Amination catalysts, their preparation and application

Abstract

A catalyst suitable for catalytic amination to prepare organic amines is disclosed, as well as its preparation and application. The catalyst comprises an aluminum- and / or silicon-containing inorganic porous support and an active metal component supported on the support. The active metal component includes at least one metal selected from Group VIII and Group IB. The ammonia adsorption capacity of the support, as measured by the NH₃-TPD method, is 0.25-0.65 mmol / g. The catalyst exhibits improved performance when used in the catalytic amination to prepare organic amines.

Description

[Technical Field]

[0001] This application relates to the technical field of amination reactions, specifically to a catalyst suitable for catalytic amination to prepare organic amines, and its preparation and application. [Previous Technology]

[0002] Amines are very important industrial organic compounds, widely used in various fields, such as solvents, pharmaceutical intermediates, resin raw materials, textile additives, pesticides, rubber stabilizers, corrosion inhibitors, and also in cleaning and plastics processing. The three main methods for preparing amines are the hydroamination of carbonyl compounds, the hydroamination of alcohols, and the hydrogenation of nitrile compounds. For example, the hydroamination of carbonyl compounds involves the reaction of acetone, hydrogen, and ammonia to produce isopropylamine. Examples of the hydroamination of alcohols include the hydrogenation of ethanol and ammonia to produce ethylamine, isopropanol and ammonia to produce isopropylamine, butanol and ammonia to produce butylamine, and hexanediol and ammonia to produce hexanediamine. Examples of the hydrogenation of nitrile compounds include the hydrogenation of acetonitrile to produce ethylamine and the hydrogenation of adiponitrile to produce hexanediamine.

[0003] US Patent 4409399 discloses a method for producing fatty amines. The catalyst used consists of (1) copper oxide or copper hydroxide, (2) nickel oxide or nickel hydroxide and (3) oxides or hydroxides of group IIA metals.

[0004] Chinese patent application CN102658162A discloses a catalyst for synthesizing ethylenediamine and a method for preparing ethylenediamine. The catalyst consists of three parts: a main active component, an auxiliary agent, and an ammoniation-treated support. The main active component is selected from one or more of the group consisting of Ni and Co, and accounts for 1-40% of the total weight of the catalyst. The auxiliary agent is selected from one or more of the group consisting of Fe, Cu, Ru, Re, K, Zn, and B, and their respective oxides, and accounts for 0.1-20% of the total weight of the catalyst. The ammoniation-treated support is selected from one or more of the group consisting of SiO2 and Al2O3, and is obtained by ammoniation treatment of the support.

[0005] However, the catalytic activity, feed conversion rate, product selectivity and catalyst stability of existing catalysts used in amination reactions still need to be improved. [Summary of the Invention]

[0006] The purpose of this application is to provide a catalyst suitable for catalytic amination to prepare organic amines, and the preparation and application thereof, wherein the catalyst has improved performance when used in the amination reaction, such as at least one of improved catalytic activity, reaction conversion, product selectivity and catalyst stability.

[0007] In order to achieve the above objectives, on the one hand, this application provides a catalyst suitable for catalytic amination to prepare organic amines, comprising an inorganic porous support containing aluminum and / or silicon and an active metal component supported on the support, wherein the active metal component comprises at least one metal selected from Group VIII and Group IB, wherein the ammonia adsorption capacity of the support, as measured by the NH3-TPD method, is 0.25-0.65 mmol / g.

[0008] Preferably, the support comprises a matrix and a dopant element. The matrix comprises a first support component and an optional second support component. The first support component is selected from alumina, silica, molecular sieve, aluminum silicate, or a combination thereof. The second support component is selected from diatomaceous earth and titanium dioxide. The dopant element is selected from a metallic element, a non-metallic element, or a combination thereof, excluding sodium and chlorine. The metallic element is selected from at least one of Group IA, Group IIA, Group VA, and lanthanide elements. The non-metallic element is selected from at least one of Group IIIA, Group VA, Group VIA, and Group VIIA non-metallic elements.

[0009] Preferably, the catalyst further includes a metal promoter supported on the support, the metal promoter comprising at least one metal selected from Group VIB, Group VIIB, Group IB, Group IIB and lanthanides.

[0010] On the other hand, a method for preparing the catalyst of this application is provided, comprising the following steps:

[0011] 1) Provide an inorganic porous support containing aluminum and / or silicon, wherein the ammonia adsorption capacity of the support, as determined by the NH3-TPD method, is 0.25-0.65 mmol / g;

[0012] 2) Loading an active metal component and optional metal additives onto the carrier; and

[0013] 3) The material obtained in step 2) is subjected to heat treatment and optional reduction treatment to obtain the catalyst.

[0014] In another aspect, this application provides a method for preparing an organic amine, comprising: in the presence of hydrogen, contacting an amination raw material, an amination reagent with a catalyst according to this application to carry out an amination reaction to obtain the organic amine, wherein the amination raw material is selected from alcohols, ketones, alkanolamines, aldehydes or combinations thereof; and the amination reagent is selected from ammonia, primary amines, secondary amines or combinations thereof.

[0015] When the catalyst of this application is used in the reaction of catalytic amination to prepare organic amines, it exhibits improved performance, particularly improved catalytic activity, reaction conversion, product selectivity and / or catalyst stability.

[0016] Other features and advantages of this application will be described in detail in the following detailed description section.

Implementation Method

[0018] The present disclosure will be further described in detail below through specific embodiments. It should be understood that the specific embodiments described herein are only for illustration and explanation of the present disclosure, and do not limit the present invention in any way.

[0019] Any specific numerical value disclosed herein (including the endpoints of a numerical range) is not limited to the exact value of that value, but should be understood to also include values ​​close to that exact value, such as all possible values ​​within ±5% of that exact value. Furthermore, with respect to the disclosed numerical range, one or more new numerical ranges can be obtained by arbitrarily combining the endpoint values ​​of the range, the endpoint values ​​with specific point values ​​within the range, and the specific point values, and these new numerical ranges should also be considered as specifically disclosed herein.

[0020] Unless otherwise stated, the terms used herein have the same meaning as commonly understood by those skilled in the art, and if a term is defined herein and its definition differs from the common understanding in the art, the definition herein shall prevail.

[0021] In this application, the ammonia adsorption capacity of the support and catalyst is determined by the NH3-TPD method, wherein the ammonia adsorption capacity is expressed as the measured ammonia desorption capacity.

[0022] In this application, the specific surface area, pore volume and the proportion of pores with different pore sizes of the carrier are measured by nitrogen adsorption-desorption method, as detailed in GB / T6609.35-2009.

[0023] In this application, "C2-20" refers to having 2 to 20 carbon atoms, for example, having 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms. Similarly, "C1-12" refers to having 1 to 12 carbon atoms.

[0024] In this application, the grain size of the active metal component and the metal additive is obtained by XRD testing.

[0025] Unless otherwise specified, all pressures given in this application are gauge pressures.

[0026] In this application, except for the contents expressly stated, any matters or issues not mentioned shall be directly applicable to those known in the art without any changes. Moreover, any implementation described herein may be freely combined with one or more other implementations described herein, and the resulting technical solutions or technical ideas shall be regarded as part of the original disclosure or original record of the present invention, and shall not be regarded as new content not disclosed or anticipated herein, unless those skilled in the art consider the combination to be obviously unreasonable.

[0027] All patent and non-patent literature mentioned in this article, including but not limited to textbooks and journal articles, are incorporated in full by way of citation.

[0028] As described above, in a first aspect, this application provides a catalyst suitable for catalytic amination to prepare organic amines, comprising an inorganic porous support containing aluminum and / or silicon and an active metal component supported on the support, wherein the active metal component comprises at least one metal selected from Group VIII and Group IB, wherein the ammonia adsorption capacity of the support, as measured by the NH3-TPD method, is 0.25-0.65 mmol / g.

[0029] According to this application, the Group VIII metal may be, for example, cobalt, nickel, or palladium, and the Group IB metal may be, for example, copper. In a preferred embodiment, the metal in the active metal component is selected from cobalt, nickel, palladium, copper, or combinations thereof, more preferably from cobalt, nickel, or combinations thereof.

[0030] In the catalyst of this application, the Group IB metal, such as copper, can be used alone as an active metal component, in which case it is usually used in a large amount; or it can be used in combination with a Group VIII metal, in which case it is usually used in a smaller amount. When the Group IB metal is used in combination with a Group VIII metal, such as cobalt, nickel and palladium, it is generally referred to herein as a metal promoter.

[0031] In a preferred embodiment, the ammonia adsorption capacity of the carrier, as measured by the NH3-TPD method, is 0.3-0.6 mmol / g.

[0032] In a preferred embodiment, the support comprises a matrix and a dopant element. The matrix comprises a first support component and an optional second support component. The first support component is selected from alumina, silica, molecular sieves, aluminum silicate, or combinations thereof. The second support component is selected from diatomaceous earth and titanium dioxide. The dopant element is selected from metallic elements, non-metallic elements, or combinations thereof, excluding sodium and chlorine. The metallic element is selected from at least one of Group IA, Group IIA, Group VA, and lanthanide elements, preferably at least one of calcium, magnesium, potassium, bismuth, strontium, barium, and lanthanum. The non-metallic element is selected from at least one of Group IIIA, Group VA, Group VIA, and Group VIIA non-metallic elements, preferably at least one of boron, fluorine, phosphorus, sulfur, and selenium.

[0033] In a further preferred embodiment, the doping element in the carrier is derived from metal cations and acid radicals, but does not include sodium ions and chloride ions; the metal cation is selected from at least one of Group IA metal cations, Group IIA metal ions, Group VA metal ions and lanthanide metal ions, preferably at least one of calcium ions, magnesium ions, potassium ions, bismuth ions, strontium ions, barium ions and lanthanum ions; the acid radical is selected from at least one of non-metallic acid radicals, preferably at least one of borate ions, fluoride ions, phosphate ions, sulfate ions and selenate ions.

[0034] In a preferred embodiment, the carrier has at least one of the following features:

[0035] The carbon dioxide adsorption capacity of the support is 0.05-0.4 mmol / g, preferably 0.05-0.3 mmol / g, more preferably 0.06-0.2 mmol / g. The carbon dioxide adsorption capacity of the support within this range is beneficial to improving the product selectivity of the catalyst and reducing the generation of by-products.

