the maximum reduction temperature is 420℃, and the temperature is kept constant for 8h. The reducing gas is a nitrogen-hydrogen mixture, in which the hydrogen volume percentage is 25%. Catalyst product A-8 is obtained.

[0100] Example 9

[0101] (1) Weigh 106.52g of boehmite, 51.25g of silica sol (JN-40), and 25.26g of calcium nitrate tetrahydrate. Place the boehmite in a kneader, add the weighed silica sol and calcium nitrate tetrahydrate to 38.89g of water to make a solution, and add the solution to the boehmite in the kneader and stir thoroughly. Then add 47.53g of an aqueous solution containing 3.20g of citric acid, knead and extrude into a cylindrical shape, dry it at 120℃ for 8h, and then calcine it in a muffle furnace at 820℃ for 6h. After cooling, the composite carrier is obtained.

[0102] (2) Weigh 79.50g of the composite carrier prepared in (1), weigh 39.41g of nickel sulfate hexahydrate, 5.01g of lanthanum acetate monohydrate, and 0.94g of indium nitrate pentahydrate, add them to 73.14g of water to prepare a solution, add both to a hydrothermal crystallization kettle, and add 1.46g of ethylenediamine at the same time. Seal the kettle and place it in an ultrasonic water bath at 150℃ for 6h. The ultrasonic power is 0.9kW and the ultrasonic frequency is 90kHz. Then dry it at 130℃ for 6h, and then calcine it in a muffle furnace at 350℃ to decompose it, obtaining The semi-finished product was obtained; 32.25g of nickel sulfate hexahydrate, 4.10g of lanthanum acetate monohydrate and 0.77g of indium nitrate pentahydrate were weighed again and added to 73.14g of water to prepare a solution. The semi-finished product and the aqueous solution were added together to the hydrothermal crystallization kettle, and 1.19g of ethylenediamine was added at the same time. The kettle was sealed and placed in an ultrasonic water bath at 150℃ for 6h. The ultrasonic power was 0.9kW and the ultrasonic frequency was 90kHz. Then it was dried at 130℃ for 6h, and then calcined in a muffle furnace at 350℃ to obtain the catalyst precursor.

[0103] (3) The catalyst precursor in (2) is reduced by a programmed temperature rise method. The heating rate is 60℃ / h, the maximum reduction temperature is 500℃, and the temperature is kept constant for 5h. The reducing gas is a nitrogen-hydrogen mixture, in which the hydrogen volume percentage is 25%. Catalyst product A-9 is obtained.

[0104] Example 10

[0105] (1) Weigh 127.83g of boehmite, 19.50g of silica sol (JN-40), and 11.28g of calcium acetate. Place the boehmite in a kneader, add the weighed silica sol and calcium acetate to 522.26g of water to make a solution, add the solution to the boehmite in the kneader and stir thoroughly. Then add 63.87g of an aqueous solution containing 3.83g of citric acid, knead and extrude into a clover shape, dry it at 110℃ for 7h, and then calcine it in a muffle furnace at 860℃ for 6h. After cooling, the composite carrier is obtained.

[0106] (2) Weigh 82.0g of the composite carrier prepared in (1), weigh 29.56g of nickel sulfate hexahydrate, 6.26g of lanthanum acetate monohydrate, and 1.87g of indium nitrate pentahydrate, add them to 65.32g of water to prepare a solution, add both to a hydrothermal crystallization kettle, and add 1.13g of ethylenediamine at the same time. Seal the kettle and place it in an ultrasonic water bath at 140℃ for 13h. The ultrasonic power is 1.6kW and the ultrasonic frequency is 50kHz. Then dry it at 120℃ for 8h, and then calcine it in a muffle furnace at 380℃ to decompose it, obtaining The semi-finished product was obtained; 24.18g of nickel sulfate hexahydrate, 5.12g of lanthanum acetate monohydrate and 1.53g of indium nitrate pentahydrate were weighed again and added to 65.32g of water to prepare a solution. The semi-finished product and the aqueous solution were added together to the hydrothermal crystallization kettle, and 0.92g of ethylenediamine was added at the same time. The kettle was sealed and placed in an ultrasonic water bath at 140℃ for 13h. The ultrasonic power was 1.6kW and the ultrasonic frequency was 50kHz. Then it was dried at 120℃ for 8h. Finally, it was calcined in a muffle furnace at 380℃ to decompose and obtain the catalyst precursor.

