Method and catalyst for preparing heterocyclic amine by catalytic amination of polyol amine

Abstract

Disclosed in the present invention is a method for preparing a heterocyclic amine by catalytic amination of a polyol amine. The method uses polyols, polyamines or alcohol amines as starting materials, and subjects same to a hydroamination reaction with ammonia or an organic amine source under the action of a catalyst so as to synthesize a product mainly comprising a heterocyclic amine. The catalyst consists of three parts: an active metal, an auxiliary agent and a carrier, wherein the active metal is one or a combination of Co, Ni, Cu, Pd, Ru and Ir, the auxiliary agent is one or a combination of Fe, Sn, In, Re, Mn, B, V, W, Nb, Cr, La, Mo and Zn, and the carrier is one or a combination of CeO2, Al2O3, TiO2, a molecular sieve, activated carbon, SiO2 and Al2O3-SiO2. During the preparation process of the catalyst, surface hydrophobic modification is implemented by introducing organosilanes or polymers, etc., to the surface of the catalyst. The catalyst prepared by the method is applied in reactions for preparing heterocyclic amines by amination of polyol amines, and has the advantages of high yield of heterocyclic amines, good stability and high activity, and thus has a broad industrial prospect.

Description

A method and catalyst for the catalytic amination of polyol amines to prepare heterocyclic amines. Technical Field

[0001] This invention relates to a method and catalyst for the catalytic amination of polyol amines to prepare heterocyclic amines. More specifically, it relates to a method for synthesizing heterocyclic amines from polyol amines using a hydrophobically modified catalyst, which is used to convert raw polyol amine sources and ammonia sources into amine products mainly composed of heterocyclic amines through a catalytic reaction under a hydrogen atmosphere. Background Technology

[0002] Heterocyclic amines are cyclic compounds composed of carbon and nitrogen atoms, including morpholines, piperazines, pyrroles, and pyridines. As a class of organic amines with special structures, they have wide applications in curing agents, polymers, pharmaceutical intermediates, and functional materials. With the continuous maturation of China's chemical industry and the gradual optimization of its industrial structure, the market demand for heterocyclic amines is increasing.

[0003] Currently reported synthetic routes for heterocyclic amines such as piperazines and morpholines typically involve the amination of alcohol feedstocks. This process is green, clean, has high atom utilization, and operates under mild conditions, attracting widespread attention from researchers. US Patent 3,155,657 reports the application of an alumina-supported ruthenium-based catalyst in the amination of diethylene glycol, achieving a diethylene glycol conversion of 96.9% and a morpholine yield of 77.2% at 257°C and 4000 psi. US Patent 8,981,093 reports a Ni-Co-Cu-Sn multi-metal supported catalyst, achieving a diethanolamine conversion of approximately 98%, a piperazine selectivity of 69%, and a heavy product yield of approximately 14% at 190 bar and 190°C. Chinese Patent CN111925341 reports the use of a Co-Ni-Mo / alumina catalyst for the diethanolamine-to-piperazine process, achieving a diethanolamine conversion of 96.4% and a piperazine selectivity of 86.6% under gas-solid reaction conditions at 1 MPa and 200°C. In summary, current catalytic systems and processes for producing heterocyclic amine compounds via alcohol amination still suffer from one or more of the following drawbacks: 1. High reaction temperature; 2. High reaction pressure; 3. High proportion of heavy components in the product; 4. Low piperazine yield; 5. Unstable catalyst; 6. Poor substrate applicability; 7. Low catalyst activity. This invention provides a new method to overcome these drawbacks. Summary of the Invention

[0004] The purpose of this invention is to provide a method and catalyst for the catalytic amination of polyol amines to prepare heterocyclic amines, wherein the method is carried out in the presence of a supported metal catalyst. This method, used for the catalytic amination of alcohols, amines, or alcoholamines as raw materials to prepare heterocyclic amines, features high cyclic amine yield, few byproducts, high catalytic activity, good stability, mild conditions, and a green and clean reaction process.

[0005] According to one aspect of the present invention, the present invention provides a supported catalyst for the catalytic amination of alcoholamines to prepare heterocyclic amines.

[0006] The catalyst consists of three parts: an active metal, an auxiliary element, and a support, with the active metal and the auxiliary element loaded on the support.

[0007] The carrier is one or more of CeO2, Al2O3, TiO2, molecular sieve, activated carbon, SiO2, and Al2O3-SiO2.

[0008] The specific surface area of ​​the carrier is 50–1800 m². 2 / g; pore volume 0.2~1.2ml / g;

[0009] Preferably, the specific surface area of ​​the carrier is 70–700 m². 2 / g; pore volume 0.3~1.0ml / g.

[0010] The active metal is one or a combination of Co, Ni, Cu, Pd, Ru, and Ir;

[0011] The active component accounts for 5-60% of the total weight of the catalyst;

[0012] Preferably, the active component accounts for 10-40% of the total weight of the catalyst.

[0013] The auxiliary agent is one or a combination of elements Fe, Sn, In, Re, Mn, B, V, W, Nb, Cr, La, Mo, and Zn;

[0014] The weight of the auxiliary agent accounts for 0.05 to 10% of the total weight of the catalyst;

[0015] Preferably, the additive accounts for 0.5 to 6% of the total weight of the catalyst.

[0016] The catalyst is characterized in that at least one or two of the impregnation method and precipitation method are used to load the active metal and the additive onto the support.

[0017] The preparation process of the catalyst is characterized by comprising the following steps: support synthesis or pretreatment, loading of metal and auxiliary precursors onto the support, sample drying, sample calcination, and sample reduction.

[0018] The catalyst is prepared as follows:

[0019] The catalyst is obtained by immersing the support in a solution containing an active metal element source and an auxiliary element source, followed by drying, calcination, and reduction.

[0020] Alternatively, a solution containing an active metal element source and an auxiliary element source can be added together with a precipitant to a suspension of the carrier, followed by precipitation, aging, washing, drying, calcination, and reduction to obtain the catalyst.

[0021] The drying conditions are: temperature 50-200℃, time 0.5-15h, and atmosphere is one or more combinations of air, oxygen, and nitrogen.

[0022] The calcination conditions are: temperature 200-600℃, time 0.5-15h, and atmosphere is one or more combinations of air, oxygen, and nitrogen.

[0023] The reduction treatment conditions are: temperature 200–600℃, pressure 0.1 MPa, time 0.5–10 h, and gas hourly space velocity 20–3000 h⁻¹. -1 The gas contains 1-100% hydrogen, and the remaining components are inert gases.

[0024] Optionally, the catalyst can be prepared by one or a combination of impregnation and precipitation methods to load the active component and auxiliary agent onto the support.

[0025] More specifically, when the impregnation method is used, the process is as follows: the support is impregnated in a solution containing an active metal element source and an auxiliary element source, and then dried, calcined, and reduced to obtain the catalyst.

[0026] Optionally, in the impregnation method implementation, the active component and additives can be loaded onto the carrier using a co-impregnation or stepwise impregnation method.

[0027] More specifically, when using the precipitation method, the process is as follows: a solution containing an active metal element source and an auxiliary element source is added together with a precipitant to a suspension of the carrier, followed by precipitation, aging, washing, drying, calcination, and reduction to obtain the catalyst.

[0028] Optionally, the precipitant used is preferably an inorganic alkali, preferably sodium hydroxide, sodium carbonate, potassium hydroxide or potassium carbonate.

[0029] Alternatively, the precipitant used may also be an ammonium salt, such as ammonium carbonate, ammonium hydroxide, or ammonium halide.

[0030] Optionally, the precipitation temperature can be 20–100°C, preferably 40–60°C.

[0031] Optionally, the active component precursor includes soluble salts of Co, Ni, Cu, Pd, Ru, and Ir.

[0032] The following explanation uses soluble salts of Co. The soluble salts of Co used can be cobalt nitrate, cobalt acetate, cobalt chloride, cobalt sulfate, or cobalt citrate, with cobalt nitrate and cobalt acetate being preferred.

[0033] The following explanation uses soluble salts of Ni as an example. The soluble salts of Ni used can be nickel nitrate, nickel acetate, nickel chloride, nickel sulfate, or nickel citrate, with nickel nitrate and nickel acetate being preferred.

[0034] Optionally, the auxiliary precursor includes soluble precursors of auxiliary elements Fe, Sn, In, Re, Mn, B, V, W, Nb, Cr, La, Mo, and Zn.

[0035] The catalyst preparation process mainly includes support synthesis or pretreatment, loading of metal and auxiliary precursors on the support, sample drying, sample calcination, and sample reduction.

[0036] The carrier synthesis includes the use of common methods such as sol-gel method, hydrolysis method, and precipitation method.

[0037] The types of carriers include CeO2, Al2O3, TiO2, molecular sieves, activated carbon, SiO2, Al2O3-SiO2, etc.

[0038] According to another aspect of the present invention, a method for hydrophobicating a catalyst is provided.

[0039] The catalyst used in the preparation of heterocyclic amines by catalytic amination of polyol amines requires hydrophobic treatment before the reaction.

[0040] The surface hydrophobication treatment is performed during the catalyst preparation process.

[0041] The surface hydrophobication treatment is as follows: the hydrophobic agent is modified on the catalyst surface by methods such as impregnation, co-hydrolysis, self-assembly, sol-gel, coating, and grafting.

[0042] Optionally, the following methods can be used: surface hydrophobic treatment can be performed during the carrier synthesis process, or surface hydrophobic treatment can be performed on the carrier, or surface hydrophobic treatment can be performed during the impregnation or precipitation process of active metals and additives, or surface hydrophobic treatment can be performed on the dried sample, or surface hydrophobic treatment can be performed on the calcined sample, or surface hydrophobic treatment can be performed on the reduced sample.

[0043] The hydrophobic agent is an organosilane or polymer.

[0044] The hydrophobic agent accounts for 0.1% to 15% of the total weight of the carrier agent;

[0045] Preferably, the hydrophobic agent accounts for 1 to 10% of the total weight of the carrier.

[0046] The hydrophobic agent is an organosilane, polymer, or long-chain fatty acid, etc.

[0047] Optionally, when an organosilane is selected as a hydrophobic agent, it includes, but is not limited to, one or more of methyltriethoxysilane, methyltrimethoxysilane, octyltriethoxysilane, octyltrimethoxysilane, diethoxydimethylsilane, trimethylchlorosilane, trifluoropropyltrichlorosilane, trifluoropropyltriethoxysilane, hexadecyltrimethoxysilane, octadecyltrimethoxysilane, etc.

[0048] Optionally, when a polymer is selected as the hydrophobic agent, it may include, but is not limited to, one or more of polypropylene, polytetrafluoroethylene, polyethylene, polystyrene, etc.

[0049] Alternatively, when choosing long-chain fatty acids as hydrophobic agents, fatty acids with more than 10 carbon atoms should be selected, such as dodecanoic acid, hexadecanoic acid, and stearic acid.

[0050] The surface hydrophobication treatment is performed during the catalyst preparation process.

[0051] Optionally, the catalyst support is hydrophobically treated with organosilane: a certain amount of organosilane is dissolved in an organic solvent, a certain amount of support is added and dispersed evenly, and after treatment for a period of time, after separation, washing, drying, etc., a sample with hydrophobically treated support surface is obtained, which is used to synthesize catalysts by impregnation or precipitation method, and the synthesis process is as described above.