[0036] Based on the total weight of the matrix, the content of doped elements in the carrier is 0.03-6% by weight, preferably 0.05-6% by weight, and more preferably 0.08-4% by weight;

[0037] The specific surface area of ​​the carrier is 120-240 m2 / g, preferably 120-210 m2 / g, and more preferably 125-200 m2 / g;

[0038] The pore volume of the carrier is 0.45-1.2 ml / g, preferably 0.45-1.1 ml / g, and more preferably 0.5-1 ml / g;

[0039] The percentage of the pore volume in the support with a pore size in the range of 7-27 nm is greater than 65%, preferably greater than or equal to 70%, more preferably 70-90%, and preferably the percentage of the pore volume with a pore size less than 7 nm is 0-10%, for example 0-8%. The support having the above-mentioned pore size distribution is beneficial to increasing the surface diffusivity of the catalyst, improving the catalyst activity and product selectivity.

[0040] The matrix of the carrier comprises alumina and titanium dioxide in a weight ratio of 1.5-5:1, preferably 2-4.5:1; and

[0041] The content of alumina in the carrier accounts for more than 70% by weight of the total matrix, preferably more than 75% by weight, and more preferably 80-100% by weight.

[0042] In a preferred embodiment of the catalyst of this application, the content of the active metal component is 5-46 g, preferably 10-42 g, for example 13-40 g, relative to 100 g of matrix.

[0043] In a preferred embodiment, the catalyst further includes a metal promoter supported on the support, the metal promoter comprising at least one metal selected from Group VIB, Group VIIB, Group IB, Group IIB and lanthanides, preferably including at least one metal selected from Cr, Mo, W, Mn, Re, Cu, Ag, Au, Zn, La and Ce. More preferably, the content of the metal promoter is 0-10 g relative to 100 g of matrix, preferably 0.1-10 g, more preferably 0.5-8 g.

[0044] In some further preferred embodiments, the metal additive comprises a combination of at least one Group VIIB metal and at least one Group IB metal, wherein, based on the metal elements, the weight ratio of the Group VIIB metal to the Group IB metal is 0.05-15:1, preferably 0.1-12:1; or the metal additive comprises a combination of at least one Group VIIB metal and at least one Group IIB metal, wherein, based on the metal elements, the weight ratio of the Group VIIB metal to the Group IIB metal is 0.2-20:1, preferably 0.3-6:1; or the metal additive comprises a combination of at least one Group VIB metal, at least one Group IB metal, and at least one Group IIB metal, wherein, based on the metal elements, the weight ratio of the Group VIB metal, the Group IB metal, and the Group IIB metal is 0.1-10:0.1-10:1, preferably 0.2-8:0.2-8:1. Particularly preferred, the Group VIIB metal is selected from manganese and / or rhenium, the Group IB metal is selected from at least one of copper, silver and gold, the Group IIB metal is selected from zinc, and the Group VIB metal is selected from molybdenum and / or tungsten.

[0045] According to this application, the catalyst support can be obtained using existing methods suitable for preparing supports with the above-mentioned properties, and this application does not impose strict limitations on this. Preferably, the support can be prepared by a method comprising the following steps: sequentially shaping, drying, and calcining a mixture containing a dopant element and a matrix or its precursor to obtain the support, wherein the matrix comprises a first support component and an optional second support component, the first support component being selected from alumina, silica, molecular sieves, aluminum silicate, or combinations thereof, and the second support component being selected from diatomaceous earth, titanium dioxide, or combinations thereof. The molecular sieve may be, for example, ZSM-5 or ZSM-11 molecular sieves. When a matrix precursor is used, the precursor of the alumina may be boehmite, and the precursor of the silica may be silicic acid, orthosilicic acid, or silica gel.

[0046] In the above method for preparing the support, the matrix precursor is preferably boehmite. The boehmite can be prepared by at least one of the following methods: carbonization, organoaluminum hydrolysis, aluminum sulfate, and nitric acid. The specific surface area of ​​the boehmite is preferably 250-410 m² / g, more preferably 260-400 m² / g, and even more preferably 260-380 m² / g, for example, 250-330 m² / g or 265-410 m² / g; the pore volume of the boehmite is preferably 0.7-1.3 ml / g, more preferably 0.7-1.2 ml / g, and even more preferably 0.8-1.2 ml / g, for example, 0.8-1.3 ml / g or 0.78-1.2 ml / g. Using boehmite with a specific pore structure can yield a catalyst with superior performance.

[0047] In the above method for preparing the carrier, if the raw material providing the matrix precursor already contains the required amount of doping element, then only this raw material needs to be used for forming. If the raw material providing the matrix precursor does not contain doping element or the content of doping element is low (insufficient), then additional doping element can be introduced.

[0048] In the above method for preparing the support, a support modifier can be used to provide the dopant element. The support modifier contains at least one compound capable of providing cations (excluding sodium ions) and / or anions (excluding chloride ions). The cation is selected from at least one of Group IA cations, Group IIA metal ions, Group VA metal ions, and lanthanide metal ions, preferably at least one of calcium ions, magnesium ions, potassium ions, bismuth ions, strontium ions, barium ions, and lanthanum ions. The anion is selected from at least one of non-metallic acid radical ions, preferably at least one of borate ions, fluoride ions, phosphate ions, sulfate ions, and selenate ions.

[0049] Preferably, the carrier modifier is selected from at least one of boric acid, nickel borate, cobalt borate, potassium borate, hydrofluoric acid, potassium fluoride, cobalt fluoride, nickel fluoride, phosphoric acid, aluminum phosphate, potassium phosphate, potassium dihydrogen phosphate, potassium hydrogen phosphate, magnesium phosphate, calcium phosphate, sulfuric acid, cobalt sulfate, nickel sulfate, aluminum sulfate, calcium sulfate, bismuth nitrate, potassium nitrate, potassium sulfate, potassium carbonate, magnesium nitrate, magnesium sulfate, basic magnesium carbonate, calcium nitrate, basic calcium carbonate, strontium nitrate, strontium phosphate, strontium sulfate, barium nitrate, lanthanum nitrate, and selenic acid.

[0050] In the above methods for preparing the carrier, the forming method can be selected from kneading, rolling, or sheeting.

[0051] In the above method for preparing the carrier, the amount of carrier modifier used is such that, based on the total weight of the matrix, the content of the dopant element is 0.03-6% by weight, preferably 0.05-6% by weight, more preferably 0.08-4% by weight, for example, 0.08-1% by weight (for example, it can be 0.08% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4% by weight, 0.45% by weight, 0.5% by weight, 0.55% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.85% by weight, 0.9% by weight, 0.95% by weight, 1% by weight, or any intermediate value of any two of the above values). Those skilled in the art can determine the amount of a certain component raw material (such as the carrier modifier) ​​based on the amount of a certain component in the final carrier; therefore, the amounts of some raw materials are not shown in this document.

[0052] In the above method for preparing the carrier, the drying conditions may include: a temperature of 80-150℃ (e.g., 80℃, 85℃, 90℃, 95℃, 100℃, 110℃, 115℃, 120℃, 125℃, 130℃, 140℃, 150℃, or any intermediate value between any two of the above values), such as 100-150℃, 80-120℃, or 100-120℃, and a time of 6-20 h (e.g., 6 h, 7 h, 7.5 h, 8 h, 8.5 h, 9 h, 9.5 h, 10 h, 10.5 h, 10 h, 11 h, 11.5 h, 12 h, 12.5 h, 13 h, 14 h, 14.5 h, 15 h, 15.5 h, 16 h, 17 h, 18 h, 19 h, 20 h, etc.). h, or any intermediate value between any two of the above values), for example, 10-20 h, 5-15 h, or 8-12 h.

[0053] In the above method for preparing the carrier, the calcination conditions may include: a temperature of 500-1100℃ (e.g., 600℃, 650℃, 680℃, 700℃, 750℃, 800℃, 850℃, 900℃, 950℃, 990℃, 1000℃, 1050℃, 1100℃, or any intermediate value of any two of the above values), such as 600-1100℃, 550-1050℃, 530-1000℃, or 550-1000℃, and a time of 2-20 h (e.g., 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, 5 h, 5.5 h, 6 h, 7 h, 8 h, 9 h, 9.5 h, 10 h, 10.5 h, 11 h, 12 h, 15 h, 18 h, 20 h). h, or any intermediate value between any two of the above numbers), for example, 4-20 h, 4-10 h, or 5-8 h.

[0054] The catalyst of this application can be used after reduction, for example, by reduction with a hydrogen-containing gas at 350-500°C, preferably at 350-450°C, such as 400-450°C. The hydrogen can be pure hydrogen or hydrogen diluted with an inert gas, such as a mixture of nitrogen and hydrogen. During reduction, the reduction temperature is gradually increased, and the temperature increase should not be too rapid, for example, not exceeding 20°C / hour. The reduction time can be determined by monitoring the production of H2O in the reduction system, that is, when the reduction system no longer produces new H2O, the reduction is ended. Those skilled in the art can select the reduction time accordingly, which will not be described in detail here. For example, at the highest temperature, the reduction time can be 2-5 hours. The reduction can be carried out directly in the reactor, followed by the catalytic reaction. It can also be reduced in a separate reactor, also known as off-reactor reduction. After reduction, before being discharged from the reactor, it can be passivated with a mixture containing oxygen at a temperature of, for example, 10-60°C, particularly 20-40°C. The externally reduced and passivated catalyst is loaded into the reactor and activated with hydrogen or a mixture of hydrogen and nitrogen before use. The activation temperature is, for example, 150-250°C, preferably 170-240°C, such as 170-200°C. The activation time can be determined by monitoring the production of H2O in the activation system. That is, the activation ends when the activation system no longer produces new H2O. Those skilled in the art can select the activation time accordingly, which will not be described in detail here. For example, at the highest temperature, the activation time is, for example, 1-5 h, preferably 2-3 h. It can also be used directly without activation, depending on the degree of oxidation of the active metal components and metal promoters in the catalyst.

[0055] In a second aspect, a method for preparing the catalyst of this application is provided, comprising the following steps:

[0056] 1) Provide an inorganic porous support containing aluminum and / or silicon, wherein the ammonia adsorption capacity of the support, as determined by the NH3-TPD method, is 0.25-0.65 mmol / g;

[0057] 2) Loading an active metal component and optional metal additives onto the carrier; and

[0058] 3) The material obtained in step 2) is subjected to heat treatment and optional reduction treatment to obtain the catalyst.

[0059] In a preferred embodiment, the ammonia adsorption capacity of the carrier, as measured by the NH3-TPD method, is 0.3-0.6 mmol / g.