[0107] (3) The catalyst precursor in (2) is reduced by a programmed temperature rise method. The heating rate is 50℃ / h, the maximum reduction temperature is 430℃, and the temperature is kept constant for 8h. The reducing gas is a nitrogen-hydrogen mixture, in which the hydrogen volume percentage is 20%. Catalyst product A-10 is obtained.

[0108] Example 11

[0109] The procedure was carried out according to Example 1, except that the support was calcined at 1050°C. The resulting catalyst product was designated A-11.

[0110] Example 12

[0111] The procedure was carried out according to Example 1, except that the maximum reduction temperature of the catalyst precursor was 560°C. The resulting catalyst product was designated A-12.

[0112] Comparative Example 1

[0113] (1) Weigh 115.22g of boehmite, 11.25g of silica sol (JN-40), and 67.37g of calcium nitrate tetrahydrate. Place the boehmite in a kneader, add the weighed silica sol and calcium nitrate tetrahydrate to 48.81g of water to make a solution, and add the solution to the boehmite in the kneader and stir thoroughly. Then add 59.66g of an aqueous solution containing 4.05g of citric acid, knead and extrude into a clover shape, dry it at 100℃ for 8h, and then calcine it in a muffle furnace at 900℃ for 6h. After cooling, the composite carrier is obtained.

[0114] (2) Weigh 67.50g of the composite carrier prepared in (1), weigh 51.30g of nickel acetate tetrahydrate, 10.01g of lanthanum acetate monohydrate and 4.68g of indium nitrate pentahydrate and add them to 62.10g of water to make a solution. Add both of them to a hydrothermal crystallization kettle and add 0.83g of ethylenediamine at the same time. Seal the kettle and place it in an ultrasonic water bath at 135℃ for 15h. The ultrasonic power is 1.2kW and the ultrasonic frequency is 110kHz. Then dry it at 130℃ for 5h and then calcine it in a muffle furnace at 410℃ to decompose it. A semi-finished product was obtained; 41.98 g of nickel acetate tetrahydrate, 8.19 g of lanthanum acetate monohydrate and 3.83 g of indium nitrate pentahydrate were weighed again and added to 62.10 g of water to prepare a solution. The semi-finished product and the aqueous solution were added together to a hydrothermal crystallization kettle, and 0.68 g of ethylenediamine was added at the same time. The kettle was sealed and placed in an ultrasonic water bath at 135°C for 15 h. The ultrasonic power was 1.2 kW and the ultrasonic frequency was 110 kHz. Then it was dried at 130°C for 5 h, and then calcined in a muffle furnace at 410°C to obtain the catalyst precursor.

[0115] (3) The catalyst precursor in (2) is reduced by a programmed temperature rise method. The heating rate is 70℃ / h, the maximum reduction temperature is 400℃, and the temperature is kept constant for 8h. The reducing gas is a nitrogen-hydrogen mixture, in which the hydrogen volume percentage is 20% to obtain catalyst product B-1.

[0116] Comparative Example 2

[0117] (1) Weigh 127.54g of boehmite, 22.67g of silica sol (JN-40), and 34.95g of calcium acetate. Place the boehmite in a kneader, add the weighed silica sol and calcium acetate to 51.65g of water to make a solution, add the solution to the boehmite in the kneader and stir thoroughly. Then add 63.13g of an aqueous solution containing 6.28g of acetic acid, knead and extrude into cylindrical strips, dry at 120℃ for 6h, and then calcine at 750℃ in a muffle furnace for 8h. After cooling, the composite carrier is obtained.