[0052] Optionally, the process of adding polymers for surface hydrophobic treatment during the impregnation or precipitation of active metals and additives can be used as an example: a certain amount of polymer emulsion is added to a solution of active metal element source and additive element source, and the mixture is dispersed evenly. The carrier is impregnated in the above solution, and after drying, calcination, and reduction, a catalyst with surface hydrophobic treatment is obtained.

[0053] Optionally, the case of treating the surface of the calcined catalyst with stearic acid to make it hydrophobic can be used as an example: a certain amount of stearic acid is dissolved in an organic solution, the calcined catalyst is added and dispersed evenly, and after treatment for a certain period of time, the sample is obtained by separation, washing, drying, etc., and then reduced and used in the reaction.

[0054] Optionally, the reduction catalyst is subjected to surface hydrophobication treatment with organosilane as an example: the organosilane is dissolved and dispersed in a certain amount of organic solvent solution, the reduced catalyst sample is added under hydrogen atmosphere, the dispersion is uniform, washed and separated, and dried under inert atmosphere to obtain the surface hydrophobicated catalyst.

[0055] The catalyst prepared by this method can be used for the catalytic amination of polyol amines to prepare heterocyclic amines. It has the advantages of high heterocyclic amine yield, good stability and high activity, and has broad industrial prospects.

[0056] According to another aspect of the present invention, a process route for synthesizing heterocyclic amines via catalytic ammoniation reaction using polyol amine sources and ammonia sources as main raw materials is provided. This method has one or more advantages, such as readily available raw materials, good substrate applicability, good economy, adjustable product distribution, high heterocyclic amine yield, continuous production capability, and simple and easy-to-operate process route.

[0057] The catalytic ammoniation reaction uses polyol amine source and ammonia as raw materials, and employs the catalyst provided by this invention. Under certain reaction conditions and in a hydrogen atmosphere, the reaction generates amine products with heterocyclic amines as the main product.

[0058] The raw materials for the catalytic amination reaction include two parts: a polyol amine source and an ammonia source.

[0059] The polyol amine source raw materials include polyols, polyamines, or alcohol amine compounds;

[0060] The polyol amine source material is characterized in that the total number of amino and hydroxyl functional groups in its chemical structure is greater than or equal to 2.

[0061] Optionally, when the polyol amine source is a polyol compound, the polyol is a compound containing two or more hydroxyl groups, including ethylene glycol, diethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexanediol, phthalic acid, etc.

[0062] Optionally, when the polyol amine source is a polyamine compound, the polyamine is a compound containing two or more amino groups, including ethylenediamine, propylenediamine, butanediamine, pentanediamine, hexanediamine, diethylenetriamine, 2,2'-oxodiethylamine, hydroxyethyldiethylenetriamine, etc.

[0063] Optionally, when the polyol amine source is an alcohol amine compound, the alcohol amine is a compound containing both hydroxyl and amino groups, including monoethanolamine, diethanolamine, triethanolamine, hydroxyethyl ethylenediamine, diethylene glycolamine, aminopropanol, aminobutanol, aminopentanol, aminohexanol, etc.

[0064] The polyol amine source includes one or more of polyols, polyamines, or alkanolamine compounds;

[0065] The ammonia source is ammonia or a primary amine.

[0066] Specifically, when the ammonia source is ammonia, it includes liquid ammonia, ammonia gas, and ammonia water;

[0067] Specifically, when the ammonia source is a primary amine, including but not limited to methylamine, ethylamine, propylamine, and benzylamine.

[0068] The molar ratio of polyol amine source to ammonia source in the reaction raw materials is 0.01 to 10:1;

[0069] Preferably, the molar ratio of polyol amine source to ammonia source in the reaction raw materials is 0.05 to 5:1.

[0070] The catalytic reaction process is carried out under hydrogen-containing conditions, wherein the molar proportion of hydrogen in the total feed material (including hydrogen and reactants) is 0.5-80%.

[0071] Preferably, the molar proportion of hydrogen in the total feed material (including hydrogen and reactants) is 1-40%.

[0072] The reaction conditions are: temperature 130–220℃, pressure 1–30 MPa;

[0073] Preferably, the reaction conditions are: temperature 150-200℃, pressure 4-25MPa.

[0074] The total liquid hourly space velocity (LHSV) of the polyol amine source in the reaction feedstock is 0.02–15 h⁻¹. -1 ;

[0075] Preferably, the total liquid hourly space velocity (LHSV) of the polyol amine source in the reaction feedstock is 0.1–10 h⁻¹. -1 .

[0076] The polyol amine catalytic amination reaction to prepare heterocyclic amines is carried out in a reactor;

[0077] The reactor includes one or more of continuous and batch reactors;

[0078] Optionally, the continuous reactor is selected from one or more of the following: fixed-bed reactor, continuous stirred tank reactor, slurry-bed reactor, and fluidized-bed reactor;

[0079] Optionally, the batch reactor is selected from the autoclave reactor.

[0080] Preferably, the reactor for the preparation of heterocyclic amines by catalytic ammoniation of polyol amines is selected from one or more of a fixed-bed reactor and a high-pressure reactor.

[0081] This invention uses polyols, polyamines, or alkanolamines as raw materials, and synthesizes heterocyclic amine-based products via hydroammoniation with ammonia or organic amine sources under the action of a catalyst. The catalyst is prepared by introducing organosilanes or polymers to hydrophobically modify its surface. The catalyst obtained by this method is used in the amination of polyol amines to prepare heterocyclic amines, exhibiting advantages such as high heterocyclic amine yield, good stability, and high activity, showing broad industrial prospects.

[0082] The beneficial effects of this invention are as follows:

[0083] 1) This invention generates a synergistic catalytic effect through the combination of active component elements, auxiliary elements and carriers, which increases the probability of intramolecular or intermolecular cyclization reaction of polyol amine sources, thereby increasing the yield of heterocyclic amines.

[0084] 2) This invention achieves the purpose of improving catalytic efficiency and increasing the selectivity of heterocyclic amines by performing surface hydrophobic treatment during catalyst synthesis, thereby regulating the adsorption-desorption rate of water or ammonia on the catalyst surface during the reaction and forming a surface hydrophobic environment.

[0085] 3) This invention optimizes the hydrophobic properties of the catalyst surface by selecting the type of hydrophobic agent, the hydrophobic treatment method, and controlling the amount of hydrophobic agent added, thereby obtaining a hydrophobic agent-modified catalytic system suitable for polyol amine source substrates;

[0086] The catalyst of this invention has good substrate applicability and is well applicable to polyols, polyamines or alkanolamines, enabling the directional synthesis of heterocyclic amines. Detailed Implementation

[0087] The present invention will be further described below through specific embodiments.

[0088] The catalysts used in the examples and comparative examples were evaluated using a fixed-bed reactor. Product analysis was performed using gas chromatography with an SE-30 capillary column, an FID detector, and N,N-dimethylformamide as an internal standard for quantification. Some analytical results are listed in Table 1. Ammonia and water were not included in the calculation of product selectivity data. A "-" is used in Table 1 to indicate that a reaction product was not detected in the product. The conversion rates in Table 1 refer to the conversion rates of the polyol amine sources in the examples.

[0089] The loading of active metals and auxiliary elements on the catalysts described in the examples and comparative examples was determined by inductively coupled plasma atomic emission spectrometry or X-ray fluorescence spectrometry. The porous supports used in the examples and comparative examples included alumina supports with a specific surface area of ​​approximately 350 μm. 2 / g, pore volume approximately 0.4ml / g; silica carrier specific surface area approximately 450m² 2 / g, pore volume approximately 0.7ml / g; alumina-silica carrier specific surface area approximately 400m². 2 / g, pore volume approximately 0.4ml / g; activated carbon carrier specific surface area approximately 650m² 2 / g, pore volume approximately 0.9ml / g; cerium oxide support specific surface area approximately 120m² 2 / g, pore volume approximately 0.4ml / g; titanium dioxide support specific surface area approximately 100m² 2 / g, pore volume approximately 0.5ml / g.

[0090] The content of active metals and auxiliary components in the catalysts in the examples and comparative examples is indicated in the catalyst name. Taking the catalyst of Example 1 as an example: Ni5Pd2-Sn2 / silica catalyst, the representative element Ni accounts for 5% of the total weight of the catalyst, the representative element Pd accounts for 2% of the total weight of the catalyst, and the representative element Sn accounts for 2% of the total weight of the catalyst.

[0091] For specific catalyst preparation and reaction conditions, please refer to the examples and comparative examples:

[0092] Example 1

[0093] The preparation method of catalyst 1 is as follows. First, the support surface is hydrophobically treated: 0.228 g of octyltrimethoxysilane is dispersed in 200 ml of toluene solution and stirred evenly at 50 °C. 9.1 g of silica support is added and dispersed in the above solution. After treatment for 12 h, the surface is centrifuged, washed, and dried at 120 °C to obtain the surface-hydrophobically treated support. 12 ml of an aqueous solution containing 2.477 g of Ni(NO3)2·6H2O, 0.488 g of Pd(NO3)2·2H2O, and 0.439 g of SnCl2 is prepared. The above surface-hydrophobically treated support is impregnated, air-dried naturally, dried at 120 °C for 10 h, and calcined at 400 °C in nitrogen for 5 h. Reduction treatment is then performed: the reduction conditions are a temperature of 400 °C, an atmosphere of atmospheric pressure hydrogen, and a volume hourly space velocity of 1000 h⁻¹. -1 The reduction time was 6 hours. Catalyst 1 was obtained: Ni5Pd2-Sn2 / silica, which was stored under nitrogen.

[0094] Reaction Evaluation: Catalyst 1 was transferred to a fixed-bed reactor under a nitrogen atmosphere. The reaction temperature was 190℃, the pressure was 10 MPa, and the liquid feed consisted of diethylene glycol and liquid ammonia, with a diethylene glycol:liquid ammonia molar ratio of 0.2:1. The liquid hourly space velocity (LHSV) of the diethylene glycol was 1 h⁻¹. -1 The molar concentration of hydrogen (which accounts for 5% of the total feed material, including both hydrogen and reactants) was 5%. Samples were taken for analysis after 50 hours of continuous reaction in the fixed-bed reactor. The results are shown in Table 1.

[0095] Example 2

[0096] The preparation method of catalyst 2 is as follows. First, the support surface is hydrophobically treated: 0.210 g of octyltrimethoxysilane is dispersed in 200 ml of toluene solution and stirred evenly at 50 °C. 8.4 g of silica support is added and dispersed in the above solution. After treatment for 12 h, the surface is centrifuged, washed, and dried at 120 °C to obtain the surface-hydrophobically treated support. 12 ml of an aqueous solution containing 4.955 g of Ni(NO3)2·6H2O, 0.976 g of Pd(NO3)2·2H2O, and 0.439 g of SnCl2 is prepared. The above surface-hydrophobically treated support is impregnated, air-dried naturally, dried at 120 °C for 10 h, and calcined at 400 °C in nitrogen for 5 h. Reduction treatment is then performed: the reduction conditions are a temperature of 400 °C, an atmosphere of atmospheric pressure hydrogen, and a volume hourly space velocity of 1000 h⁻¹. -1 The reduction time was 6 hours. Catalyst 2 was obtained: Ni10Pd4-Sn2 / silica, which was stored under nitrogen.