[0060] In a preferred embodiment, step 1) of "providing an inorganic porous support containing aluminum and / or silicon" includes sequentially shaping, drying, and calcining a mixture containing dopant elements and a matrix or its precursor to obtain the support. The matrix comprises a first support component and an optional second support component. The first support component is selected from alumina, silicon oxide, molecular sieves, aluminum silicate, or combinations thereof. The second support component is selected from diatomaceous earth, titanium dioxide, or combinations thereof. Preferably, the first support component is alumina. The precursor of the first support component has a specific surface area of ​​250-410 m² / g, preferably 260-400 m² / g, more preferably 260-380 m² / g, and a specific surface area of ​​0.7-1.3 ml / g, preferably 0.7-1.2 ml / g, more preferably 0.8-1.2 ml / g. The dopant is a pseudoboehmite with a pore volume of ml / g; the doping element is selected from metallic elements, non-metallic elements, or combinations thereof, excluding sodium and chlorine; the metallic element is selected from at least one of Group IA, Group IIA, Group VA and lanthanide elements, preferably at least one of calcium, magnesium, potassium, bismuth, strontium, barium and lanthanum; the non-metallic element is selected from at least one of Group IIIA, Group VA, Group VIA and Group VIIA non-metallic elements, preferably at least one of boron, fluorine, phosphorus, sulfur and selenium.

[0061] In a further preferred embodiment, a carrier modifier is used to provide the dopant element. The dopant element and the carrier modifier can be selected as described in the first aspect above, and will not be repeated here. More preferably, the amount of carrier modifier is such that, based on the total weight of the matrix, the content of the dopant element in the resulting carrier is 0.03-6% by weight, preferably 0.05-6% by weight, more preferably 0.08-4% by weight, for example, 0.08-1% by weight (for example, it can be 0.08% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4% by weight, 0.45% by weight, 0.5% by weight, 0.55% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.85% by weight, 0.9% by weight, 0.95% by weight, 1% by weight, or any intermediate value of any two of the above values).

[0062] In a further preferred embodiment, the forming method may be selected from kneading, rolling, or sheet forming, etc.

[0063] In a further preferred embodiment, the drying conditions in step 1) include: a temperature of 80-150°C and a time of 6-20 h; and / or the calcination conditions include: a temperature of 500-1100°C and a time of 2-20 h.

[0064] In a further preferred embodiment, step 1) has the features described in the first aspect above for the method of preparing the carrier, which will not be repeated here.

[0065] In a preferred embodiment, the loading in step 2) comprises impregnating the carrier with a solution containing a precursor of the active metal component and optionally a metal auxiliary agent, preferably with a pH value in the range of 3.5-5.5. Controlling the pH value of the impregnation solution within the above range can further improve the dispersibility of the active metal component.

[0066] According to this application, impregnation involves immersing the support in a suitable solution containing the active metal component and the metal additive, with the precursor adsorbed and loaded onto the support. Impregnation methods are further subdivided, including dry impregnation, wet impregnation, multiple impregnation, mixed impregnation, and spray impregnation. Dry and wet impregnation refer to the state of the support before impregnation with the active metal component precursor, whether it is dry or pre-wetted with water. Multiple impregnation refers to impregnating a mixed solution of one or more precursor components multiple times, or impregnating different precursor groups in batches. Multiple impregnation requires drying and calcination after each impregnation to "anchor" the impregnated components. Mixed impregnation involves impregnating the active metal component and the precursor used for the metal additive together without a precipitation reaction. Spray impregnation uses a spray gun to spray the impregnation solution onto a continuously rotating support, ensuring the impregnation solution just fills the pore volume of the support to saturation. The catalyst of this application can reasonably select these impregnation methods according to actual conditions.

[0067] In a preferred embodiment, the precursors of the active metal component and the metal additive are soluble salts of the corresponding metals, such as nitrates, formates, oxalates, lactates, etc. Water is preferably used as the solvent for forming the metal salt solution of the impregnation carrier; some organic solvents, such as ethanol, can also be used. The metal salt solution impregnation of the carrier can be carried out in any desired order, or it can be carried out continuously with multiple solutions containing one or more metal salts. All or a single impregnation step can be performed in several steps, and the impregnation order can also be changed. The concentration of the solution is selected to load the required amount of metal onto the carrier.

[0068] According to this application, in step 3), the carrier loaded with the active metal component and optional metal additives is subjected to heat treatment, which preferably includes calcination, or a combination of drying and calcination. For example, the heat treatment may include drying the impregnated carrier at 80-150°C, more preferably at 80-120°C. The drying time can be reasonably selected according to the drying temperature, the amount of material to be dried, and the drying equipment, for example, it can be 6-20 hours, such as 8 hours, as long as the moisture content after drying does not affect the subsequent calcination. Further, after drying, calcination can be performed at 150-500°C to remove the water of crystallization in the salt or to decompose the salt into oxides, preferably calcination at 300-500°C for 1-6 hours. In the case of multiple impregnations, it is best to perform drying and calcination after each impregnation.

[0069] In this application, the loading operation of the active metal component and the metal promoter has little effect on the microstructure of the catalyst. Therefore, the obtained catalyst has a similar pore structure to the support.

[0070] In the case of a cooperating manufacturer, this application provides a carrier, which is an inorganic porous material comprising aluminum and / or silicon, wherein the ammonia adsorption capacity of the carrier, as measured by the NH3-TPD method, is 0.25-0.65 mmol / g.

[0071] In a preferred embodiment, the ammonia adsorption capacity of the carrier, as measured by the NH3-TPD method, is 0.3-0.6 mmol / g.

[0072] In a preferred embodiment, the support comprises a matrix and a dopant element. The matrix comprises a first support component and an optional second support component. The first support component is selected from alumina, silica, molecular sieves, aluminum silicate, or combinations thereof. The second support component is selected from diatomaceous earth and titanium dioxide. The dopant element is selected from metallic elements, non-metallic elements, or combinations thereof, excluding sodium and chlorine. The metallic element is selected from at least one of Group IA, Group IIA, Group VA, and lanthanide elements, preferably at least one of calcium, magnesium, potassium, bismuth, strontium, barium, and lanthanum. The non-metallic element is selected from at least one of Group IIIA, Group VA, Group VIA, and Group VIIA non-metallic elements, preferably at least one of boron, fluorine, phosphorus, sulfur, and selenium.

[0073] In a further preferred embodiment, the doping element in the carrier is derived from metal cations and acid radicals, but does not include sodium ions and chloride ions; the metal cation is selected from at least one of Group IA metal cations, Group IIA metal ions, Group VA metal ions and lanthanide metal ions, preferably at least one of calcium ions, magnesium ions, potassium ions, bismuth ions, strontium ions, barium ions and lanthanum ions; the acid radical is selected from at least one of non-metallic acid radicals, preferably at least one of borate ions, fluoride ions, phosphate ions, sulfate ions and selenate ions.

[0074] In a preferred embodiment, the carrier has at least one of the following features:

[0075] The carbon dioxide adsorption capacity of the carrier is 0.05-0.4 mmol / g, preferably 0.05-0.3 mmol / g, and more preferably 0.06-0.2 mmol / g.

[0076] Based on the total weight of the matrix, the content of doped elements in the carrier is 0.03-6% by weight, preferably 0.05-6% by weight, and more preferably 0.08-4% by weight.

[0077] The specific surface area of ​​the carrier is 120-240 m2 / g, preferably 120-210 m2 / g, and more preferably 125-200 m2 / g;

[0078] The pore volume of the carrier is 0.45-1.2 ml / g, preferably 0.45-1.1 ml / g, and more preferably 0.5-1 ml / g;

[0079] The percentage of the pore volume in the carrier with a pore size in the range of 7-27 nm is greater than 65%, preferably greater than or equal to 70%, more preferably 70-90%, and preferably the percentage of the pore volume in the carrier with a pore size less than 7 nm is 0-10%, for example 0-8%;

[0080] The matrix of the carrier comprises alumina and titanium dioxide in a weight ratio of 1.5-5:1, preferably 2-4.5:1; and

[0081] The alumina content in the carrier accounts for more than 70% by weight of the total matrix, preferably more than 75% by weight, and more preferably 80-100% by weight.

[0082] In a fourth aspect, this application provides the use of the catalyst according to this application or the support according to this application in the catalytic amination to prepare organic amines.

[0083] In a fifth aspect, this application provides a method for preparing an organic amine, comprising: in the presence of hydrogen, contacting an amination raw material, an amination reagent, and a catalyst according to this application to carry out an amination reaction to obtain the organic amine.

[0084] In a preferred embodiment, the amination raw material is selected from alcohols, ketones, alkanolamines, aldehydes or combinations thereof, more preferably from C2-20 alcohols, C3-20 ketones, C2-20 alkanolamines, C2-20 aldehydes and various mixtures thereof. More preferably, the amination raw material is selected from ethanol, acetaldehyde, n-propanol, propionaldehyde, isopropanol, n-butanol, butyraldehyde, isobutanol, isobutyraldehyde, 2-ethylhexanol, 2-ethylhexanol, octanol, octanol, dodecanol, dodecanol, hexadecanol, hexadecanol, cyclopentanol, cyclohexanol, cyclooctanol, cyclododecanol, benzyl alcohol, benzaldehyde, phenethyl alcohol, phenylacetaldehyde, 1,4-butanediol, 1,4-butanedialdehyde, 1,5-pentanediol, 1,5-pentanedialdehyde, 1,6-hexanediol, 1,6-hexanedialdehyde, 1,8-octanediol, 1,8-octanedialdehyde, 1,12-dodecanediol, 1,12-dodecanedialdehyde, ethanolamine, propanolamine, isopropanolamine, 6-aminohexanol, diethanolamine, diisopropanolamine, dimethylethanolamine, acetone, ethylene glycol, 1,3-propanediol, and various mixtures thereof.

[0085] In this application, the amination agent refers to a reactant capable of providing an amino group and / or an amino group. Preferably, the amination agent is selected from ammonia, primary amines, secondary amines, or combinations thereof; more preferably, it is selected from ammonia, C1-12 primary amines, C2-12 secondary amines, and various mixtures thereof, such as at least one of alkylamines, cycloalkylamines, and aralkylamines; and even more preferably, C1-4 alkylamines. Particularly preferably, the amination agent is selected from ammonia, monomethylamine, dimethylamine, methylethylamine, monoethylamine, diethylamine, and various mixtures thereof.

[0086] In a preferred embodiment, the conditions for the amination reaction include: a molar ratio of hydrogen, amination reagent, and amination raw material of 1-5 : 2-35 : 1, preferably 1-5 : 2-33 : 1, more preferably 1-5 : 2-30 : 1; a temperature of 105-220°C, preferably 110-220°C, more preferably 130-200°C; a pressure of 0.7-25 MPa, preferably 0.8-25 MPa, more preferably 1-15 MPa; and a liquid hourly space velocity of the amination raw material of 0.06-1 m3 / (m3·h).