[0118] (2) Weigh 65.0g of the composite carrier prepared in (1), weigh 69.96g of nickel acetate tetrahydrate, 5.01g of lanthanum acetate monohydrate, and 1.87g of indium nitrate pentahydrate, add them to 59.80g of water to prepare a solution, add both to a hydrothermal crystallization kettle, and add 0.72g of ethylenediamine at the same time. Seal the kettle and place it in an ultrasonic water bath at 150℃ for 10h. The ultrasonic power is 1.4kW and the ultrasonic frequency is 80kHz. Then dry it at 130℃ for 4h, and then calcine it in a muffle furnace at 430℃ to decompose it, obtaining The semi-finished product was obtained; 57.24g of nickel acetate tetrahydrate, 4.1g of lanthanum acetate monohydrate and 1.53g of indium nitrate pentahydrate were weighed again and added to 59.80g of water to prepare a solution. The semi-finished product and the aqueous solution were added together to the hydrothermal crystallization kettle, and 0.59g of ethylenediamine was added at the same time. The kettle was sealed and placed in an ultrasonic water bath at 150℃ for 10h. The ultrasonic power was 1.4kW and the ultrasonic frequency was 80kHz. Then it was dried at 130℃ for 4h, and then calcined in a muffle furnace at 430℃ to obtain the catalyst precursor.

[0119] (3) The catalyst precursor in (2) is reduced by a programmed temperature rise method. The heating rate is 60℃ / h, the maximum reduction temperature is 430℃, and the temperature is kept constant for 5h. The reducing gas is a nitrogen-hydrogen mixture, in which the hydrogen volume percentage is 20% to obtain catalyst product B-2.

[0120] Comparative Example 3

[0121] (1) Weigh 123.91g of boehmite and 35.26g of silica sol (JN-40). Place the boehmite in a kneader, add the weighed silica sol to 45.97g of water to make a solution, add it to the boehmite in the kneader and stir thoroughly. Then add 56.19g of an aqueous solution containing 4.96g of dilute nitric acid, knead and extrude into a clover shape, dry it at 110℃ for 6h, and then calcine it in a muffle furnace at 800℃ for 6h. After cooling, the composite carrier is obtained.

[0122] (2) Weigh 61.0g of the composite carrier prepared in (1), weigh 88.68g of nickel sulfate hexahydrate, 2.50g of lanthanum acetate monohydrate, and 1.87g of indium nitrate pentahydrate, add them to 56.12g of water to prepare a solution, add both to a hydrothermal crystallization kettle, and add 1.12g of ethylenediamine at the same time. Seal the kettle and place it in an ultrasonic water bath at 140℃ for 20h. The ultrasonic power is 0.8kW and the ultrasonic frequency is 130kHz. Then dry it at 140℃ for 5h, and then calcine it in a muffle furnace at 450℃ to decompose it, obtaining The semi-finished product was obtained; 72.55g of nickel sulfate hexahydrate, 2.05g of lanthanum acetate monohydrate and 1.53g of indium nitrate pentahydrate were weighed again and added to 56.12g of water to prepare a solution. The semi-finished product and the aqueous solution were added together to the hydrothermal crystallization kettle, and 0.91g of ethylenediamine was added at the same time. The kettle was sealed and placed in an ultrasonic water bath at 140℃ for 16h. The ultrasonic power was 0.8kW and the ultrasonic frequency was 130kHz. Then it was dried at 140℃ for 5h. Finally, it was calcined in a muffle furnace at 450℃ to decompose and obtain the catalyst precursor.

[0123] (3) The catalyst precursor in (2) is reduced by a programmed temperature rise method. The heating rate is 80℃ / h, the maximum reduction temperature is 440℃, and the temperature is kept constant for 5h. The reducing gas is a nitrogen-hydrogen mixture, in which the hydrogen volume percentage is 20%. Catalyst product B-3 is obtained.

[0124] Comparative Example 4

[0125] The method was carried out according to Example 1, except that in step (1), the silica sol and calcium nitrate tetrahydrate were replaced with boehmite (i.e., the amount of boehmite used was 144.93 g). The resulting catalyst product was designated as B-4.