[0097] Catalyst 2 was used for reaction evaluation. The reaction conditions were the same as in Example 1. The results are shown in Table 1.

[0098] Example 3

[0099] The preparation method of catalyst 3 is as follows. First, the support surface is hydrophobically treated: 0.193 g of octyltrimethoxysilane is dispersed in 200 ml of toluene solution and stirred evenly at 50 °C. 7.7 g of silica support is added and dispersed in the above solution. After treatment for 12 h, the surface is centrifuged, washed, and dried at 120 °C to obtain the surface-hydrophobically treated support. 12 ml of an aqueous solution containing 7.432 g of Ni(NO3)2·6H2O, 1.463 g of Pd(NO3)2·2H2O, and 0.439 g of SnCl2 is prepared. The above surface-hydrophobically treated support is impregnated, air-dried naturally, dried at 120 °C for 10 h, and calcined at 400 °C in nitrogen for 5 h. Reduction treatment is then performed: the reduction conditions are a temperature of 400 °C, an atmosphere of atmospheric pressure hydrogen, and a volume hourly space velocity of 1000 h⁻¹. -1 The reduction time was 6 hours. Catalyst 3 was obtained: Ni15Pd6-Sn2 / silica, which was stored under nitrogen.

[0100] Catalyst 3 was used for reaction evaluation. The reaction conditions were the same as in Example 1. The results are shown in Table 1.

[0101] Example 4

[0102] The preparation method of catalyst 4 is as follows. First, the support surface is hydrophobically treated: 0.140 g of octyltrimethoxysilane is dispersed in 200 ml of toluene solution and stirred evenly at 50 °C. 5.6 g of silica support is added and dispersed in the above solution. After treatment for 12 h, centrifugation, washing, and drying at 120 °C are performed to obtain the surface-hydrophobically treated support. 24 ml of an aqueous solution containing 14.864 g of Ni(NO3)2·6H2O, 2.927 g of Pd(NO3)2·2H2O, and 0.439 g of SnCl2 is prepared and divided into two equal portions. The following process is repeated twice: one portion of the solution is used to impregnate the above surface-hydrophobically treated support, air-dried naturally, dried at 120 °C for 10 h, and calcined at 400 °C in nitrogen for 5 h. Reduction treatment is then performed: the reduction conditions are a temperature of 400 °C, an atmosphere of atmospheric pressure hydrogen, and a volume hourly space velocity of 1000 h⁻¹. -1 The reduction time was 6 hours. Catalyst 4 was obtained: Ni30Pd12-Sn2 / silica, which was nitrogen-sealed and stored.

[0103] Catalyst 4 was used for reaction evaluation. The reaction conditions were the same as in Example 1. The results are shown in Table 1.

[0104] Example 5

[0105] The preparation method of catalyst 5 is as follows. First, the support surface is hydrophobically treated: 0.105 g of octyltrimethoxysilane is dispersed in 200 ml of toluene solution and stirred evenly at 50 °C. 4.2 g of silica support is added and dispersed in the above solution. After treatment for 12 h, centrifugation, washing, and drying at 120 °C are performed to obtain the surface-hydrophobically treated support. Prepare 36 ml of an aqueous solution containing 19.819 g of Ni(NO3)2·6H2O, 3.902 g of Pd(NO3)2·2H2O, and 0.439 g of SnCl2. Divide the solution into 3 equal portions and repeat the following process 3 times: take one portion of the solution to impregnate the above surface-hydrophobically treated support, air dry naturally, dry at 120 °C for 10 h, and calcine at 400 °C in nitrogen for 5 h. Then, perform reduction treatment: the reduction conditions are a temperature of 400 °C, an atmosphere of atmospheric pressure hydrogen, and a volume hourly space velocity of 1000 h⁻¹. -1 The reduction time was 6 hours. Catalyst 5 was obtained: Ni40Pd16-Sn2 / silica, which was nitrogen-sealed and stored.

[0106] Catalyst 5 was used for reaction evaluation. The reaction conditions were the same as in Example 1. The results are shown in Table 1.

[0107] Example 6

[0108] The preparation method of catalyst 6 is as follows: Take 8.160 g of alumina support. Prepare 12 ml of an aqueous solution containing 4.941 g of Co(NO3)2·6H2O, 2.477 g of Ni(NO3)2·6H2O, 0.776 g of RuCl3·3H2O, 0.029 g of NH4ReO4, and 0.065 g of Mn(NO3)2. Impregnate the above alumina support with the solution, air dry naturally, dry at 120℃ for 10 h, and calcine at 350℃ in air for 8 h. Perform surface hydrophobic treatment on the calcined sample: Disperse 0.326 g of methyltriethoxysilane in 200 ml of toluene solution, stir evenly at 80℃, disperse the calcined sample in the toluene solution, treat for 8 h, centrifuge, wash, and dry at 120℃ to obtain the surface hydrophobic treated sample. Perform reduction treatment: The reduction conditions are temperature 450℃, atmosphere is atmospheric pressure hydrogen, and volume hourly space velocity is 1500 h⁻¹. -1 The reduction time was 8 hours. Catalyst 6 was obtained: Co10Ni5Ru3-Re0.2Mn0.2 / alumina, which was nitrogen-sealed and stored.

[0109] Catalyst 6 was transferred to the reactor under a nitrogen atmosphere. The reaction temperature was 170℃, the pressure was 15 MPa, and the liquid feed consisted of hydroxyethyl ethylenediamine and liquid ammonia, with a molar ratio of hydroxyethyl ethylenediamine to liquid ammonia of 0.12:1. The liquid hourly space velocity (LHSV) of the hydroxyethyl ethylenediamine was 1.2 h⁻¹. -1 The hydrogen molar concentration was 10%. Samples were taken for analysis after 50 hours of continuous reaction in a fixed-bed reactor. The results are shown in Table 1.

[0110] Example 7

[0111] The preparation method of catalyst 7 is as follows: Take 8.120 g of alumina support. Prepare 12 ml of an aqueous solution containing 4.941 g Co(NO3)2·6H2O, 2.477 g Ni(NO3)2·6H2O, 0.776 g RuCl3·3H2O, 0.058 g NH4ReO4, and 0.130 g Mn(NO3)2. Impregnate the above alumina support with the solution, air dry naturally, dry at 120℃ for 10 h, and calcine at 350℃ in air for 8 h. Perform surface hydrophobic treatment on the calcined sample: Disperse 0.325 g methyltriethoxysilane in 200 ml toluene solution, stir evenly at 80℃, disperse the calcined sample in the toluene solution, treat for 8 h, centrifuge, wash, and dry at 120℃ to obtain the surface hydrophobic treated sample. Perform reduction treatment: The reduction conditions are temperature 450℃, atmosphere is atmospheric pressure hydrogen, and volume hourly space velocity is 1500 h⁻¹. -1 The reduction time was 8 hours. Catalyst 7 was obtained: Co10Ni5Ru3-Re0.4Mn0.4 / alumina, which was nitrogen-sealed and stored.

[0112] Catalyst 7 was used for reaction evaluation. The reaction conditions were the same as in Example 6. The results are shown in Table 1.

[0113] Example 8

[0114] The preparation method of catalyst 8 is as follows: Take 8.0 g of alumina support. Prepare 12 ml of an aqueous solution containing 4.941 g Co(NO3)2·6H2O, 2.477 g Ni(NO3)2·6H2O, 0.776 g RuCl3·3H2O, 0.058 g NH4ReO4, and 0.130 g Mn(NO3)2. Impregnate the above alumina support with the solution, air dry naturally, dry at 120℃ for 10 h, and calcine in air at 350℃ for 8 h. Perform surface hydrophobic treatment on the calcined sample: Disperse 0.320 g methyltriethoxysilane in 200 ml toluene solution, stir evenly at 80℃, disperse the calcined sample in the toluene solution, treat for 8 h, centrifuge, wash, and dry at 120℃ to obtain the surface hydrophobic treated sample. Perform reduction treatment: The reduction conditions are temperature 450℃, atmosphere is atmospheric pressure hydrogen, and volume hourly space velocity is 1500 h⁻¹. -1 The reduction time was 8 hours. Catalyst 8 was obtained: Co10Ni5Ru3-Re1Mn1 / alumina, which was nitrogen-sealed and stored.

[0115] Catalyst 8 was used for reaction evaluation. The reaction conditions were the same as in Example 6. The results are shown in Table 1.

[0116] Example 9

[0117] The preparation method of catalyst 9 is as follows: Take 7.7 g of alumina support. Prepare 12 ml of an aqueous solution containing 4.941 g Co(NO3)2·6H2O, 2.477 g Ni(NO3)2·6H2O, 0.776 g RuCl3·3H2O, 0.058 g NH4ReO4, and 0.130 g Mn(NO3)2. Impregnate the above alumina support with the solution, air dry naturally, dry at 120℃ for 10 h, and calcine at 350℃ in air for 8 h. Perform surface hydrophobic treatment on the calcined sample: Disperse 0.308 g methyltriethoxysilane in 200 ml toluene solution, stir evenly at 80℃, disperse the calcined sample in the toluene solution, treat for 8 h, centrifuge, wash, and dry at 120℃ to obtain the surface hydrophobic treated sample. Perform reduction treatment: The reduction conditions are temperature 450℃, atmosphere is atmospheric pressure hydrogen, and volume hourly space velocity is 1500 h⁻¹. -1 The reduction time was 8 hours. Catalyst 9 was obtained: Co10Ni5Ru3-Re2.5Mn2.5 / alumina, which was nitrogen-sealed and stored.

[0118] Catalyst 9 was used for reaction evaluation. The reaction conditions were the same as in Example 6. The results are shown in Table 1.

[0119] Example 10

[0120] The preparation method of catalyst 10 is as follows: Take 7.4 g of alumina support. Prepare 12 ml of an aqueous solution containing 4.941 g Co(NO3)2·6H2O, 2.477 g Ni(NO3)2·6H2O, 0.776 g RuCl3·3H2O, 0.058 g NH4ReO4, and 0.130 g Mn(NO3)2. Impregnate the above alumina support with the solution, air dry naturally, dry at 120℃ for 10 h, and calcine at 350℃ in air for 8 h. Perform surface hydrophobic treatment on the calcined sample: Disperse 0.296 g methyltriethoxysilane in 200 ml toluene solution, stir evenly at 80℃, disperse the calcined sample in the toluene solution, treat for 8 h, centrifuge, wash, and dry at 120℃ to obtain the surface hydrophobic treated sample. Perform reduction treatment: The reduction conditions are temperature 450℃, atmosphere is atmospheric pressure hydrogen, and volume hourly space velocity is 1500 h⁻¹. -1 The reduction time was 8 hours. Catalyst 10 was obtained: Co10Ni5Ru3-Re4Mn4 / alumina, which was nitrogen-sealed and stored.

[0121] Catalyst 10 was used for reaction evaluation. The reaction conditions were the same as in Example 6. The results are shown in Table 1.