[0087] In some preferred embodiments, the amination feedstock is a monohydric alcohol, and the conditions for the amination reaction include: a molar ratio of hydrogen, amination reagent and amination feedstock of 1-4 : 2-10 : 1, preferably 1-4 : 2-9 : 1, more preferably 1-4 : 2-8 : 1; a temperature of 130-210°C, preferably 130-200°C; a pressure of 1-4 MPa, preferably 1-3.5 MPa, more preferably 1-2.5 MPa; and a liquid hourly space velocity of the amination feedstock of 0.1-0.8 m3 / (m3·h).

[0088] In some preferred embodiments, the amination raw material is a ketone or aldehyde, and the conditions for the amination reaction include: a molar ratio of hydrogen, amination reagent and amination raw material of 1-4 : 2-6 : 1, preferably 1-4 : 2-5 : 1; a temperature of 105-180℃, preferably 110-180℃, more preferably 110-170℃; a pressure of 0.7-3.5 MPa, preferably 0.7-2.5 MPa, more preferably 0.8-2.5 MPa; and a liquid hourly space velocity of the amination raw material of 0.1-1 m3 / (m3·h), preferably 0.1-0.8 m3 / (m3·h).

[0089] In some preferred embodiments, the amination feedstock is an alcoholic amine, and the conditions for the amination reaction include: a molar ratio of hydrogen, amination reagent and amination feedstock of 1-4 : 3-25 : 1, preferably 1-4 : 3-20 : 1; a temperature of 130-200°C, preferably 135-200°C; a pressure of 1-18 MPa, preferably 1-15 MPa, more preferably 1-11 MPa; and a liquid hourly space velocity of the amination feedstock of 0.06-0.8 m3 / (m3·h).

[0090] In some preferred embodiments, the amination feedstock is a diol, and the conditions for the amination reaction include: a molar ratio of hydrogen, amination reagent and amination feedstock of 0.3-4 : 3-45 : 1, preferably 1-4 : 3-35 : 1, more preferably 1-4 : 3-33 : 1; a temperature of 130-220°C, preferably 130-210°C; a pressure of 1-15 MPa, preferably 4-25 MPa; and a liquid hourly space velocity of the amination feedstock of 0.06-0.8 m³ / (m³·h), preferably 0.1-0.8 m³ / (m³·h).

[0091] In some preferred embodiments, the amination feedstock is a mixture of 1,6-hexanediol, cycloheximine, and 6-amino-1-hexanol, and the amination reaction conditions include: a molar ratio of hydrogen, amination reagent, and amination feedstock of 0.3-4 : 3-45 : 1, preferably 1-4 : 3-35 : 1, more preferably 1-4 : 3-33 : 1, further preferably 1-4 : 3-30 : 1; a temperature of 130-220°C, preferably 130-210°C; a pressure of 1-25 MPa, preferably 2-25 MPa, more preferably 4-25 MPa; and a liquid hourly space velocity of the amination feedstock of 0.06-0.8 m³ / (m³·h), preferably 0.1-0.8 m³ / (m³·h).

[0092] Type I Implementation

[0093] In a Type I embodiment of this application, a catalyst is provided that catalyzes the hydroamination of alcohols to produce organic amines. The catalyst comprises a support and an active metal component supported on the support and optional metal additives. The support is characterized in that it is selected from at least one of doped alumina, doped silica, doped molecular sieve, and doped aluminum silicate; the ammonia adsorption capacity of the support is 0.25-0.6 mmol / g, and the carbon dioxide adsorption capacity of the support is 0.05-0.3 mmol / g; the active metal component is cobalt and / or nickel.

[0094] The catalyst of the Type I embodiment of this application exhibits high catalytic activity and high selectivity in hydroamination reactions. For example, in the hydroamination of ethanol, it shows higher reactivity and produces less of the compounds containing methylethylamine, methyldiethylamine, ethyl n-propylamine, and ethyl dibutylamine, with higher selectivity for ethylamine formation. In the hydroamination of 1,6-hexanediol, it produces fewer heavy components and other impurities, with higher selectivity for hexanediamine formation. Through long-cycle life testing, the catalyst of the Type I embodiment of this application demonstrates more stable catalytic performance. By controlling the acidity and basicity of the catalyst within a certain range, its adsorption-desorption properties are improved, thereby promoting diffusion in the reaction system, accelerating the reaction rate, reducing carbon deposition, and mitigating pore blockage.

[0095] Preferably, the ammonia adsorption capacity of the carrier is 0.3-0.5 mmol / g, more preferably 0.3-0.42 mmol / g.

[0096] Preferably, the carbon dioxide adsorption capacity of the carrier is 0.06-0.2 mmol / g, more preferably 0.06-0.17 mmol / g.

[0097] Preferably, the support comprises a matrix and a dopant element, wherein the matrix is ​​selected from at least one of alumina, silica, molecular sieve, and aluminum silicate, and the dopant element comprises a metallic element and a non-metallic element. Preferably, the weight ratio of the metallic element to the non-metallic element can be 1:0.05-50, more preferably 1:0.2-8.

[0098] More preferably, the metal element is selected from at least one of Group IA metal elements, Group IIA metal elements, Group VA metal elements and lanthanide metal elements, and even more preferably at least one of calcium, magnesium, potassium, bismuth, strontium, barium and lanthanum.

[0099] More preferably, the non-metallic element is selected from at least one of Group IIIA, Group VA, Group VIA and Group VIIA non-metallic elements, and is further preferably at least one of boron, fluorine, phosphorus, sulfur and selenium.

[0100] More preferably, the impurity elements added to the support are derived from metal cations and acid radicals, and do not include sodium ions and chloride ions. Since the impurity elements are introduced during the preparation of the support, they mainly exist in the bulk phase of the support. More preferably, the metal cation can be selected from at least one of Group IA metal cations, Group IIA metal ions, Group VA metal ions, and lanthanide metal ions, and more preferably at least one of calcium ions, magnesium ions, potassium ions, bismuth ions, strontium ions, barium ions, and lanthanum ions; the acid radical ions can be selected from at least one of non-metallic acid radical ions, and more preferably at least one of borate ions, fluoride ions, phosphate ions, sulfate ions, and selenate ions.

[0101] Preferably, based on the total weight of the matrix, the content of doped elements in the carrier is 0.03-2% by weight, more preferably 0.08-1% by weight.

[0102] Preferably, the specific surface area of ​​the carrier is 120-240 m2 / g.

[0103] Preferably, the pore volume of the carrier is 0.5-1 ml / g.

[0104] According to the Type I embodiment of this application, the content of the active metal component may be 5-42 g, preferably 10-35 g, and more preferably 10-30 g, relative to 100 g of matrix.

[0105] According to a Type I embodiment of this application, in order to better utilize the performance of the catalyst, optimize the ratio of reaction products, and reduce unwanted side reactions, the catalyst may further contain a metal promoter. The metal promoter may be selected from at least one element from Group VIB, Group VIIB, Group IB, Group IIB, and the lanthanides, preferably at least one from Cr, Mo, W, Mn, Re, Cu, Ag, Au, Zn, La, and Ce. Preferably, the content of the metal promoter may be 0-10 g relative to 100 g of matrix, more preferably 0.5-6 g.

[0106] In a Type I embodiment of this application, a method for preparing an organic amine is also provided, characterized in that the method comprises: in the presence of hydrogen, contacting an amination raw material, an amination reagent, and a catalyst as described above to carry out an amination reaction.

[0107] According to the Type I embodiment of this application, the amination raw material or amination reagent can be selected as described above, and will not be repeated here.

[0108] According to the Type I embodiment of this application, the conditions for the amination reaction may include: a molar ratio of hydrogen, amination reagent and amination raw material of 1-5 : 2-35 : 1, a temperature of 130-200°C, a pressure of 1-15 MPa, and a liquid hourly space velocity of the amination raw material of 0.06-1 m3 / (m3·h).

[0109] Preferably, the amination raw material is a monohydric alcohol, and the conditions for the amination reaction include: a molar ratio of hydrogen, amination reagent and amination raw material of 1-4 : 2-10 : 1, preferably 2-3 : 4-6 : 1, a temperature of 130-200℃, preferably 160-180℃, a pressure of 1-4 MPa, preferably 1-2 MPa, and a liquid hourly space velocity of the amination raw material of 0.1-0.8 m3 / (m3·h), preferably 0.4-0.6 m3 / (m3·h).

[0110] Preferably, the amination raw material is a ketone or an aldehyde, and the conditions for the amination reaction include: a molar ratio of hydrogen, amination reagent and amination raw material of 1-4: 2-6: 1, a temperature of 110-180℃, a pressure of 1-3.5 MPa, and a liquid hourly space velocity of the amination raw material of 0.1-1 m3 / (m3·h).

[0111] Preferably, the amination raw material is an alcoholic amine, and the conditions for the amination reaction include: a molar ratio of hydrogen, amination reagent and amination raw material of 1-4 : 3-20 : 1, preferably 2-3 : 10-15 : 1, a temperature of 135-200℃, preferably 170-190℃, a pressure of 1-11 MPa, preferably 8-10 MPa, and a liquid hourly space velocity of the amination raw material of 0.06-0.8 m3 / (m3·h), preferably 0.4-0.6 m3 / (m3·h).

[0112] Preferably, the amination raw material is a diol, and the conditions for the amination reaction include: a molar ratio of hydrogen, amination reagent and amination raw material of 0.3-4 : 3-45 : 1, preferably 1-4 : 3-35 : 1, more preferably 2-3 : 10-15 : 1; a temperature of 130-210℃, preferably 180-190℃; a pressure of 1-15 MPa, preferably 8-10 MPa; and a liquid hourly space velocity of the amination raw material of 0.1-0.8 m3 / (m3·h), preferably 0.4-0.6 m3 / (m3·h).

[0113] Preferably, the amination raw material is a mixture of 1,6-hexanediol, cycloheximine and 6-amino-1-hexanol (abbreviated as aminohexanol), and the conditions of the amination reaction include: the molar ratio of hydrogen, amination reagent and amination raw material is 0.3-4 : 3-45 : 1, preferably 1-4 : 3-35 : 1, more preferably 3-4 : 10-20 : 1, the temperature is 130-210℃, preferably 180-200℃, the pressure is 1-15 MPa, preferably 5-10 MPa, and the liquid hourly space velocity of the amination raw material is 0.1-0.8 m3 / (m3·h), preferably 0.4-0.6 m3 / (m3·h).