[0126] Comparative Example 5

[0127] The procedure was carried out according to Example 1, except that in step (2), nickel sulfate hexahydrate was not added. Instead, 71g of the composite carrier prepared in (1) was weighed, 25.03g of lanthanum acetate monohydrate and 16.85g of indium nitrate pentahydrate were added to 65.32g of water to prepare a solution, and both were added to a hydrothermal crystallization vessel. At the same time, 0.98g of ethylenediamine was added, the vessel was sealed and placed in an ultrasonic water bath at 120°C for 20h. The ultrasonic power was 1.0kW and the ultrasonic frequency was 100kHz. Then it was dried at 120°C for 5h. The semi-finished product was obtained by calcination at 400℃ in a muffle furnace. 20.48g of lanthanum acetate monohydrate and 13.79g of indium nitrate pentahydrate were then added to 65.32g of water to prepare a solution. The semi-finished product and the aqueous solution were added to a hydrothermal crystallization reactor along with 0.80g of ethylenediamine. The reactor was sealed and placed in an ultrasonic water bath at 120℃ for 20 hours (ultrasonic power 1.0kW, ultrasonic frequency 100kHz). The mixture was then dried at 120℃ for 4 hours, followed by calcination at 400℃ in a muffle furnace to obtain the catalyst precursor. The resulting catalyst product was designated B-5.

[0128] Comparative Example 6

[0129] The method was carried out according to Example 1, except that in step (2), lanthanum acetate monohydrate was not added. That is, 71g of the composite carrier prepared in (1) was weighed, 54.19g of nickel sulfate hexahydrate and 13.11g of indium nitrate pentahydrate were weighed and added to 65.32g of water to make a solution. Both were added to a hydrothermal crystallization kettle, and 0.98g of ethylenediamine was added at the same time. The kettle was sealed and placed in an ultrasonic water bath at 120°C for 20h. The ultrasonic power was 1.0kW and the ultrasonic frequency was 100kHz. Then it was dried at 120°C for 5h, and then... The catalyst precursor was obtained by calcination and decomposition at 400℃ in a muffle furnace. 44.34g of nickel sulfate hexahydrate and 10.72g of indium nitrate pentahydrate were weighed and added to 65.32g of water to prepare a solution. The decomposed semi-finished product and the aqueous solution were added to a hydrothermal crystallization reactor along with 0.80g of ethylenediamine. The reactor was sealed and placed in an ultrasonic water bath at 120℃ for 20 hours (ultrasonic power 1.0kW, ultrasonic frequency 100kHz). It was then dried at 120℃ for 4 hours and subsequently calcined and decomposed at 400℃ in a muffle furnace to obtain the catalyst precursor. The obtained catalyst product was designated B-6.

[0130] Test Example 1

[0131] The catalyst products prepared in the above examples and comparative examples were subjected to the following measurements:

[0132] The weight ratio of alumina, silica, and calcium oxide in the carrier was calculated by X-ray fluorescence analysis (XRF) of the test carrier.

[0133] The content and ratio of metal elements supported on the catalysts were analyzed by X-ray fluorescence analysis. Among the catalysts, except for nickel, lanthanum, and indium, the rest served as supports.

[0134] The results are shown in Table 1-2.

[0135] Table 1

[0136]

[0137] Table 2

[0138]

[0139]

[0140] In the following test examples, all sampling and analysis were performed using gas chromatography.

[0141] BHT conversion rate:

[0142]

[0143] The selectivity of cyclohexylimine is:

[0144]

[0145] The selectivity of hexamethylenediamine is:

[0146]

[0147] The selectivity of C12 amines is:

[0148]

[0149] The selectivity of C18 amines is:

[0150]

[0151] Test Example 2

[0152] The catalysts prepared in the above examples and comparative examples were subjected to the following experiments:

[0153] 100 mL of catalyst was measured and loaded into a fixed-bed reactor. Activation was performed with hydrogen at 220 °C for 2 hours, followed by cooling to 190 °C. The system pressure was then increased to 16.0 MPa using hydrogen. Ammonia was metered and fed into the reaction system via a metering pump, and after preheating, it entered the upper part of the reactor. Bis(hexamethylene)triamine (BHT) was then metered and fed into the upper part of the reactor. Hydrogen was steadily introduced via a gas mass flow meter. The molar ratio of hydrogen to ammonia to BHT was 3:90:1, and the liquid hourly space velocity (LHSV) of BHT was 0.3 h⁻¹. -1The three substances were reacted in a catalyst bed. After the reaction stabilized, samples were taken for analysis, and the results are listed in Table 3.