[0122] Example 11

[0123] The preparation method of catalyst 11 is as follows: Take 7.90 g of alumina support. Prepare 12 ml of an aqueous solution containing 3.964 g Ni(NO3)2·6H2O, 3.041 g Cu(NO3)2·3H2O, 0.367 g IrCl3·3H2O, 0.866 g Fe(NO3)3, and 0.573 g H3BO3. Impregnate the above alumina support with the solution, air dry naturally, dry at 120℃ for 10 h, and calcine in air at 450℃ for 10 h. Perform reduction treatment: The reduction conditions are 350℃, atmospheric hydrogen atmosphere, and volume hourly space velocity (VHSV) of 2500 h⁻¹. -1 The reduction time was 5 h, and the sample was stored under nitrogen. The reduced sample underwent surface hydrophobic treatment: 0.040 g of trifluoropropyltriethoxysilane was dispersed in 200 ml of toluene solution and stirred at 60 °C until homogeneous. The reduced sample was then dispersed in the toluene solution and treated for 24 h. After centrifugation, washing, and drying at 120 °C, catalyst 11: Ni8Cu8Ir2-Fe2B1 / activated carbon-1 was obtained and stored under nitrogen.

[0124] Catalyst 11 was transferred to the reactor under a nitrogen atmosphere. The reaction temperature was 200℃, the pressure was 12MPa, and the liquid feed consisted of diethanolamine and liquid ammonia, with a diethanolamine:liquid ammonia molar ratio of 0.07:1. The liquid hourly space velocity (LHSV) of the diethanolamine was 2 h⁻¹. -1 The hydrogen molar concentration was 3%. Samples were taken for analysis after 50 hours of continuous reaction in a fixed-bed reactor. The results are shown in Table 1.

[0125] Example 12

[0126] The preparation method of catalyst 12 is as follows: Take 7.90 g of alumina support. Prepare 12 ml of an aqueous solution containing 3.964 g Ni(NO3)2·6H2O, 3.041 g Cu(NO3)2·3H2O, 0.367 g IrCl3·3H2O, 0.866 g Fe(NO3)3, and 0.573 g H3BO3. Impregnate the above alumina support with the solution, air dry naturally, dry at 120℃ for 10 h, and calcine in air at 450℃ for 10 h. Perform reduction treatment: The reduction conditions are 350℃, atmospheric hydrogen atmosphere, and volume hourly space velocity (VHSV) of 2500 h⁻¹. -1 The reduction time was 5 h, and the sample was stored under nitrogen. The reduced sample underwent surface hydrophobic treatment: 0.119 g of trifluoropropyltriethoxysilane was dispersed in 200 ml of toluene solution and stirred at 60 °C until homogeneous. The reduced sample was then dispersed in the toluene solution and treated for 24 h. After centrifugation, washing, and drying at 120 °C, catalyst 12: Ni8Cu8Ir2-Fe2B1 / activated carbon-2 was obtained and stored under nitrogen.

[0127] Catalyst 12 was used for reaction evaluation. The reaction conditions were the same as in Example 11. The results are shown in Table 1.

[0128] Example 13

[0129] The preparation method of catalyst 13 is as follows: Take 7.90 g of alumina support. Prepare 12 ml of an aqueous solution containing 3.964 g Ni(NO3)2·6H2O, 3.041 g Cu(NO3)2·3H2O, 0.367 g IrCl3·3H2O, 0.866 g Fe(NO3)3, and 0.573 g H3BO3. Impregnate the above alumina support with the solution, air dry naturally, dry at 120℃ for 10 h, and calcine in air at 450℃ for 10 h. Perform reduction treatment: The reduction conditions are 350℃, atmospheric hydrogen atmosphere, and volume hourly space velocity (VHSV) of 2500 h⁻¹. -1 The reduction time was 5 h, and the sample was stored under nitrogen. The reduced sample underwent surface hydrophobic treatment: 0.316 g of trifluoropropyltriethoxysilane was dispersed in 200 ml of toluene solution and stirred at 60 °C until homogeneous. The reduced sample was then dispersed in the toluene solution and treated for 24 h. After centrifugation, washing, and drying at 120 °C, catalyst 13: Ni8Cu8Ir2-Fe2B1 / activated carbon-3 was obtained and stored under nitrogen.

[0130] Catalyst 13 was used for reaction evaluation. The reaction conditions were the same as in Example 11. The results are shown in Table 1.

[0131] Example 14

[0132] The preparation method of catalyst 14 is as follows: Take 7.90 g of alumina support. Prepare 12 ml of an aqueous solution containing 3.964 g Ni(NO3)2·6H2O, 3.041 g Cu(NO3)2·3H2O, 0.367 g IrCl3·3H2O, 0.866 g Fe(NO3)3, and 0.573 g H3BO3. Impregnate the above alumina support with the solution, air dry naturally, dry at 120℃ for 10 h, and calcine in air at 450℃ for 10 h. Perform reduction treatment: The reduction conditions are 350℃, atmospheric hydrogen atmosphere, and volume hourly space velocity (VHSV) of 2500 h⁻¹. -1 The reduction time was 5 h, and the sample was stored under nitrogen. The reduced sample underwent surface hydrophobic treatment: 0.632 g of trifluoropropyltriethoxysilane was dispersed in 200 ml of toluene solution and stirred at 60 °C until homogeneous. The reduced sample was then dispersed in the toluene solution and treated for 24 h. After centrifugation, washing, and drying at 120 °C, catalyst 14 was obtained: Ni8Cu8Ir2-Fe2B1 / activated carbon-4, which was then stored under nitrogen.

[0133] Catalyst 14 was used for reaction evaluation. The reaction conditions were the same as in Example 11. The results are shown in Table 1.

[0134] Example 15

[0135] The preparation method of catalyst 15 is as follows: Take 7.90 g of alumina support. Prepare 12 ml of an aqueous solution containing 3.964 g Ni(NO3)2·6H2O, 3.041 g Cu(NO3)2·3H2O, 0.367 g IrCl3·3H2O, 0.866 g Fe(NO3)3, and 0.573 g H3BO3. Impregnate the above alumina support with the solution, air dry naturally, dry at 120℃ for 10 h, and calcine in air at 450℃ for 10 h. Perform reduction treatment: The reduction conditions are: temperature 350℃, atmosphere of atmospheric pressure hydrogen, and volume hourly space velocity (VHSV) of 2500 h⁻¹. -1 The reduction time was 5 h, and the sample was stored under nitrogen. The reduced sample underwent surface hydrophobic treatment: 1.027 g of trifluoropropyltriethoxysilane was dispersed in 200 ml of toluene solution and stirred at 60 °C until homogeneous. The reduced sample was then dispersed in the toluene solution and treated for 24 h. After centrifugation, washing, and drying at 120 °C, catalyst 15: Ni8Cu8Ir2-Fe2B1 / activated carbon-5 was obtained and stored under nitrogen.

[0136] Catalyst 15 was used for reaction evaluation. The reaction conditions were the same as in Example 11. The results are shown in Table 1.

[0137] Example 16

[0138] The preparation method of catalyst 16 is as follows. The support is subjected to surface hydrophobic treatment: 0.10 g of diethoxydimethylsilane and 0.119 g of trifluoropropyltriethoxysilane are dissolved in 200 ml of n-hexane solution and stirred evenly at 30°C. 7.30 g of titanium dioxide support is dispersed in the n-hexane solution, treated for 18 h, centrifuged, washed, and dried at 120°C to obtain the surface-hydrophobic supported. 24 ml of an aqueous solution containing 7.412 g of Co(NO3)2·6H2O, 4.955 g of Ni(NO3)2·6H2O, 0.262 g of In(NO3)3, and 0.312 g of La(NO3)3·6H2O is prepared and divided into two equal portions. The following process is repeated twice: one portion of the solution is used to impregnate the above surface-hydrophobic supported, air-dried naturally, dried at 120°C for 10 h, and calcined in nitrogen at 200°C for 10 h. Reduction treatment was carried out under the following conditions: temperature 400℃, atmosphere of atmospheric pressure hydrogen, and volume hourly space velocity (VHSV) of 500 h⁻¹. -1 The reduction time was 10 h. Catalyst 16 was obtained: Co15Ni10-In1La1 / titanium dioxide-1, which was stored under nitrogen.

[0139] Catalyst 16 was transferred to the reactor under a nitrogen atmosphere. The reaction temperature was 160℃, the pressure was 8 MPa, and the liquid feed consisted of ethylene glycol and liquid ammonia, with a molar ratio of ethylene glycol to liquid ammonia of 0.3:1. The liquid hourly space velocity (LHSV) of the ethylene glycol was 0.5 h⁻¹. -1 The hydrogen molar concentration was 12%. Samples were taken for analysis after 50 hours of continuous reaction in a fixed-bed reactor. The results are shown in Table 1.

[0140] Example 17

[0141] The preparation method of catalyst 17 is as follows. The support is subjected to surface hydrophobic treatment: 0.05 g of trimethylchlorosilane and 0.169 g of polytetrafluoroethylene emulsion (calculated as polytetrafluoroethylene) are dissolved in 50 ml of tetrahydrofuran solution and stirred evenly at 30 °C. 7.30 g of titanium dioxide support is dispersed in the tetrahydrofuran solution, impregnated by evaporation, and the sample is dried at 120 °C to obtain the surface-hydrophobicated support. 24 ml of an aqueous solution containing 7.412 g of Co(NO3)2·6H2O, 4.955 g of Ni(NO3)2·6H2O, 0.262 g of In(NO3)3, and 0.312 g of La(NO3)3·6H2O is prepared and divided into two equal portions. The following process is repeated twice: one portion of the solution is used to impregnate the above surface-hydrophobicated support, air-dried naturally, dried at 120 °C for 10 h, and calcined at 200 °C in nitrogen for 10 h. Reduction treatment was carried out under the following conditions: temperature 400℃, atmosphere of atmospheric pressure hydrogen, and volume hourly space velocity (VHSV) of 500 h⁻¹. -1 The reduction time was 10 h. Catalyst 17 was obtained: Co15Ni10-In1La1 / titanium dioxide-2, which was stored under nitrogen.

[0142] Catalyst 17 was used for reaction evaluation. The reaction conditions were the same as in Example 16. The results are shown in Table 1.

[0143] Example 18

[0144] The preparation method of catalyst 18 is as follows. The support is subjected to surface hydrophobic treatment: 0.10 g of polystyrene emulsion (calculated as polystyrene), 0.69 g of polytetrafluoroethylene emulsion (calculated as polytetrafluoroethylene), and 0.05 g of polypropylene emulsion (calculated as polypropylene) are dissolved in 12 ml of aqueous solution. 7.30 g of titanium dioxide support is impregnated in this solution, and the mixture is dried at 120 °C to obtain a surface-hydrophobic supported material. 24 ml of an aqueous solution containing 7.412 g of Co(NO3)2·6H2O, 4.955 g of Ni(NO3)2·6H2O, 0.262 g of In(NO3)3, and 0.312 g of La(NO3)3·6H2O is prepared and divided into two equal portions. The following process is repeated twice: one portion of the solution is used to impregnate the above surface-hydrophobic supported material, air-dried naturally, dried at 120 °C for 10 h, and calcined in nitrogen at 200 °C for 10 h. Reduction treatment was carried out under the following conditions: temperature 400℃, atmosphere of atmospheric pressure hydrogen, and volume hourly space velocity (VHSV) of 500 h⁻¹. -1 The reduction time was 10 h. Catalyst 18 was obtained: Co15Ni10-In1La1 / titanium dioxide-3, which was stored under nitrogen.

[0145] Catalyst 18 was used for reaction evaluation. The reaction conditions were the same as in Example 16. The results are shown in Table 1.