[0114] Type II Implementation Method

[0115] In a Type II embodiment of this application, a catalyst with the function of catalytic amination to prepare amine is provided. The catalyst includes a support and an active metal component and a metal promoter supported on the support. The active metal component is cobalt and / or nickel. The metal promoter is a combination of at least one group VIIB metal and at least one group IB metal. The ammonia adsorption capacity of the support is 0.3-0.6 mmol / g.

[0116] Preferably, the ammonia adsorption capacity of the carrier is 0.3-0.56 mmol / g, more preferably 0.35-0.45 mmol / g.

[0117] The catalyst of the Type II embodiment of this application uses a specific metal promoter and has high catalytic activity and high selectivity.

[0118] Preferably, the support comprises a matrix and a dopant element, wherein the matrix comprises alumina and optional other supports, wherein the other supports are selected from silicon oxide and / or molecular sieves. More preferably, the content of the dopant element in the support is 0.05-6% by weight, more preferably 0.08-4% by weight, based on the weight of the matrix.

[0119] More preferably, the support is mainly composed of (doped) alumina, and may be further combined with (doped) silicon oxide, etc., thereby further improving the pore structure and structural stability of the catalyst. Particularly preferably, the content of alumina in the support accounts for more than 75% by weight of the total matrix, preferably 80-100% by weight.

[0120] Preferably, the dopant element in the support is a non-metallic element, preferably selected from at least one of boron, fluorine, phosphorus, sulfur, and selenium. More preferably, the dopant element is doped during the support preparation process in the manner of at least one of borate ions, fluoride ions, phosphate ions, sulfate ions, and selenate ions.

[0121] Preferably, the percentage of the pore volume in the carrier with a pore size in the range of 7-27 nm is 70-90% of the total pore volume of the carrier.

[0122] Preferably, the percentage of the pore volume with a pore size of less than 7 nm to the pore volume of the carrier is 0-8%.

[0123] Preferably, the pore volume with a pore size greater than 27 nm accounts for 15-30% of the pore volume of the carrier.

[0124] Preferably, the specific surface area of ​​the carrier is 125-200 m2 / g.

[0125] Preferably, the pore volume of the carrier is 0.45-1.1 ml / g.

[0126] Preferably, the content of the active metal component relative to every 100 g of matrix can be 8-45 g (for example, it can be any value among 8, 9, 15, 18, 20, 23, 25, 26, 30, 35, 36, 38, 40, 42, 45, or any intermediate value between any two of the above values).

[0127] Preferably, the content of the metal additive can be 0.1-10 g relative to every 100 g of matrix (for example, any value among 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 8.5, 8.7, 9, 10, or any intermediate value between any two of the above values).

[0128] According to a Type II embodiment of this application, in order to better utilize the performance of the catalyst, optimize the reaction product ratio, and reduce unwanted side reactions, the catalyst further contains a metal promoter. The metal promoter is selected from at least one group VIIB metal and a mixture of at least one group IB metal, wherein the weight ratio of the group VIIB metal to the group IB metal in the metal promoter is preferably 0.05-15:1, more preferably 0.1-12:1, and even more preferably 0.5-2:1. Preferably, the group VIIB metal is selected from manganese and / or rhenium. Preferably, the group IB metal is selected from at least one of copper, silver, and gold. The inventors of this application have discovered that using this preferred combination of metal promoters can yield a catalyst with superior catalytic effect.

[0129] According to the Type II embodiment of this application, by using a support with a specific pore structure and ammonia adsorption capacity, the catalyst can exhibit higher catalytic activity and selectivity in the hydroamination reaction of alcohols. In the hydroamination reaction of ethanol, the amount of byproducts such as methylethylamine, methyldiethylamine, ethyl n-propylamine, and ethyl dibutylamine generated is significantly reduced. In the hydroamination reaction of 1,6-hexanediol, fewer heavy components and other impurities are generated. Long-term life testing shows that the catalyst exhibits more stable catalytic performance, controlling the acidity of the catalyst (especially the ammonia adsorption capacity) within a certain range, improving the adsorption-desorption performance of the catalyst, and promoting diffusion in the reaction system in conjunction with the specific pore structure, accelerating the reaction rate, reducing carbon deposition, and mitigating pore blockage.

[0130] In a Type II embodiment of this application, a method for preparing an organic amine is also provided, characterized in that the method comprises: in the presence of hydrogen, contacting an amination raw material, an amination reagent, and a catalyst as described above to carry out an amination reaction.

[0131] According to the Type II embodiment of this application, the amination raw material or amination reagent can be selected as described above, and will not be repeated here.

[0132] According to the Type II embodiment of this application, the conditions for the amination reaction may include: a molar ratio of hydrogen, amination reagent and amination raw material of 1-5 : 2-33 : 1, a temperature of 110-220°C, a pressure of 0.8-25 MPa, and a liquid hourly space velocity of the amination raw material of 0.06-1 m3 / (m3·h).

[0133] Preferably, when the amination feedstock is a monohydric alcohol, the conditions for the amination reaction include: a molar ratio of hydrogen, amination reagent and amination feedstock of 1-4 : 2-10 : 1, a temperature of 130-210℃, a pressure of 1-3.5 MPa, and a liquid hourly space velocity of the amination feedstock of 0.1-0.8 m3 / (m3·h).

[0134] Preferably, when the amination raw material is a ketone or aldehyde, the conditions for the amination reaction include: a molar ratio of hydrogen, amination reagent and amination raw material of 1-4 : 2-5 : 1, a temperature of 110-170℃, a pressure of 0.8-2.5 MPa, and a liquid hourly space velocity of the amination raw material of 0.1-1 m3 / (m3·h).

[0135] Preferably, when the amination raw material is an alcoholic amine, the conditions for the amination reaction include: a molar ratio of hydrogen, amination reagent and amination raw material of 1-4 : 3-25 : 1, a temperature of 130-200℃, a pressure of 1-18 MPa, and a liquid hourly space velocity of the amination raw material of 0.06-0.8 m3 / (m3·h).

[0136] Preferably, when the amination raw material is a mixture or diol of 1,6-hexanediol, cycloheximine and 6-amino-1-hexanol, the conditions for the amination reaction include: a molar ratio of hydrogen, amination reagent and amination raw material of 1-4 : 3-33 : 1, a temperature of 130-220℃, a pressure of 4-25 MPa, and a liquid hourly space velocity of the amination raw material of 0.06-0.8 m3 / (m3·h).

[0137] Type III Implementation

[0138] In a Type III embodiment of this application, a catalyst with the function of catalyzing the hydroamination of alcohols is provided. The catalyst includes a support and a metal active component and a metal promoter supported on the support. The metal active component is cobalt and / or nickel. The metal promoter is a combination of at least one group VIIB metal and at least one group IIB metal. The ammonia adsorption capacity of the support is 0.3-0.7 mmol / g.

[0139] The catalyst of the Type III embodiment of this application uses a specific metal promoter, has high catalytic activity, high selectivity, and few by-products.

[0140] Preferably, the ammonia adsorption capacity of the carrier is 0.3-0.6 mmol / g, and the carbon dioxide adsorption capacity is 0.05-0.3 mmol / g.

[0141] Preferably, the support comprises a matrix and a dopant element, wherein the matrix comprises an alumina support and optional other supports, wherein the other supports are selected from at least one of silica, molecular sieves and diatomaceous earth. More preferably, based on the total weight of the matrix, the content of the dopant element in the support is 0.05-6% by weight, more preferably 0.08-4% by weight.

[0142] More preferably, the support is mainly composed of (doped) alumina support, and can be further combined with (doped) silicon oxide, etc., thereby further improving the pore diffusion and pore structure stability of the catalyst. Particularly preferably, the content of alumina support in the support accounts for more than 70% by weight of the total matrix, preferably 80-100% by weight.

[0143] Preferably, the dopant element in the support is selected from metallic and non-metallic elements, excluding sodium and chlorine. The weight ratio of the metallic element to the non-metallic element is preferably 1:0.1-40. The dopant element appears in the support precursor or is added during the preparation of the support, such that the dopant element is mainly present in the bulk phase of the support.

[0144] More preferably, the metal element may be selected from at least one of Group IA metal elements, Group IIA metal elements, Group VA metal elements and lanthanide metal elements, and more preferably at least one of calcium, magnesium, potassium, bismuth, strontium, barium and lanthanum.

[0145] More preferably, the non-metallic element may be derived from at least one of non-metallic acid anions, and more preferably from at least one of borate ions, fluoride ions, phosphate ions, sulfate ions, and selenate ions. The non-metallic element is selected from at least one of boron, fluorine, phosphorus, sulfur, and selenium.

[0146] Preferably, the percentage of pore volume with a pore size in the range of 7-27 nm in the carrier is greater than 65%, more preferably 70-90%, and even more preferably 70-75%. More preferably, the percentage of pore volume with a pore size less than 7 nm in the carrier is 0-10%, preferably 5-8%. More preferably, the percentage of pore volume with a pore size greater than 27 nm in the carrier is 10-30%, preferably 20-30%.

[0147] Preferably, the specific surface area of ​​the carrier is 120-205 m2 / g.

[0148] Preferably, the pore volume of the carrier is 0.45-1.2 ml / g.

[0149] Preferably, the carbon dioxide adsorption capacity of the carrier is 0.05-0.4 mmol / g.

[0150] Preferably, the content of the metal active component relative to every 100 g of matrix can be 14-46 g (for example, 14, 15, 20, 25, 30, 32, 35, 38, 40, 42, 45, 46, or any intermediate value of any two of the above values).

[0151] Preferably, the content of the metal additive per 100 grams of matrix can be 0.1-10 g (for example, 0.1, 0.5, 1, 1.2, 1.5, 1.8, 2, 3, 4, 5, 6, 7, 7.2, 7.5, 7.8, 8, 9, 10, or any intermediate value between any two of the above values).

[0152] According to a Type III embodiment of this application, in order to better utilize the performance of the catalyst, optimize the ratio of reaction products, and reduce unwanted side reactions, the catalyst further contains the metal promoter as described above. The weight ratio of Group VIIB metals to Group IIB metals in the metal promoter is preferably 0.2-20:1, more preferably 0.3-6:1, and even more preferably 1-5:1. Preferably, the Group VIIB metal is selected from manganese and / or rhenium. Preferably, the Group IIB metal is selected from zinc.

[0153] According to the Type III embodiment of this application, by using a support with specific pore structure, ammonia adsorption capacity, and carbon dioxide adsorption capacity, the catalyst can exhibit higher catalytic activity and selectivity when used in the hydroamination reaction of alcohols. In the hydroamination reaction of n-propanol, it generates fewer other impurities. In the hydroamination reaction of 1,6-hexanediol, it generates fewer heavy components and other impurities. Through long-cycle lifetime testing, the catalyst exhibits more stable catalytic performance. By controlling the acidity and basicity of the catalyst within a certain range, the adsorption-desorption performance of reaction intermediates on the catalyst surface is improved, thereby promoting diffusion in the reaction system, accelerating the reaction rate, reducing carbon deposition and pore blockage, and effectively extending the catalyst's lifetime.