[0154] Table 3

[0155]

[0156] Test Example 3

[0157] 100 mL of catalyst A-5 prepared in Example 5 was measured and placed in a fixed-bed reactor. Activation and reaction were carried out in the manner described in Test Example 2, but the temperature, pressure, molar ratio of hydrogen:ammonia:BHT, and liquid hourly space velocity of BHT were changed. The reaction sampling and analysis results are shown in Table 4.

[0158] Table 4

[0159]

[0160] Test Example 4

[0161] 100 mL of catalyst A-8 prepared in Example 8 was measured and placed in a fixed-bed reactor. It was activated with hydrogen at 220°C for 2 hours, then cooled to 190°C. The system pressure was increased to 16 MPa with hydrogen. Ammonia was then metered and fed into the reaction system via a metering pump, preheated, and introduced into the upper part of the reactor. BHT was also metered and fed into the upper part of the reactor. Hydrogen was steadily introduced via a gas mass flow meter. The molar ratio of hydrogen to ammonia to BHT was 3:100:1, and the liquid hourly space velocity (LHSV) of BHT was 0.3 h⁻¹. -1 The three substances were reacted in a catalyst bed. After the reaction stabilized, samples were taken for analysis at regular intervals. The analysis results are listed in Table 5.

[0162] Table 5

[0163]

[0164] Furthermore, the inventors of this invention have discovered that the catalysts prepared in the embodiments of this invention, particularly those prepared in Examples 1-8, also exhibit high conversion rates and selectivity under the conditions of Test Example 3. Moreover, the catalysts prepared in Examples 1-7 and 9, similar to the catalyst prepared in Example 8, also exhibit high stability.

[0165] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A process for the aminolysis of bis(hexamethylene)triamine to produce hexamethylenediamine and cyclohexylideneimine, characterized by, The method includes: subjecting bis(hexamethylene)triamine to an ammonolysis reaction under ammonolysis conditions and in the presence of a catalyst that catalyzes ammonolysis; The catalyst comprises a support and a primary metal element Ni, a secondary metal element La, and an in catalyst supported on the support. The content of Ni accounts for 10-40 wt% of the total weight of the catalyst; the weight of La accounts for 1-15 wt% of the total weight of the catalyst; and the weight of In accounts for 0.1-5 wt% of the total weight of the catalyst. The carrier includes alumina, silicon dioxide and calcium oxide, and the weight ratio of alumina, silicon dioxide and calcium oxide is (7-25):(0.8-5):

1.

2. The method according to claim 1, wherein the weight ratio of alumina, silicon dioxide and calcium oxide is (9-23):(1-4):

1.

3. The method of claim 1 or 2, wherein, The Ni content accounts for 11.5-30 wt% of the total catalyst weight; And / or, the weight ratio of Ni, La and In is (10-35):(1.5-10):

1.

4. The method of claim 1 or 2, wherein, The weight of La accounts for 3-10 wt% of the total weight of the catalyst; And / or, In accounts for 0.5-2.5 wt% of the total weight of the catalyst.

5. The method of claim 1, wherein, The preparation method of the catalyst with catalytic ammonolysis function includes: loading the main metal element Ni, the secondary metal element La and In onto a support, such that the loading amount of Ni accounts for 10-40 wt% of the total weight of the catalyst; the support includes alumina, silica and calcium oxide, and the weight ratio of alumina, silica and calcium oxide is (7-25):(0.8-5):1; the preparation method of the support includes: sequentially mixing, extruding, first drying and first calcining aluminum source, silicon source and calcium source, such that the weight ratio of alumina, silica and calcium oxide in the support is (7-25):(0.8-5):

1.

6. The method of claim 5, wherein, The weight ratio of aluminum oxide, silicon dioxide and calcium oxide is (9-23):(1-4):

1.

7. The method of claim 5, wherein, The temperature for the first roasting is 700-1000℃.

8. The method of claim 7, wherein, The temperature for the first roasting is 750-950℃.

9. The method of claim 5, wherein, The extrusion is carried out in the presence of an extrusion aid selected from at least one of citric acid, acetic acid, nitric acid, and phosphoric acid.