[0146] Example 19

[0147] The preparation method of catalyst 19 is as follows. The support is subjected to surface hydrophobic treatment: 0.05 g of methyltriethoxysilane, 0.05 g of octyltrimethoxysilane, and 0.119 g of octadecyltrimethoxysilane are dissolved in 200 ml of n-hexane solution and stirred evenly at 30°C. 7.30 g of titanium dioxide support is dispersed in the n-hexane solution and treated for 18 h. After centrifugation, washing, and drying at 120°C, a surface hydrophobic support is obtained. 24 ml of an aqueous solution containing 7.412 g of Co(NO3)2·6H2O, 4.955 g of Ni(NO3)2·6H2O, 0.262 g of In(NO3)3, and 0.312 g of La(NO3)3·6H2O is prepared and divided into two equal portions. The following process is repeated twice: one portion of the solution is used to impregnate the above surface hydrophobic support, air-dried naturally, dried at 120°C for 10 h, and calcined in nitrogen at 200°C for 10 h. Reduction treatment was carried out under the following conditions: temperature 400℃, atmosphere of atmospheric pressure hydrogen, and volume hourly space velocity (VHSV) of 500 h⁻¹. -1 The reduction time was 10 h. Catalyst 19 was obtained: Co15Ni10-In1La1 / titanium dioxide-4, which was stored under nitrogen.

[0148] Catalyst 19 was used for reaction evaluation. The reaction conditions were the same as in Example 16. The results are shown in Table 1.

[0149] Example 20

[0150] The preparation method of catalyst 20 is as follows: Take 7.30 g of cerium oxide support, prepare 12 ml of an aqueous solution containing 3.801 g Cu(NO3)2·3H2O, 2.478 g Ni(NO3)2·6H2O, 1.035 g RuCl3·3H2O, 0.409 g (NH4)2MoO4, and 1.145 g H3BO3, impregnate the cerium oxide support, air dry naturally, dry at 120℃ for 5 h, and calcine in air at 300℃ for 5 h. Reduce treatment is then performed: the reduction conditions are a temperature of 250℃, an atmosphere of atmospheric pressure hydrogen, and a volume hourly space velocity (VHSV) of 200 h⁻¹. -1 The reduction time was 5 h, and the sample was stored under nitrogen. The reduced sample underwent surface hydrophobic treatment: 0.385 g of hexadecyltrimethoxysilane was dissolved in 200 ml of toluene solution and stirred at 80 °C. The reduced sample was then dispersed in the toluene solution and treated for 20 h. After centrifugation, washing, and drying at 120 °C, catalyst 20: Cu10Ni5Ru4-Mo2B2 / cerium oxide was obtained and stored under nitrogen.

[0151] Catalyst 20 was transferred to the reactor under a nitrogen atmosphere. The reaction temperature was 180℃, the pressure was 12MPa, and the liquid feed consisted of diethylenetriamine and liquid ammonia, with a diethylenetriamine:liquid ammonia molar ratio of 0.17:1. The liquid hourly space velocity (LHSV) of the diethylenetriamine was 2.5 h⁻¹. -1 The hydrogen molar concentration was 15%. Samples were taken for analysis after 50 hours of continuous reaction in a fixed-bed reactor. The results are shown in Table 1.

[0152] Example 21

[0153] Catalyst 20 was transferred to the reactor under a nitrogen atmosphere. The reaction temperature was 180℃, the pressure was 12MPa, and the liquid feed consisted of 1,6-hexanediol and liquid ammonia, with a 1,6-hexanediol:liquid ammonia molar ratio of 0.17:1. The liquid hourly space velocity (LHSV) of the 1,6-hexanediol was 0.8 h⁻¹. -1 The hydrogen molar concentration was 15%. Samples were taken for analysis after 50 hours of continuous reaction in a fixed-bed reactor. The results are shown in Table 1.

[0154] Example 22

[0155] Catalyst 20 was transferred to the reactor under a nitrogen atmosphere. The reaction temperature was 180℃, the pressure was 12MPa, and the liquid feed consisted of monoethanolamine and liquid ammonia, with a monoethanolamine:liquid ammonia molar ratio of 0.17:1. The liquid hourly space velocity (LISH) of the monoethanolamine was 1 h⁻¹. -1 The hydrogen molar concentration was 15%. Samples were taken for analysis after 50 hours of continuous reaction in a fixed-bed reactor. The results are shown in Table 1.

[0156] Example 23

[0157] Catalyst 20 was transferred to the reactor under a nitrogen atmosphere. The reaction temperature was 180℃, the pressure was 12MPa, and the liquid feed consisted of diethylene glycolamine and liquid ammonia, with a diethylene glycolamine:liquid ammonia molar ratio of 0.17:1. The liquid hourly space velocity (LHSV) of the diethylene glycolamine was 2 h⁻¹. -1 The hydrogen molar concentration was 15%. Samples were taken for analysis after 50 hours of continuous reaction in a fixed-bed reactor. The results are shown in Table 1.

[0158] Example 24

[0159] The preparation method of catalyst 21 is as follows: 27.38 g of tetraethyl silicate and 0.316 g of methyltrimethoxysilane were dissolved in 100 ml of ethanol, 100 ml of water and 10 ml of ammonia were added, and the mixture was stirred at room temperature for 24 h. After filtration and washing, the mixture was dried at 100 °C for 10 h and calcined at 400 °C under nitrogen atmosphere to obtain a silica support with hydrophobic surface modification. 12 ml of an aqueous solution containing 4.955 g of Ni(NO3)2·6H2O, 0.976 g of Pd(NO3)2·2H2O, 0.734 g of IrCl3·3H2O, 0.309 g of (NH4)2WO4 and 0.458 g of Cr(NO3)3 was prepared, and the above support was impregnated. The solution was air-dried, dried at 120 °C for 5 h, and calcined at 350 °C under nitrogen atmosphere for 5 h. Reduction treatment was carried out under the following conditions: temperature 450℃, atmosphere of atmospheric pressure hydrogen, and volume hourly space velocity (VHSV) of 1000 h⁻¹. -1 The reduction time was 5 hours to obtain catalyst 21: Ni10Pd4Ir4-W2Cr1 / silica, which was then nitrogen-sealed and stored.

[0160] Catalyst 21 was transferred to the reactor under a nitrogen atmosphere. The reaction temperature was 140℃, the pressure was 10 MPa, and the liquid feed consisted of 6-amino-1-hexanol and liquid ammonia, with a molar ratio of 6-amino-1-hexanol to liquid ammonia of 0.2:1. The liquid hourly space velocity (LHSV) of 6-amino-1-hexanol was 1.5 h⁻¹. -1 The hydrogen molar concentration was 5%. Samples were taken for analysis after 50 hours of continuous reaction in a fixed-bed reactor. The results are shown in Table 1.

[0161] Example 25

[0162] The preparation method of catalyst 21 is as follows: 27.38 g of tetraethyl silicate and 0.316 g of methyltrimethoxysilane were dissolved in 100 ml of ethanol, 100 ml of water and 10 ml of ammonia were added, and the mixture was stirred at room temperature for 24 h. After filtration and washing, the mixture was dried at 100 °C for 10 h and calcined at 400 °C under nitrogen atmosphere to obtain a silica support with hydrophobic surface modification. 12 ml of an aqueous solution containing 4.955 g of Ni(NO3)2·6H2O, 0.976 g of Pd(NO3)2·2H2O, 0.734 g of IrCl3·3H2O, 0.309 g of (NH4)2WO4 and 0.458 g of Cr(NO3)3 was prepared, and the above support was impregnated. The solution was air-dried, dried at 120 °C for 5 h, and calcined at 350 °C under nitrogen atmosphere for 5 h. Reduction treatment was carried out under the following conditions: temperature 450℃, atmosphere of atmospheric pressure hydrogen, and volume hourly space velocity (VHSV) of 1000 h⁻¹. -1 The reduction time was 5 hours to obtain catalyst 21: Ni10Pd4Ir4-W2Cr1 / silica, which was then nitrogen-sealed and stored.

[0163] Catalyst 21 was transferred to the reactor under a nitrogen atmosphere. The reaction temperature was 170℃, the pressure was 10 MPa, and the liquid feed consisted of 6-amino-1-hexanol and liquid ammonia, with a molar ratio of 6-amino-1-hexanol to liquid ammonia of 0.2:1. The liquid hourly space velocity (LHSV) of 6-amino-1-hexanol was 1.5 h⁻¹. -1 The hydrogen molar concentration was 5%. Samples were taken for analysis after 50 hours of continuous reaction in a fixed-bed reactor. The results are shown in Table 1.

[0164] Example 26

[0165] The preparation method of catalyst 21 is as follows: 27.38 g of tetraethyl silicate and 0.316 g of methyltrimethoxysilane were dissolved in 100 ml of ethanol, 100 ml of water and 10 ml of ammonia were added, and the mixture was stirred at room temperature for 24 h. After filtration and washing, the mixture was dried at 100 °C for 10 h and calcined at 400 °C under nitrogen atmosphere to obtain a silica support with hydrophobic surface modification. 12 ml of an aqueous solution containing 4.955 g of Ni(NO3)2·6H2O, 0.976 g of Pd(NO3)2·2H2O, 0.734 g of IrCl3·3H2O, 0.309 g of (NH4)2WO4 and 0.458 g of Cr(NO3)3 was prepared, and the above support was impregnated. The solution was air-dried, dried at 120 °C for 5 h, and calcined at 350 °C under nitrogen atmosphere for 5 h. Reduction treatment was carried out under the following conditions: temperature 450℃, atmosphere of atmospheric pressure hydrogen, and volume hourly space velocity (VHSV) of 1000 h⁻¹. -1 The reduction time was 5 hours to obtain catalyst 21: Ni10Pd4Ir4-W2Cr1 / silica, which was then nitrogen-sealed and stored.

[0166] Catalyst 21 was transferred to the reactor under a nitrogen atmosphere. The reaction temperature was 210℃, the pressure was 10 MPa, and the liquid feed consisted of 6-amino-1-hexanol and liquid ammonia, with a molar ratio of 6-amino-1-hexanol to liquid ammonia of 0.2:1. The liquid hourly space velocity (LHSV) of 6-amino-1-hexanol was 1.5 h⁻¹. -1 The hydrogen molar concentration was 5%. Samples were taken for analysis after 50 hours of continuous reaction in a fixed-bed reactor. The results are shown in Table 1.

[0167] Example 27

[0168] The preparation method of catalyst 22 is as follows: Take 8.3g of molecular sieve ZSM-5 support, and prepare 12ml of a mixture containing 0.249g of polytetrafluoroethylene emulsion (calculated as polytetrafluoroethylene), 2.471g of Co(NO3)2·6H2O, 2.477g of Ni(NO3)2·6H2O, 1.900g of Cu(NO3)2·3H2O, 0.144g of NH4ReO4, and 0.404g of C6H4NNbO. 12 The ZSM-5 support was impregnated with an aqueous solution to obtain a hydrophobic surface-treated sample, which was then dried at 120℃ and calcined at 400℃ for 6 hours in nitrogen. Reduction treatment was then performed under the following conditions: temperature 500℃, atmosphere of atmospheric pressure hydrogen, and volume hourly space velocity (VHSV) of 3000 h⁻¹. -1 The reduction time was 5 h to obtain catalyst 22: Co5Ni5Cu5-Re1Nb1 / ZSM-5, which was then nitrogen-sealed and stored.