[0154] In a type III embodiment of this application, a method for preparing an organic amine is also provided, characterized in that the method comprises: in the presence of hydrogen, contacting an amination raw material, an amination reagent, and a catalyst as described above to carry out an amination reaction.

[0155] According to the Type III embodiment of this application, the amination raw material or amination reagent can be selected as described above, and will not be repeated here.

[0156] According to the Type III embodiment of this application, the conditions for the amination reaction may include: a molar ratio of hydrogen, amination reagent and amination raw material of 1-5 : 2-30 : 1, a temperature of 110-220°C, a pressure of 0.8-25 MPa, and a liquid hourly space velocity of the amination raw material of 0.06-1 m3 / (m3·h).

[0157] Preferably, the amination feedstock is a monohydric alcohol, and the conditions for the amination reaction include: a molar ratio of hydrogen, amination reagent and amination feedstock of 1-4 : 2-9 : 1, a temperature of 130-200℃, a pressure of 1-2.5 MPa, and a liquid hourly space velocity of the amination feedstock of 0.1-0.8 m3 / (m3·h).

[0158] Preferably, the amination raw material is a ketone or an aldehyde, and the conditions for the amination reaction include: a molar ratio of hydrogen, amination reagent and amination raw material of 1-4 : 2-6 : 1, a temperature of 110-180℃, a pressure of 0.8-2.5 MPa, and a liquid hourly space velocity of the amination raw material of 0.1-0.8 m3 / (m3·h).

[0159] Preferably, the amination raw material is an alcoholic amine, and the conditions for the amination reaction include: a molar ratio of hydrogen, amination reagent and amination raw material of 1-4 : 3-20 : 1, a temperature of 130-200℃, a pressure of 1-15 MPa, and a liquid hourly space velocity of the amination raw material of 0.06-0.8 m3 / (m3·h).

[0160] Preferably, the amination feedstock is a mixture or diol of 1,6-hexanediol, cycloheximine and 6-amino-1-hexanol, and the amination reaction conditions include: a molar ratio of hydrogen, amination reagent and amination feedstock of 1-4 : 3-30 : 1, a temperature of 130-220℃, a pressure of 1-25 MPa, and a liquid hourly space velocity of the amination feedstock of 0.1-0.8 m3 / (m3·h).

[0161] Type IV Implementation Method

[0162] In a Class IV embodiment of this application, a catalyst with catalytic alcohol amination function is provided. The catalyst includes a support and an active metal component and a metal promoter supported on the support. The active metal component is cobalt and / or nickel. The metal promoter is a combination of at least one group VIB metal, at least one group IB metal, and at least one group IIB metal. The ammonia adsorption capacity of the support is 0.25-0.6 mmol / g.

[0163] The catalyst in the fourth embodiment of this application uses a specific metal promoter, has high catalytic activity, high selectivity, and few byproducts.

[0164] Preferably, the ammonia adsorption capacity of the carrier is 0.3-0.6 mmol / g.

[0165] Preferably, the support includes a matrix and doping elements, the matrix includes an alumina support and other supports, and the other supports are selected from silicon oxide and / or molecular sieves.

[0166] Preferably, the alumina precursor used in the support is doped with silicon oxide precursor and / or molecular sieve precursor during preparation, which can further significantly improve the diffusion and pore structure stability of the catalyst after preparation into a support. Preferably, the content of alumina support in the support accounts for more than 70% by weight of the total matrix, preferably 80-97% by weight.

[0167] Preferably, based on the total weight of the matrix, the content of doped elements in the carrier is 0.05-5% by weight, preferably 0.08-3% by weight.

[0168] Preferably, the dopant element is doped in a manner that is at least one selected from borate ions, fluoride ions, phosphate ions, sulfate ions, and selenate ions. The dopant element is preferably selected from at least one selected from boron, fluorine, phosphorus, sulfur, and selenium. According to a Type IV embodiment of this application, a non-metallic element is doped during the preparation of the precursor of the support, such that the dopant element is mainly present in the bulk phase of the support, rather than attached to the surface.

[0169] Preferably, the percentage of pore volume with a pore size in the range of 7-27 nm in the carrier pore volume is greater than 65%, more preferably 70-90%. More preferably, the percentage of pore volume with a pore size less than 7 nm in the carrier pore volume is 0-8%, more preferably 0-5%.

[0170] Preferably, the specific surface area of ​​the carrier is 120-210 m2 / g.

[0171] Preferably, the pore volume of the carrier is 0.45-1.1 ml / g.

[0172] Preferably, the content of the active metal component is 10-46 g, more preferably 18-38 g, relative to 100 g of matrix.

[0173] Preferably, the content of the metal additive may be 0.1-10 g, more preferably 0.5-6 g, relative to 100 g of matrix.

[0174] According to the Type IV embodiment of this application, in order to better utilize the performance of the catalyst of this application, optimize the reaction product ratio, and reduce unwanted side reactions, the catalyst further contains the metal promoter as described above. The weight ratio of Group VIB metals, Group IB metals, and Group IIB metals in the metal promoter is preferably 0.1-10:0.1-10:1, more preferably 0.2-8:0.2-8:1, and even more preferably 0.5-4:0.5-6:1. Preferably, the Group VIB metal is selected from molybdenum and / or tungsten. Preferably, the Group IB metal is selected from at least one of copper, silver, and gold. Preferably, the Group IIB metal is selected from zinc.

[0175] According to the Type IV embodiment of this application, using a support with a specific pore structure and ammonia adsorption capacity allows the catalyst to exhibit higher catalytic activity and selectivity in the hydroamination reaction of alcohols. In the hydroamination reaction of n-propanol, less other impurities are generated compared to the former. In the hydroamination reaction of 1,6-hexanediol, less heavy components and other impurities are generated. Long-term lifespan testing shows that the catalyst has more stable catalytic performance. Support modification not only improves the adsorption-desorption performance of the catalyst but also promotes diffusion in the reaction system, accelerates the reaction rate, reduces carbon deposition, and alleviates pore blockage.

[0176] In a Class IV embodiment of this application, a method for preparing an organic amine is also provided, characterized in that the method comprises: in the presence of hydrogen, contacting an amination raw material, an amination reagent, and a catalyst as described above to carry out an amination reaction.

[0177] According to the Type IV embodiment of this application, the amination raw material or amination reagent can be selected as described above, and will not be repeated here.

[0178] According to the Type IV embodiment of this application, the conditions for the amination reaction may include: a molar ratio of hydrogen, amination reagent and amination raw material of 1-5 : 2-35 : 1, a temperature of 105-220°C, a pressure of 0.7-25 MPa, and a liquid hourly space velocity of the amination raw material of 0.06-1 m3 / (m3·h).

[0179] Preferably, the amination feedstock is a monohydric alcohol, and the conditions for the amination reaction include: a molar ratio of hydrogen, amination reagent and amination feedstock of 1-4 : 2-8 : 1, a temperature of 130-200℃, a pressure of 1-2.5 MPa, and a liquid hourly space velocity of the amination feedstock of 0.1-0.8 m3 / (m3·h);

[0180] Preferably, the amination raw material is a ketone or an aldehyde, and the conditions for the amination reaction include: a molar ratio of hydrogen, amination reagent and amination raw material of 1-4 : 2-5 : 1, a temperature of 105-180℃, a pressure of 0.7-2.5 MPa, and a liquid hourly space velocity of the amination raw material of 0.1-0.8 m3 / (m3·h);

[0181] Preferably, the amination raw material is an alcoholic amine, and the conditions for the amination reaction include: a molar ratio of hydrogen, amination reagent and amination raw material of 1-4 : 3-25 : 1, a temperature of 130-200℃, a pressure of 5-18 MPa, and a liquid hourly space velocity of the amination raw material of 0.06-0.8 m3 / (m3·h);

[0182] Preferably, the amination feedstock is a mixture or diol of 1,6-hexanediol, cycloheximine and 6-amino-1-hexanol, and the amination reaction conditions include: a molar ratio of hydrogen, amination reagent and amination feedstock of 0.3-4 : 3-45 : 1, preferably 1-4 : 3-35 : 1, a temperature of 130-220℃, a pressure of 2-25 MPa, and a liquid hourly space velocity of the amination feedstock of 0.1-0.8 m3 / (m3·h).

[0183] Type V Implementation

[0184] In a type V embodiment of this application, a titanium-containing catalyst with amination function is provided. The catalyst contains a support and an active metal component and optional metal additives supported on the support. The support comprises a matrix and optional dopant elements, wherein the matrix comprises alumina and titanium dioxide in a weight ratio of 1.5-5:1, the active metal component is cobalt and / or nickel, and the ammonia adsorption capacity of the catalyst is 0.2-0.7 mmol / g, preferably 0.3-0.4 mmol / g.

[0185] The catalyst of the Type V embodiment of this application exhibits high catalytic activity and high selectivity in the hydroamination reaction of alcohols. In particular, it generates fewer heavy components and other impurities in the hydroamination reaction of 1,6-hexanediol, resulting in higher selectivity for the formation of hexanediamine. Long-term life testing has demonstrated that the catalyst exhibits more stable catalytic performance, accelerates the reaction rate, reduces carbon buildup, and mitigates pore blockage.

[0186] Titanium dioxide has strong acidity, exhibiting both Brønsted (B) and Lewis (L) acids, and interacts strongly with the components dispersed on it, unlike alumina. The composite support formed by alumina and titanium dioxide exhibits different catalytic effects in different reactions. Through careful research and subtle differentiation, the inventors of this application have proposed that incorporating a specific amount of titanium dioxide into the boehmite during the support formation process will particularly effectively improve the catalytic performance of the resulting catalyst. Preferably, the weight ratio of alumina to titanium dioxide is 2-4.5:1. Using this specific ratio will further improve the catalytic performance of the resulting catalyst.

[0187] Preferably, the content of the active metal component is 13-40 g, more preferably 20-36 g, relative to 100 g of matrix.

[0188] Preferably, the content of the metal additive may be 0-10 g relative to 100 g of matrix, preferably 2.5-8 g.

[0189] According to the Type V embodiment of this application, in order to better utilize the performance of the catalyst of this application, optimize the reaction product ratio, and reduce unwanted side reactions, the titanium-containing catalyst may further contain a metal promoter. The metal promoter may be selected from at least one of Group VIB, Group VIIB, Group IB, Group IIB, and lanthanides, preferably at least one of Cr, Mo, W, Mn, Re, Cu, Ag, Au, Zn, La, and Ce, and more preferably at least one of Mo, Mn, Re, Cu, Ag, Zn, and La.