10. The method of claim 5, wherein, The aluminum source is selected from at least one of boehmite, alumina powder, boehmite, and aluminum hydroxide.

11. The method of claim 5, wherein, The silicon source is selected from at least one of silica sol, water glass, tetraethyl orthosilicate, and methyltrimethoxysilane.

12. The method of claim 5, wherein, The calcium source is selected from at least one of calcium nitrate tetrahydrate, calcium bicarbonate, calcium acetate, calcium bisulfate, calcium bisulfite, calcium dihydrogen phosphate, calcium permanganate, and calcium gluconate.

13. The method of claim 5, wherein, The method of loading Ni, La and In onto a support includes: mixing the support with Ni salt, La salt and In salt, performing hydrothermal crystallization, and performing a second drying and a second calcination.

14. The method of claim 13, wherein, The amounts of the support and Ni, La and In salts are such that: Ni accounts for 11.5-30 wt% of the total weight of the obtained catalyst; La accounts for 3-10 wt% of the total weight of the obtained catalyst; and In accounts for 0.5-2.5 wt% of the total weight of the obtained catalyst.

15. The method of claim 13, wherein, Ni salt is selected from at least one of nickel nitrate, nickel sulfate, and nickel acetate.

16. The method of claim 13, wherein, La salt is selected from at least one of lanthanum nitrate, lanthanum acetate, lanthanum sulfate, and lanthanum chloride.

17. The method of claim 13, wherein, The indium salt is selected from indium nitrate and / or indium sulfate.

18. The method of claim 13, wherein, Hydrothermal crystallization is carried out in multiple stages.

19. The method of claim 18, wherein, The conditions for hydrothermal crystallization include: being carried out under ultrasound, with an ultrasound power of 0.1-2.0KW, an ultrasound frequency of 35-130KHz, a temperature of 100-200℃, and a total hydrothermal crystallization time of 10-48h.

20. The method of claim 19, wherein, The conditions for hydrothermal crystallization include a temperature of 120-160℃.

21. The method of claim 18, wherein, After each hydrothermal crystallization, the material undergoes a second drying and a second calcination.

22. The method of claim 18, wherein, Hydrothermal crystallization is carried out in two separate processes, each lasting 6-22 hours.

23. The method of claim 22, wherein, Hydrothermal crystallization is carried out in the presence of a structure-directing agent selected from ethylenediamine and / or hexamethylenediamine, with the ratio of the total mass of the structure-directing agent to the mass of the carrier being (0.001-0.1):

1.

24. The method of claim 21, wherein, The preparation method further includes: reducing the product after the final second calcination.

25. The method of claim 24, wherein, The reduction method includes: using a nitrogen-hydrogen mixture as the reducing gas, with hydrogen accounting for 1-50% of the volume in the reducing gas, heating the material to 300-600℃ at a heating rate of 10-100℃ / h, and maintaining the temperature for 3-10h.

26. The method of claim 25, wherein, The reduction method includes: using a nitrogen-hydrogen mixture as the reducing gas, with hydrogen accounting for 15-30% of the volume in the reducing gas, heating the material to 400-500℃ at a heating rate of 40-80℃ / h, and maintaining the temperature at a constant temperature for 4-8h.

27. The method of claim 1, wherein, Ammonolysis conditions include: temperature 150-250℃; pressure 10-25MPa; and a feed liquid hourly space velocity (LHSV) of 0.01-1h for bis(hexamethylene)triamine. -1 The reaction is carried out in the presence of hydrogen and ammonia, with the molar ratio of hydrogen, ammonia and bis(hexamethylene)triamine being (1-15):(50-150):

1.

28. The method of claim 27, wherein, The ammonolysis conditions include: a temperature of 170-230℃; a pressure of 15-22 MPa; and a feed liquid hourly space velocity (LHSV) of 0.1-0.8 h⁻¹ for bis(hexamethylene)triamine. -1 The reaction is carried out in the presence of hydrogen and ammonia, with the molar ratio of hydrogen, ammonia and bis(hexamethylene)triamine being (2-10):(80-120):1.

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