[0169] Catalyst 22 was transferred to the reactor under a nitrogen atmosphere. The reaction temperature was 190℃, the pressure was 4 MPa, and the liquid feed consisted of phenylenediamine and liquid ammonia, with a phenylenediamine:liquid ammonia molar ratio of 0.1:1. The liquid hourly space velocity (LHSV) of phenylenediamine was 1.8 h⁻¹. -1 The hydrogen molar concentration was 8%. Samples were taken for analysis after 50 hours of continuous reaction in a fixed-bed reactor. The results are shown in Table 1.

[0170] Example 28

[0171] Catalyst 22 was transferred to the reactor under a nitrogen atmosphere. The reaction temperature was 190℃, the pressure was 10 MPa, and the liquid feed consisted of phenylenediamine and liquid ammonia, with a phenylenediamine:liquid ammonia molar ratio of 0.1:1. The liquid hourly space velocity (LHSV) of phenylenediamine was 1.8 h⁻¹. -1 The hydrogen molar concentration was 8%. Samples were taken for analysis after 50 hours of continuous reaction in a fixed-bed reactor. The results are shown in Table 1.

[0172] Example 29

[0173] Catalyst 22 was transferred to the reactor under a nitrogen atmosphere. The reaction temperature was 190℃, the pressure was 20 MPa, and the liquid feed consisted of phenylenediamine and liquid ammonia, with a phenylenediamine:liquid ammonia molar ratio of 0.1:1. The liquid hourly space velocity (LHSV) of phenylenediamine was 1.8 h⁻¹. -1 The hydrogen molar concentration was 8%. Samples were taken for analysis after 50 hours of continuous reaction in a fixed-bed reactor. The results are shown in Table 1.

[0174] Example 30

[0175] The preparation method of catalyst 23 is as follows: Take 7.8 g of alumina-silica support, prepare 12 ml of aqueous solution containing 0.39 g of polystyrene emulsion (calculated as polystyrene), impregnate the alumina-silica support, and dry at 100 °C to obtain a surface-hydrophobic support. Disperse the surface-hydrophobic support in water to form a suspension, and stir at medium speed at a constant temperature of 50 °C. Prepare a precursor solution containing 3.964 g Ni(NO3)2·6H2O, 3.041 g Cu(NO3)2·3H2O, 0.367 g IrCl3·3H2O, and 0.460 g NH4VO3. The precipitant used is a 3 mol / L NaOH solution. Add the precursor solution and precipitant dropwise to the above suspension at a rate of 1 ml / min, maintain the pH value at 9, until precipitation is complete. Wash the precipitate with deionized water until neutral, filter, air dry, dry at 120 °C for 10 h, and calcine at 300 °C in nitrogen for 15 h. Reduction treatment was carried out under the following conditions: temperature 400℃, atmosphere of atmospheric pressure hydrogen, and volume hourly space velocity (VHSV) of 1500 h⁻¹. -1 The reduction time was 5 hours to obtain catalyst 23: Ni8Cu8Ir2-V2Sn2 / alumina-silica, which was then nitrogen-sealed and stored.

[0176] Catalyst 23 was transferred to the reactor under a nitrogen atmosphere. The reaction temperature was 180℃, the pressure was 10MPa, and the liquid feed consisted of butanediol and liquid ammonia, with a butanediol:liquid ammonia molar ratio of 0.05:1. The liquid hourly space velocity (LISH) of the butanediol was 2 h⁻¹. -1 The hydrogen molar concentration was 5%. Samples were taken for analysis after 50 hours of continuous reaction in a fixed-bed reactor. The results are shown in Table 1.

[0177] Example 31

[0178] Catalyst 23 was transferred to the reactor under a nitrogen atmosphere. The reaction temperature was 180℃, the pressure was 10MPa, and the liquid feed consisted of butanediol and liquid ammonia, with a butanediol:liquid ammonia molar ratio of 1:1. The liquid hourly space velocity (LHSV) of the butanediol was 2 h⁻¹. -1 The hydrogen molar concentration was 5%. Samples were taken for analysis after 50 hours of continuous reaction in a fixed-bed reactor. The results are shown in Table 1.

[0179] Example 32

[0180] Catalyst 23 was transferred to the reactor under a nitrogen atmosphere. The reaction temperature was 180℃, the pressure was 10 MPa, and the liquid feed consisted of butanediol and liquid ammonia, with a butanediol:liquid ammonia molar ratio of 3:1. The liquid hourly space velocity (LISH) of the butanediol was 2 h⁻¹. -1 The hydrogen molar concentration was 5%. Samples were taken for analysis after 50 hours of continuous reaction in a fixed-bed reactor. The results are shown in Table 1.

[0181] Example 33

[0182] The preparation method of catalyst 24 is as follows: 7.7 g of molecular sieve SBA-15 support was dispersed in water to form a suspension, and stirred at a medium speed at a constant temperature of 50 °C. A precursor solution containing 3.801 g Cu(NO3)2·3H2O, 4.955 g Ni(NO3)2·6H2O, 0.910 g Zn(NO3)2·6H2O, and 0.573 g H3BO3 was prepared. The precipitant used was a 1.5 mol / L Na2CO3 solution. The precursor solution and precipitant were simultaneously added dropwise to the above suspension at a rate of 1 ml / min, maintaining the pH at 9 until precipitation was complete. The precipitate was washed with deionized water until neutral, filtered, air-dried, dried at 120 °C for 10 h, and calcined in air at 420 °C for 6 h. Reduction treatment was performed: the reduction conditions were a temperature of 350 °C, an atmosphere of atmospheric pressure hydrogen, and a volume hourly space velocity (VHSV) of 500 h⁻¹. -1 The reduction time was 5 h, and the sample was nitrogen-sealed for preservation. The reduced sample underwent surface hydrophobic treatment: 0.231 g of trifluoropropyltrichlorosilane was dispersed in 200 ml of toluene solution and stirred evenly at 80 °C. The calcined sample was then dispersed in the toluene solution, treated for 15 h, centrifuged, washed, and dried at 120 °C to obtain catalyst 24: Cu10Ni10-Zn2B1 / SBA-15.

[0183] Catalyst 24 was transferred to the reactor under a nitrogen atmosphere. The reaction temperature was 185℃, the pressure was 12 MPa, and the liquid feed consisted of diethanolamine and ammonia water, with a diethanolamine:ammonia molar ratio of 0.1:1 and a liquid hourly space velocity (LHSV) of 2.2 h⁻¹. -1 The hydrogen molar concentration was 20%. Samples were taken for analysis after 50 hours of continuous reaction in a fixed-bed reactor. The results are shown in Table 1.

[0184] Example 34

[0185] Catalyst 24 was transferred to the reactor under a nitrogen atmosphere. The reaction temperature was 185℃, the pressure was 12 MPa, and the liquid feed consisted of diethanolamine and methylamine, with a diethanolamine:methylamine molar ratio of 0.1:1 and a liquid hourly space velocity (LHSV) of 2.2 h⁻¹. -1 The hydrogen molar concentration was 20%. Samples were taken for analysis after 50 hours of continuous reaction in a fixed-bed reactor. The results are shown in Table 1.

[0186] Example 35

[0187] Catalyst 24 was transferred to the reactor under a nitrogen atmosphere. The reaction temperature was 185℃, the pressure was 12 MPa, and the liquid feed consisted of diethanolamine and ethylamine, with a diethanolamine:ethylamine molar ratio of 0.1:1. The liquid hourly space velocity (LHSV) of the diethanolamine was 2.2 h⁻¹. -1 The hydrogen molar concentration was 20%. Samples were taken for analysis after 50 hours of continuous reaction in a fixed-bed reactor. The results are shown in Table 1.

[0188] Comparative Example 1

[0189] The preparation method of catalyst 25 is as follows. First, the support surface is hydrophobically treated: 0.236 g of octyltrimethoxysilane is dispersed in 200 ml of toluene solution and stirred evenly at 50 °C. 9.45 g of silica support is added and dispersed in the above solution. After treatment for 12 h, the surface is centrifuged, washed, and dried at 120 °C to obtain the surface-hydrophobically treated support. 12 ml of an aqueous solution containing 1.239 g of Ni(NO3)2·6H2O, 0.244 g of Pd(NO3)2·2H2O, and 0.439 g of SnCl2 is prepared. The above surface-hydrophobically treated support is impregnated, air-dried naturally, dried at 120 °C for 10 h, and calcined at 400 °C in nitrogen for 5 h. Reduction treatment is then performed: the reduction conditions are a temperature of 400 °C, an atmosphere of atmospheric pressure hydrogen, and a volume hourly space velocity of 1000 h⁻¹. -1 The reduction time was 6 hours. Catalyst 25 was obtained: Ni2.5Pd1-Sn2 / silica, which was nitrogen-sealed and stored.

[0190] Catalyst 25 was used for reaction evaluation. The reaction conditions were the same as in Example 1. The results are shown in Table 1.

[0191] Comparative Example 2

[0192] The preparation method of catalyst 26 is as follows. First, the support surface is hydrophobically treated: 0.070 g of octyltrimethoxysilane is dispersed in 200 ml of toluene solution and stirred evenly at 50 °C. 2.8 g of silica support is added and dispersed in the above solution. After treatment for 12 h, the surface is centrifuged, washed, and dried at 120 °C to obtain the surface-hydrophobically treated support. 48 ml of an aqueous solution containing 24.773 g of Ni(NO3)2·6H2O, 4.878 g of Pd(NO3)2·2H2O, and 0.439 g of SnCl2 is prepared. The above surface-hydrophobically treated support is impregnated, air-dried naturally, dried at 120 °C for 10 h, and calcined at 400 °C in nitrogen for 5 h. Reduction treatment is then performed: the reduction conditions are a temperature of 400 °C, an atmosphere of atmospheric pressure hydrogen, and a volume hourly space velocity (VHSV) of 1000 h⁻¹. -1 The reduction time was 6 hours. Catalyst 26 was obtained: Ni50Pd20-Sn2 / silica, which was nitrogen-sealed and stored.

[0193] Catalyst 26 was used for reaction evaluation. The reaction conditions were the same as in Example 1. The results are shown in Table 1.

[0194] Comparative Example 3

[0195] The preparation method of catalyst 27 is as follows. First, the support surface is hydrophobically treated: 0.193 g of octyltrimethoxysilane is dispersed in 200 ml of toluene solution and stirred evenly at 50 °C. 7.70 g of silica support is added and dispersed in the above solution. After treatment for 12 h, the surface is centrifuged, washed, and dried at 120 °C to obtain the surface-hydrophobically treated support. 12 ml of an aqueous solution containing 6.497 g of Fe(NO3)3, 1.519 g of RhCl3·3H2O, and 0.439 g of SnCl2 is prepared. The above surface-hydrophobically treated support is impregnated, air-dried naturally, dried at 120 °C for 10 h, and calcined at 400 °C in nitrogen for 5 h. Reduction treatment is then performed: the reduction conditions are a temperature of 400 °C, an atmosphere of atmospheric pressure hydrogen, and a volume hourly space velocity of 1000 h⁻¹. -1 The reduction time was 6 hours. Catalyst 27 was obtained: Fe15Rh6-Sn2 / silica, which was nitrogen-sealed and stored.