[0190] Preferably, the titanium-containing catalyst has a carbon dioxide adsorption capacity of 0.07-0.2 mmol / g.

[0191] Preferably, the specific surface area of ​​the titanium-containing catalyst is 130-180 m2 / g.

[0192] Preferably, the pore volume of the titanium-containing catalyst is 0.55-0.75 ml / g.

[0193] Preferably, in the titanium-containing catalyst, the percentage of pore volume with a pore radius less than 4 nm in the total pore volume is preferably less than 20% (e.g., 3%, 5%, 7%, 8.5%, 10.5%, 11.5%, 12.5%, 15.5%, 18.5%, 19%, 19.5% or any value between the above values), the percentage of pore volume with a pore radius greater than 10 nm in the total pore volume is preferably less than 15% (e.g., 3%, 5%, 7%, 8.5%, 9%, 10.5%, 11.5%, 12.5%, 13.5%, 14%, 14.5% or any value between the above values), and the percentage of pore volume with a pore radius of 4-10 nm in the total pore volume is ≥65% (e.g., 66%, 70%, 72%, 73%, 75%, 76.5%, 77%, 77.5%, 78.5%, 79%, 80% or any value between the above values).

[0194] Preferably, the support of the titanium-containing catalyst is doped with sulfur, and the sulfur content is 0.1-0.5 g per 100 g of matrix, more preferably 0.15-0.4 g.

[0195] In the V-type embodiment of this application, the loading of the active metal component and the metal promoter has little effect on the ammonia adsorption capacity, carbon dioxide adsorption capacity, specific surface area and pore structure properties of the catalyst. Therefore, the relevant properties of the catalyst support are similar to those described above (e.g., the difference is within ±5%), and will not be repeated here.

[0196] Preferably, the titanium-containing catalyst can be strip-shaped, sheet-shaped, clover-shaped, or toothed spherical.

[0197] The catalyst according to the V-type embodiment of this application can be prepared by a loading method, firstly providing a support including a matrix and optional dopant elements, the matrix including alumina and titanium dioxide in a weight ratio of 2-5:1, and then loading the active metal component and optional metal additives onto the support.

[0198] In the V-type embodiment of this application, a method for preparing a titanium-containing catalyst with amination function is provided, comprising:

[0199] 1) The pseudoboehmite and titanium dioxide are mixed, shaped and calcined to obtain a carrier, wherein the amount of pseudoboehmite and titanium dioxide is such that the weight ratio of alumina to titanium dioxide in the obtained carrier is 1.5-5:1.

[0200] 2) Loading an active metal component and an optional metal additive onto the resulting support, wherein the active metal component includes cobalt and / or nickel.

[0201] Preferably, the amount of boehmite and titanium dioxide used is such that the weight ratio of alumina and titanium dioxide in the resulting carrier is 2-4.5:1.

[0202] Preferably, the pseudoboehmite is prepared by at least one of the following methods: carbonization, organoaluminum hydrolysis, aluminum sulfate, and nitric acid. The organoaluminum is preferably a C1-C10 organoaluminum, and more preferably aluminum isopropoxide.

[0203] Preferably, the titanium dioxide is provided by titanium dioxide, which is prepared by precipitation and / or sol-gel method. The raw material used in this method that can provide titanium can be an organic titanium source (e.g., an organic titanate ester) and / or an inorganic titanium source (e.g., an inorganic titanium salt). The inorganic titanium source can be one or more of TiCl4, Ti(SO4)2, TiOSO4, TiOCl2, titanium hydroxide, titanium nitrate, and titanium phosphate, etc. The organic titanium source can be one or more of fatty alcohol titanium and organic titanate esters. The organic titanate ester is preferably an organic titanate ester with the structural formula M4TiO4, wherein M is preferably an alkyl group having 1-4 carbon atoms, and the four Ms can be the same or different. Preferably, the organic titanate ester is selected from one or more of isopropyl titanate, n-propyl titanate, tetrabutyl titanate, and tetraethyl titanate. Specific examples of the raw materials that can provide titanium may include, but are not limited to, one or more of the following: TiOCl2, titanium tetrachloride, titanium sulfate, titanium oxysulfate, tetrapropyl titanate (including various isomers of tetrapropyl titanate, such as tetraisopropyl titanate and tetran-propyl titanate), tetrabutyl titanate (various isomers of tetrabutyl titanate, such as tetran-butyl titanate), and tetraethyl titanate.

[0204] Preferably, the content of sulfate in the titanium dioxide is 0.2-3 wt%. More preferably, the titanium dioxide is titanium sulfate or titanium oxysulfate prepared by the ammonia hydrolysis method, and using this titanium dioxide can obtain a catalyst with a more reasonable carrier pore structure and better catalytic performance.

[0205] Preferably, the amount of the active metal component is such that, relative to every 100 grams of carrier, the content of the active metal component can be 13-40 g (e.g., 13 g, 15 g, 18 g, 20 g, 24 g, 25 g, 26 g, 27 g, 28 g, 30 g, 33 g, 35 g, 36 g, 37 g, 38 g, 40 g or any value between the above values).

[0206] Preferably, in order to better utilize the performance of the catalyst, optimize the ratio of reaction products, and reduce unwanted side reactions, a metal additive can also be loaded onto the support. The amount of the metal additive is such that, relative to 100 grams of support, the content of the metal additive can be 0-10 g (e.g., 1 g, 2 g, 2.5 g, 3 g, 4 g, 5 g, 6 g, 7 g, 8 g, 8.5 g, 9 g, 10 g, or any value between the above values).

[0207] Preferably, the metal additive may be selected from at least one of Group VIB, Group VIIB, Group IB, Group IIB and lanthanide elements, preferably at least one of Cr, Mo, W, Mn, Re, Cu, Ag, Au, Zn, La and Ce, more preferably at least one of Mo, Mn, Re, Cu, Ag, Zn and La.

[0208] Preferably, in step 1), there are no special requirements for the conditions of kneading, shaping, and calcination. To obtain a carrier of suitable strength, the kneading is also carried out in the presence of an acid (especially at least one of inorganic acids such as nitric acid, sulfuric acid, and hydrofluoric acid, and organic acids such as formic acid, acetic acid, and citric acid), with the amount of acid being 2-10 g per 100 g of powder. The calcination temperature in step 1) can be 550-1100°C, preferably 800-1050°C. The calcination time in step 1) can be 2-6 h.

[0209] Preferably, in step 2), the loading method can be impregnation, that is, impregnating the carrier with a solution containing an active metal component precursor and an optional metal auxiliary agent precursor, followed by drying and calcination.

[0210] Preferably, the method may further include a step of reducing the product obtained in step 2) to obtain a catalyst in a reduced state of the active metal component and the reducible metal auxiliaries. Reduction can be performed using a gas containing hydrogen at 350-500°C, preferably at 350-450°C. The hydrogen can be pure hydrogen or hydrogen diluted with an inert gas, such as a mixture of nitrogen and hydrogen. During reduction, the reduction temperature should be gradually increased, and the increase should not be too rapid, for example, not exceeding 20°C / hour. The reduction time can be determined by monitoring the generation of H2O in the reduction system; that is, the reduction ends when the reduction system no longer generates new H2O. Those skilled in the art can select the reduction time accordingly, which will not be elaborated further. For example, at the highest temperature, the reduction time can be 2-5 hours.

[0211] Reduction can be carried out directly in the reactor, followed by a catalytic reaction. Reduction can also be performed in a separate reactor, also known as off-reactor reduction. After reduction, the catalyst can be passivated with an oxygen-containing mixture before being discharged from the reactor. The passivation temperature is, for example, 10-60°C, particularly 20-40°C. The off-reactored and passivated catalyst is loaded into the reactor and activated with hydrogen or a mixture of hydrogen and nitrogen before use. The activation temperature is, for example, 150-250°C, preferably 170-200°C. The activation time can be determined by monitoring the generation of H2O in the activation system; that is, activation ends when no new H2O is generated. Those skilled in the art can select the activation time accordingly, which will not be detailed further. For example, at the highest temperature, the activation time is, for example, 1-5 h, preferably 2-3 h. Alternatively, it can be used directly without activation, depending on the degree of oxidation of the active metal components and metal promoters in the catalyst.

[0212] In the V-type embodiment of this application, a method for preparing an organic amine is also provided, comprising: contacting ammonia and / or an organic amine with an alcohol in the presence of a titanium-containing catalyst as described above to carry out an amination reaction.

[0213] Preferably, the alcohol can be at least one of a monohydric alcohol having 2-20 carbon atoms, either substituted or unsubstituted, and a dihydric alcohol having 2-20 carbon atoms, either substituted or unsubstituted (the substituted group can be an amino group). For example, at least one of ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-ethylhexanol, octanol, dodecyl alcohol, hexadecyl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, phenethyl alcohol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,12-dodecanediol, ethanolamine (2-aminoethanol), 6-amino-1-hexanol (abbreviated as aminohexanol), etc.

[0214] Preferably, the organic amine can be a primary amine and / or a secondary amine. For example, alkylamines having 1-4 carbon atoms can be used, such as at least one of monomethylamine, dimethylamine, methylethylamine, monoethylamine, diethylamine, etc. The amination reaction preferably uses excess ammonia or amine; for example, the amount of ammonia or organic amine relative to each mole of hydroxyl group in the alcohol can be 1-50 moles, preferably 3-20 moles, more preferably 3-15 moles. The amination reaction of the alcohol is carried out in the presence of hydrogen, i.e., under hydrogen-dependent conditions. The amount of hydrogen relative to each mole of hydroxyl group in the alcohol can be 1-10 mol. The partial pressure of hydrogen is, for example, 0.05-2 MPa. The temperature of the amination reaction can be 100-300°C. The pressure of the amination reaction can be 0.1-25 MPa, preferably 1-15 MPa. The liquid hourly space velocity of the alcohol can be 0.1-0.8 m³ / (m³·h).

[0215] For example, the amination reaction is, for instance, the hydroamination of ethanol to prepare ethylamine, the hydroamination of n-propanol to prepare n-propylamine, the hydroamination of isopropanol to prepare isopropylamine, the hydroamination of n-butanol to prepare n-butylamine, the hydroamination of ethylene glycol to prepare ethylenediamine, the hydroamination of ethanolamine to prepare ethylene glycol, the hydroamination of 1,3-propanediol to prepare 1,3-propanediamine, the hydroamination of 1,4-butanediol to prepare 1,4-butanediamine, the hydroamination of 1,6-hexanediol to prepare 1,6-hexanediamine, or the hydroamination of 1,12-dodecanediol to prepare 1,12-dodecanediamine.