[0196] Catalyst 27 was used for reaction evaluation. The reaction conditions were the same as in Example 1. The results are shown in Table 1.

[0197] Comparative Example 4

[0198] The Ni-Cu-Cr and Ru / C combined catalyst described in Example 1 of US5071980 was used, and the reaction conditions were the same as in Example 1. The results are shown in Table 1.

[0199] Comparative Example 5

[0200] The preparation method of catalyst 28 is as follows: Take 8.196 g of alumina support. Prepare 12 ml of an aqueous solution containing 4.941 g Co(NO3)2·6H2O, 2.477 g Ni(NO3)2·6H2O, 0.776 g RuCl3·3H2O, 0.003 g NH4ReO4, and 0.007 g Mn(NO3)2. Impregnate the alumina support with this solution, allow it to air dry naturally, dry at 120℃ for 10 h, and calcine in air at 350℃ for 8 h. Perform surface hydrophobic treatment on the calcined sample: Disperse 0.328 g methyltriethoxysilane in 200 ml toluene solution, stir evenly at 80℃, disperse the calcined sample in the toluene solution, treat for 8 h, centrifuge, wash, and dry at 120℃ to obtain the surface hydrophobic treated sample. Perform reduction treatment: The reduction conditions are: temperature 450℃, atmosphere: atmospheric pressure hydrogen, volume hourly space velocity (VHSV): 1500 h⁻¹. -1 The reduction time was 8 hours. Catalyst 28 was obtained: Co10Ni5Ru3-Re0.02Mn0.02 / alumina, which was stored under nitrogen.

[0201] Catalyst 28 was used for reaction evaluation. The reaction conditions were the same as in Example 6. The results are shown in Table 1.

[0202] Comparative Example 6

[0203] The preparation method of catalyst 29 is as follows: Take 6.80 g of alumina support. Prepare 12 ml of an aqueous solution containing 4.941 g Co(NO3)2·6H2O, 2.477 g Ni(NO3)2·6H2O, 0.776 g RuCl3·3H2O, 1.008 g NH4ReO4, and 2.280 g Mn(NO3)2. Impregnate the above alumina support with the solution, air dry naturally, dry at 120℃ for 10 h, and calcine at 350℃ in air for 8 h. Perform surface hydrophobic treatment on the calcined sample: Disperse 0.272 g methyltriethoxysilane in 200 ml toluene solution, stir evenly at 80℃, disperse the calcined sample in the toluene solution, treat for 8 h, centrifuge, wash, and dry at 120℃ to obtain the surface hydrophobic treated sample. Perform reduction treatment: The reduction conditions are temperature 450℃, atmosphere is atmospheric pressure hydrogen, and volume hourly space velocity is 1500 h⁻¹. -1 The reduction time was 8 hours. Catalyst 29 was obtained: Co10Ni5Ru3-Re7Mn7 / alumina, which was nitrogen-sealed and stored.

[0204] Catalyst 29 was used for reaction evaluation. The reaction conditions were the same as in Example 6. The results are shown in Table 1.

[0205] Comparative Example 7

[0206] The preparation method of catalyst 30 is as follows: Take 8.0 g of alumina support. Prepare 12 ml of an aqueous solution containing 4.941 g Co(NO3)2·6H2O, 2.477 g Ni(NO3)2·6H2O, 0.776 g RuCl3·3H2O, 0.190 g Ba(NO3)2, and 0.609 g Mg(NO3)2. Impregnate the above alumina support with the solution, air dry naturally, dry at 120℃ for 10 h, and calcine at 350℃ in air for 8 h. Perform surface hydrophobic treatment on the calcined sample: Disperse 0.320 g methyltriethoxysilane in 200 ml toluene solution, stir evenly at 80℃, disperse the calcined sample in the toluene solution, treat for 8 h, centrifuge, wash, and dry at 120℃ to obtain the surface hydrophobic treated sample. Perform reduction treatment: The reduction conditions are temperature 450℃, atmosphere is atmospheric pressure hydrogen, and volume hourly space velocity is 1500 h⁻¹. -1 The reduction time was 8 hours. Catalyst 30 was obtained: Co10Ni5Ru3-Ba1Mg1 / alumina, which was stored under nitrogen.

[0207] Catalyst 30 was used for reaction evaluation. The reaction conditions were the same as in Example 6. The results are shown in Table 1.

[0208] Comparative Example 8

[0209] The preparation method of catalyst 31 is as follows: Take 7.90 g of alumina support. Prepare 12 ml of an aqueous solution containing 3.964 g Ni(NO3)2·6H2O, 3.041 g Cu(NO3)2·3H2O, 0.367 g IrCl3·3H2O, 0.866 g Fe(NO3)3, and 0.573 g H3BO3. Impregnate the above alumina support with the solution, air dry naturally, dry at 120℃ for 10 h, and calcine in air at 450℃ for 10 h. Perform reduction treatment: The reduction conditions are a temperature of 350℃, an atmosphere of atmospheric pressure hydrogen, and a volume hourly space velocity of 2500 h⁻¹. -1 The reduction time was 5 h, and the sample was stored under nitrogen. The reduced sample underwent surface hydrophobic treatment: 0.006 g of trifluoropropyltriethoxysilane was dispersed in 200 ml of toluene solution and stirred at 60 °C until homogeneous. The reduced sample was then dispersed in the toluene solution and treated for 24 h. After centrifugation, washing, and drying at 120 °C, catalyst 31: Ni8Cu8Ir2-Fe2B1 / activated carbon-6 was obtained and stored under nitrogen.

[0210] Catalyst 31 was used for reaction evaluation. The reaction conditions were the same as in Example 11. The results are shown in Table 1.

[0211] Comparative Example 9

[0212] The preparation method of catalyst 32 is as follows: Take 7.90 g of alumina support. Prepare 12 ml of an aqueous solution containing 3.964 g Ni(NO3)2·6H2O, 3.041 g Cu(NO3)2·3H2O, 0.367 g IrCl3·3H2O, 0.866 g Fe(NO3)3, and 0.573 g H3BO3. Impregnate the above alumina support with the solution, air dry naturally, dry at 120℃ for 10 h, and calcine in air at 450℃ for 10 h. Perform reduction treatment: The reduction conditions are: temperature 350℃, atmosphere of atmospheric pressure hydrogen, and volume hourly space velocity (VHSV) of 2500 h⁻¹. -1 The reduction time was 5 h, and the sample was stored under nitrogen. The reduced sample underwent surface hydrophobic treatment: 1.422 g of trifluoropropyltriethoxysilane was dispersed in 200 ml of toluene solution and stirred at 60 °C until homogeneous. The reduced sample was then dispersed in the toluene solution and treated for 24 h. After centrifugation, washing, and drying at 120 °C, catalyst 32: Ni8Cu8Ir2-Fe2B1 / activated carbon-7 was obtained and stored under nitrogen.

[0213] Catalyst 32 was used for reaction evaluation. The reaction conditions were the same as in Example 11. The results are shown in Table 1.

[0214] Comparative Example 10

[0215] The preparation method of catalyst 33 is as follows: Take 7.90 g of alumina support. Prepare 12 ml of an aqueous solution containing 3.964 g Ni(NO3)2·6H2O, 3.041 g Cu(NO3)2·3H2O, 0.367 g IrCl3·3H2O, 0.866 g Fe(NO3)3, and 0.573 g H3BO3. Impregnate the above alumina support with the solution, air dry naturally, dry at 120℃ for 10 h, and calcine in air at 450℃ for 10 h. Perform reduction treatment: The reduction conditions are 350℃, atmospheric hydrogen atmosphere, and volume hourly space velocity (VHSV) of 2500 h⁻¹. -1 The reduction time was 5 hours, and catalyst 33 was obtained: Ni8Cu8Ir2-Fe2B1 / activated carbon-8, which was then nitrogen-sealed and stored.

[0216] Catalyst 33 was used for reaction evaluation. The reaction conditions were the same as in Example 11. The results are shown in Table 1.

[0217] Comparative Example 11

[0218] The Co-Ni-Mo / alumina catalyst described in Example 4 of CN 111925341 was used for reaction evaluation. The reaction conditions were the same as in Example 11. The results are shown in Table 1.

[0219] Comparative Example 12

[0220] The niobium phosphate catalyst described in Example 1 of CN 94108721.2 was used for reaction evaluation. The reaction conditions were the same as in Example 11. The results are shown in Table 1.

[0221] Comparative Example 13

[0222] Catalyst 21 was transferred to the reactor under a nitrogen atmosphere. The reaction temperature was 120℃, the pressure was 10 MPa, and the liquid feed consisted of 6-amino-1-hexanol and liquid ammonia, with a molar ratio of 6-amino-1-hexanol to liquid ammonia of 0.2:1. The liquid hourly space velocity (LHSV) of 6-amino-1-hexanol was 1.5 h⁻¹. -1 The hydrogen molar concentration was 5%. Samples were taken for analysis after 50 hours of continuous reaction in a fixed-bed reactor. The results are shown in Table 1.

[0223] Comparative Example 14

[0224] Catalyst 21 was transferred to the reactor under a nitrogen atmosphere. The reaction temperature was 240℃, the pressure was 10 MPa, and the liquid feed consisted of 6-amino-1-hexanol and liquid ammonia, with a molar ratio of 6-amino-1-hexanol to liquid ammonia of 0.2:1. The liquid hourly space velocity (LHSV) of 6-amino-1-hexanol was 1.5 h⁻¹. -1 The hydrogen molar concentration was 5%. Samples were taken for analysis after 50 hours of continuous reaction in a fixed-bed reactor. The results are shown in Table 1.

[0225] Comparative Example 15

[0226] Catalyst 22 was transferred to the reactor under a nitrogen atmosphere. The reaction temperature was 190℃, the pressure was 0.5 MPa, and the liquid feed consisted of phenylenediamine and liquid ammonia, with a phenylenediamine:liquid ammonia molar ratio of 0.1:1. The liquid hourly space velocity (LHSV) of the phenylenediamine was 1.8 h⁻¹. -1 The hydrogen molar concentration was 8%. Samples were taken for analysis after 50 hours of continuous reaction in a fixed-bed reactor. The results are shown in Table 1.

[0227] Comparative Example 16

[0228] Catalyst 22 was transferred to the reactor under a nitrogen atmosphere. The reaction temperature was 190℃, the pressure was 35 MPa, and the liquid feed consisted of phenylenediamine and liquid ammonia, with a phenylenediamine:liquid ammonia molar ratio of 0.1:1. The liquid hourly space velocity (LHSV) of phenylenediamine was 1.8 h⁻¹. -1 The hydrogen molar concentration was 8%. Samples were taken for analysis after 50 hours of continuous reaction in a fixed-bed reactor. The results are shown in Table 1.

[0229] Comparative Example 17

[0230] Catalyst 23 was transferred to the reactor under a nitrogen atmosphere. The reaction temperature was 180℃, the pressure was 10MPa, and the liquid feed consisted of butanediol and liquid ammonia, with a butanediol:liquid ammonia molar ratio of 0.005:1. The liquid hourly space velocity (LISH) of the butanediol was 2 h⁻¹. -1 The hydrogen molar concentration was 5%. Samples were taken for analysis after 50 hours of continuous reaction in a fixed-bed reactor. The results are shown in Table 1.

[0231] Comparative Example 18

[0232] Catalyst 23 was transferred to the reactor under a nitrogen atmosphere. The reaction temperature was 180℃, the pressure was 10 MPa, and the liquid feed consisted of butanediol and liquid ammonia, with a butanediol:liquid ammonia molar ratio of 15:1. The liquid hourly space velocity (LHSV) of the butanediol was 2 h⁻¹. -1 The hydrogen molar concentration was 5%. Samples were taken for analysis after 50 hours of continuous reaction in a fixed-bed reactor. The results are shown in Table 1.

[0233] The beneficial effects of this patent are improved conversion rate of polyol amine source substrates and selectivity of heterocyclic amines. According to the reaction evaluation results of the catalyst in Table 1, as shown in Examples 1-5 and Comparative Examples 1-4, when the active metal loading is less than 5%, the catalyst exhibits low activity; as the active metal loading increases, the diethylene glycol conversion rate first increases and then decreases, and the morpholine selectivity also first increases and then decreases; compared to the effect of an active metal loading range of 5-60%, the catalyst exhibits higher conversion rate and morpholine selectivity when the active metal loading is within the preferred range of 10-40%; when an active metal combination outside the scope defined in this patent is selected, the catalyst exhibits lower activity and selectivity.

[0234] As shown in Examples 6-10 and Comparative Examples 5-7, when the loading of the auxiliary element is less than 0.05%, the catalyst exhibits low activity and piperazine selectivity. As the loading of the auxiliary element increases, the conversion rate first increases and then decreases, and the piperazine selectivity also first increases and then decreases. Compared with the effect of the auxiliary element loading range of 0.05-10%, the catalyst has higher conversion rate and piperazine selectivity when the auxiliary element loading range of 0.5-6% is preferred. When the loading of the auxiliary element is greater than 10% or when elements outside the scope of this invention are selected as auxiliary agents, the conversion rate and piperazine selectivity decrease significantly.

[0235] Examples 11-15 and Comparative Examples 8-12 show that when no hydrophobic agent is added or the amount of hydrophobic agent added is less than 0.1%, the catalyst exhibits low activity and piperazine selectivity, failing to increase the yield of heterocyclic amines. As the amount of hydrophobic agent added increases, the conversion rate first increases and then decreases, and the piperazine selectivity also first increases and then decreases. Compared with the effect of the hydrophobic agent addition range of 0.1-15%, the catalyst has higher conversion rate and piperazine selectivity when the hydrophobic agent addition range of 1-10% is preferred. When the amount of hydrophobic agent added is greater than 15%, a decrease in conversion rate occurs.

[0236] As demonstrated in Examples 16-19, the use of combinations of various types of hydrophobic agents also effectively improved the conversion rate and piperazine selectivity. As demonstrated in Examples 20-23, the catalytic system of this invention exhibits good applicability to polyamines, polyols, and alkanolamine substrates, effectively improving the conversion rate and heterocyclic amine selectivity.

[0237] As can be seen from Examples 24-26 and Comparative Examples 13-14, when the reaction temperature is below 130°C, the catalyst exhibits low activity and selectivity; as the reaction temperature increases, the conversion rate gradually increases, and the hexamethyleneimine content first increases and then decreases; when the reaction temperature is above 220°C, although near-complete conversion occurs, the selectivity of hexamethyleneimine decreases significantly.

[0238] As can be seen from Examples 27-29 and Comparative Examples 15-16, when the reaction pressure is below 1 MPa, the catalyst exhibits low activity and selectivity; as the reaction pressure increases, the conversion rate gradually increases, and the isoindoline selectivity gradually decreases; when the reaction pressure is above 30 MPa, the conversion rate is high, but the isoindoline selectivity decreases significantly, and primary amine products are mainly generated.

[0239] As shown in Examples 30-32 and Comparative Examples 17-18, when the butanediol:ammonia molar ratio is below 0.01:1, the butanediol conversion is high, but the tetrahydropyrrole selectivity is low. As the butanediol:ammonia molar ratio increases, the conversion gradually decreases, while the tetrahydropyrrole selectivity remains high. When the butanediol:ammonia molar ratio is greater than 15:1, the conversion decreases significantly, which is due to insufficient ammonia source. As shown in Examples 33-35, the catalyst of this invention exhibits excellent substrate suitability when using different ammonia sources.

[0240] As shown in Examples 13 and 17, the catalyst of the present invention exhibits good stability in the 2000-h stability evaluation. Based on the above analysis, the catalyst prepared by the described method for the catalytic amination of polyol amines to heterocyclic amines can achieve one or more of the following: (1) simple and easy-to-operate catalyst preparation process; (2) high selectivity for heterocyclic amines; (3) high catalyst activity; (4) good process economy; (5) good catalyst stability; (6) mild reaction conditions; (7) continuous production capability; (8) green and clean reaction process.

Claims

1. A catalyst for the catalytic amination of polyol amines to prepare heterocyclic amines, characterized in that: The catalyst consists of three parts: an active metal, an auxiliary element, and a support, with the active metal and the auxiliary element loaded on the support. The support is one or more of CeO2, Al2O3, TiO2, molecular sieve, activated carbon, SiO2, and Al2O3-SiO2; The active metal is one or more of Co, Ni, Cu, Pd, Ru, and Ir; The auxiliary agent is one or more of the elements Fe, Sn, In, Re, Mn, B, V, W, Nb, Cr, La, Mo, and Zn; The catalyst is prepared by the following process: loading the precursors of active metals and auxiliary elements onto a support by impregnation and / or precipitation, followed by drying, calcination, and reduction to obtain the catalyst. The catalyst needs to undergo surface hydrophobication treatment during and / or after preparation; the hydrophobic agent is an organosilane or polymer.

2. The catalyst according to claim 1, characterized in that: The surface hydrophobication treatment involves modifying the catalyst surface with a hydrophobic agent through one or more of the following methods: impregnation, co-hydrolysis, self-assembly, sol-gel, coating, grafting, etc.; the hydrophobic agent is one or more of the following: organosilane, polymer, or long-chain fatty acid. The surface hydrophobication treatment can be performed in the following catalyst preparation processes: during the support synthesis process, or during the surface hydrophobication treatment of the support, or during the impregnation and / or precipitation process of the active metal and additives, or during the surface hydrophobication treatment of the dried catalyst sample, or during the surface hydrophobication treatment of the calcined catalyst sample, or during the surface hydrophobication treatment of the reduced catalyst sample.

3. The catalyst according to claim 1, characterized in that: The active component accounts for 5-60% of the total weight of the catalyst, preferably 10-40%; The additive accounts for 0.05-10% of the total weight of the catalyst, preferably 0.5-6%; The specific surface area of ​​the carrier is 50–1800 m². 2 / g, preferably 70-700m 2 / g; pore volume 0.2~1.2ml / g, preferably 0.3~1.0ml / g; The hydrophobic agent accounts for 0.1% to 15% of the weight of the carrier, preferably 1% to 10%. The total weight of the catalyst includes the sum of the weight of the support, the weight of the active metal element, and the weight of the auxiliary element.

4. The catalyst according to claim 1 or 2, characterized in that, The hydrophobication treatment method is as follows: during the catalyst preparation process, a hydrophobic agent is modified on the catalyst surface by one or more of the following methods: impregnation, self-assembly, sol-gel, coating, grafting, etc. The hydrophobic agent is one or more of organosilanes, polymers, or long-chain fatty acids. Among them, organosilanes include one or more of methyltriethoxysilane, methyltrimethoxysilane, octyltriethoxysilane, octyltrimethoxysilane, diethoxydimethylsilane, trimethylchlorosilane, trifluoropropyltrichlorosilane, trifluoropropyltriethoxysilane, hexadecyltrimethoxysilane, and octadecyltrimethoxysilane; polymers include one or more of polypropylene, polytetrafluoroethylene, polyethylene, and polystyrene; and long-chain fatty acids include fatty acids with 10 or more (12-20) carbon atoms, such as stearic acid and dodecanoic acid.

5. The catalyst according to any one of claims 1-4, characterized in that, The active metal and additives are loaded onto the carrier using at least one or two of the impregnation and precipitation methods: specifically, The catalyst is obtained by immersing the support in a solution containing an active metal element source and an auxiliary element source, followed by drying, calcination, and reduction. Alternatively, a solution containing an active metal element source and an auxiliary element source can be added together with a precipitant to a suspension of the carrier, followed by precipitation, aging, washing, drying, calcination, and reduction to obtain the catalyst. The drying conditions are: temperature 50-200℃, time 0.5-15h, and atmosphere is one or more combinations of air, oxygen, and nitrogen. The calcination conditions are: temperature 200-600℃, time 0.5-15h, and atmosphere is one or more combinations of air, oxygen, and nitrogen. The reduction treatment conditions are: temperature 200–600℃, pressure 0.1 MPa, time 0.5–10 h, and gas hourly space velocity 20–3000 h⁻¹. -1 The gas contains 1-100% hydrogen, and the remaining components are inert gases (such as nitrogen and / or argon).

6. A method for preparing heterocyclic amines by catalytic amination of polyol amines using any one of the catalysts described in claims 1-5, characterized in that: The method is carried out in the presence of any one of the catalysts described in claims 1-5; The reaction raw materials for the preparation of heterocyclic amines by catalytic ammoniation of polyol amines include two parts: a polyol amine source and an ammonia source. The polyol amine source has a chemical structure in which the total number of amino and hydroxyl functional groups is greater than or equal to 2. The polyol amine source is one or more of polyols, polyamines, or alcoholamine compounds; The polyols are compounds containing two or more hydroxyl groups, including ethylene glycol, diethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexanediol, and phenylenediol; the polyamines are compounds containing two or more amino groups, including ethylenediamine, propylenediamine, butylenediamine, pentanediamine, hexanediamine, diethylenetriamine, 2,2'-oxodiethylamine, and hydroxyethyldiethylenetriamine, among others, and one or more thereof; the alcohol-amine compounds are compounds containing both hydroxyl and amino groups, including monoethanolamine, diethanolamine, triethanolamine, hydroxyethylethylenediamine, diethylene glycolamine, aminopropanol, aminobutanol, aminopentanol, and aminohexanol, among others, and one or more thereof. The ammonia source is one or more of ammonia or primary amines, including one or more of ammonia, ammonia water, methylamine, ethylamine, propylamine, benzylamine, etc. The molar ratio of polyol amine source to ammonia source in the reaction raw materials is 0.01 to 20:1, preferably 0.05 to 10:1; The catalytic reaction process is carried out under hydrogen-containing conditions, wherein the molar proportion of hydrogen in the total feed material (including hydrogen and reactants) is 0.5-80%, preferably 1-40%; The reaction conditions are: temperature 130–220°C, preferably 150–200°C; pressure 1–30 MPa, preferably 4–25 MPa. The total liquid hourly space velocity of the polyol amine source was 0.02–15 h⁻¹. -1 Preferably 0.1–10 h -1 .

7. The method according to claim 6, characterized in that, The reaction of preparing heterocyclic amines by catalytic amination of polyol amines is carried out in a reactor, which includes one or more of continuous and batch reactors; wherein the continuous reactor is selected from one or more of fixed-bed reactors, continuous stirred tank reactors, slurry-bed reactors, and fluidized-bed reactors; the batch reactor is selected from autoclave reactors; preferably one or more of fixed-bed reactors and autoclave reactors.

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