[0216] According to the Type V embodiment of this application, the amination reaction can be carried out intermittently or continuously. The amination reaction can be a gas-phase reaction or a liquid-phase trickle bed reaction.

[0217] This application also provides some specific technical solutions for amination reactions using the catalyst of the V-type embodiment of this application.

[0218] For example, this application provides a method for producing 1,6-hexanediamine from 1,6-hexanediol using a catalyst according to the V-type embodiment of this application. The method involves a hydrogenation-amination reaction of 1,6-hexanediol, ammonia, and hydrogen at a reaction temperature of 130-200°C, a reaction pressure of 1-11 MPa, a feed liquid hourly space velocity of 1,6-hexanediol of 0.1-0.8 m³ / (m³·h), and a molar ratio of hydrogen:ammonia:hexanediol of 1-4:3-20:1, thereby generating hexanediamine, 6-amino-1-hexanol, and cycloheximine.

[0219] This application provides a method for producing 1,6-hexanediamine using a catalyst according to a type V embodiment of this application with a mixture of 1,6-hexanediamine, cycloheximine, and 6-amino-1-hexanol as raw material. The method involves subjecting the mixture, ammonia, and hydrogen to a hydrogenation-amination reaction. The mixture is a mixture of 1,6-hexanediamine, cycloheximine, and 6-amino-1-hexanol. The reaction temperature is 130-200°C, the reaction pressure is 1-11 MPa, the feed liquid hourly space velocity of the mixture is 0.1-0.8 m³ / (m³·h), and the molar ratio of hydrogen to ammonia to the mixture is 1-4 : 3-20 : 1, generating a reaction solution containing 1,6-hexanediamine, 6-amino-1-hexanol, and cycloheximine.

[0220] In a particularly preferred embodiment, this application discloses the following technical solution:

[0221] A1. A catalyst having the function of catalyzing the hydroamination of alcohols to produce organic amines, the catalyst comprising a support and an active metal component supported on the support and optional metal promoters, characterized in that the support is selected from at least one of doped alumina, doped silica, doped molecular sieve and doped aluminum silicate; the ammonia adsorption capacity of the support is 0.25-0.6 mmol / g, the carbon dioxide adsorption capacity of the support is 0.05-0.3 mmol / g; the active metal component is cobalt and / or nickel.

[0222] A2. The catalyst according to Project A1, wherein the ammonia adsorption capacity of the support is 0.3-0.5 mmol / g;

[0223] and / or, the carbon dioxide adsorption capacity of the carrier is 0.06-0.2 mmol / g;

[0224] and / or, the content of the impurity element added to the carrier accounts for 0.03-2% by weight of the total weight of the non-impurity element components in the carrier, preferably 0.08-1% by weight;

[0225] and / or, the impurity elements added to the support include metallic and non-metallic elements, wherein the metallic element is selected from at least one of Group IA, Group IIA, Group VA and lanthanide elements, preferably at least one of calcium, magnesium, potassium, bismuth, strontium, barium and lanthanum; the non-metallic element is selected from at least one of Group IIIA, Group VA, Group VIA and Group VIIA non-metallic elements, preferably at least one of boron, fluorine, phosphorus, sulfur and selenium; preferably, the impurity elements added to the support are derived from metal cations and acid radicals and do not include sodium ions and chloride ions; the metal cation is selected from at least one of Group IA, Group IIA, Group VA and lanthanide elements, preferably at least one of calcium ions, magnesium ions, potassium ions, bismuth ions, strontium ions, barium ions and lanthanum ions; the acid radical is selected from at least one of non-metallic acid radicals, preferably at least one of borate ions, fluoride ions, phosphate ions, sulfate ions and selenate ions;

[0226] and / or, the specific surface area of ​​the carrier is 120-240 m2 / g;

[0227] and / or, the pore volume of the carrier is 0.5-1 ml / g;

[0228] and / or, relative to each 100 g of matrix, the content of the active metal component is 5-42 g, preferably 10-35 g.

[0229] A3. The catalyst according to Project A1 or A2, wherein the support is prepared by a method comprising the following steps: sequentially shaping, drying and calcining a mixture containing a dopant element and a support source, wherein the support source is selected from at least one of boehmite, silica, molecular sieve and aluminum silicate.

[0230] A4. The catalyst according to Project A3, wherein the dopant element is provided by a support modifier, and the support modifier is preferably at least one of a compound capable of providing cations and anions, wherein the cation is selected from at least one of Group IA cations, Group IIA metal ions, Group VA metal ions and lanthanide metal ions, preferably at least one of calcium ions, magnesium ions, potassium ions, bismuth ions, strontium ions, barium ions and lanthanum ions;

[0231] and / or, the anion is selected from at least one of non-metallic acid radicals, preferably at least one of borate, fluoride, phosphate, sulfate and selenate.

[0232] A5. The catalyst according to Project A4, wherein the carrier modifier is selected from at least one of boric acid, nickel borate, cobalt borate, potassium borate, hydrofluoric acid, potassium fluoride, cobalt fluoride, nickel fluoride, phosphoric acid, aluminum phosphate, potassium phosphate, potassium dihydrogen phosphate, potassium hydrogen phosphate, magnesium phosphate, calcium phosphate, sulfuric acid, cobalt sulfate, nickel sulfate, aluminum sulfate, calcium sulfate, bismuth nitrate, potassium nitrate, potassium sulfate, potassium carbonate, magnesium nitrate, magnesium sulfate, basic magnesium carbonate, calcium nitrate, basic calcium carbonate, strontium nitrate, strontium phosphate, strontium sulfate, barium nitrate, lanthanum nitrate, and selenic acid;

[0233] Preferably, the pseudoboehmite has a specific surface area of ​​250-330 m2 / g and a pore volume of 0.8-1.3 ml / g.

[0234] A6. The catalyst according to any one of A3 to A5, wherein the drying conditions include: a temperature of 80-150°C and a time of 6-20 h;

[0235] and / or, the calcination conditions include: a temperature of 600-1100℃ and a time of 2-20 h.

[0236] A7. A method for preparing the catalyst according to any one of items A1 to A6, the method comprising: loading an active metal component and an optional metal promoter onto a support.

[0237] A8, The carrier defined by any one of items A1 to A6.

[0238] A9. The application of the catalyst described in any one of items A1 to A6, the method described in item A7, or the support described in item A8 in the amination to produce organic amines.

[0239] A10. A method for preparing organic amines, characterized in that the method comprises: in the presence of hydrogen, contacting the amination raw material, the amination reagent, and the catalyst described in any one of items A1 to A6 to carry out an amination reaction;

[0240] Alternatively, the method includes: screening a catalyst with a support defined in any one of items A1 to A6, and contacting the amination feedstock, the amination reagent, and the screened catalyst in the presence of hydrogen to carry out an amination reaction.

[0241] A11. According to the method described in Project A10, the conditions for the amination reaction include: the molar ratio of hydrogen, amination reagent and amination raw material is 1-5 : 2-35 : 1, the temperature is 130-200℃, the pressure is 1-15 MPa, and the liquid hourly space velocity of the amination raw material is 0.06-1 m3 / (m3·h);

[0242] and / or, the amination raw material is selected from at least one of C2-20 alcohols, C3-20 ketones, C2-20 alkanolamines, and C2-20 aldehydes, preferably ethanol, acetaldehyde, n-propanol, propionaldehyde, isopropanol, n-butanol, butyraldehyde, isobutanol, isobutyraldehyde, 2-ethylhexanol, 2-ethylhexanaldehyde, octanol, octanaldehyde, dodecanool, dodecaldehyde, hexadecanool, hexadecaldehyde, cyclopentanol, cyclohexanol, cyclooctanol, cyclododecanool At least one of the following: benzyl alcohol, benzaldehyde, phenylethanol, phenylacetaldehyde, 1,4-butanediol, 1,4-butanedialdehyde, 1,5-pentanediol, 1,5-pentanedialdehyde, 1,6-hexanediol, 1,6-hexanedialdehyde, 1,8-octanediol, 1,8-octanedialdehyde, 1,12-dodecanediol, 1,12-dodecanedialdehyde, ethanolamine, propanolamine, isopropanolamine, 6-aminohexanol, diethanolamine, acetone, ethylene glycol, and 1,3-propanediol;

[0243] and / or, the amination agent is selected from at least one of ammonia, a C1-12 primary amine and a C2-12 secondary amine, preferably at least one of ammonia, monomethylamine, dimethylamine, methylethylamine, monoethylamine and diethylamine.

[0244] A12. According to the method described in Project A11, when the amination raw material is a monohydric alcohol, the conditions for the amination reaction include: the molar ratio of hydrogen, amination reagent and amination raw material is 1-4 : 2-10 : 1, the temperature is 130-200℃, the pressure is 1-4 MPa, and the liquid hourly space velocity of the amination raw material is 0.1-0.8 m3 / (m3·h);

[0245] Or, when the amination raw material is a ketone or aldehyde, the conditions for the amination reaction include: the molar ratio of hydrogen, amination reagent and amination raw material is 1-4 : 2-6 : 1, the temperature is 110-180℃, the pressure is 1-3.5 MPa, and the liquid hourly space velocity of the amination raw material is 0.1-1 m3 / (m3·h);

[0246] Or, when the amination raw material is an alcoholamine, the conditions for the amination reaction include: the molar ratio of hydrogen, amination reagent and amination raw material is 1-4 : 3-20 : 1, the temperature is 135-200℃, the pressure is 1-11 MPa, and the liquid hourly space velocity of the amination raw material is 0.06-0.8 m3 / (m3·h);

[0247] Or, when the amination feedstock is a diol, the conditions for the amination reaction include: a molar ratio of hydrogen, amination reagent and amination feedstock of 1-4 : 3-35 : 1, a temperature of 130-210℃, a pressure of 1-15 MPa, and a liquid hourly space velocity of the amination feedstock of 0.1-0.8 m3 / (m3·h);

[0248] Alternatively, when the amination feedstock is a mixture of 1,6-hexanediol, cycloheximine, and 6-amino-1-hexanol, the conditions for the amination reaction include: a molar ratio of hydrogen, amination reagent, and amination feedstock of 1-4 : 3-35 : 1, a temperature of 130-210℃, a pressure of 1-15 MPa, and a liquid hourly space velocity of the amination feedstock of 0.1-0.8 m3 / (m3·h).

[0249] B1. A catalyst having the function of catalyzing amination to prepare amines, the catalyst comprising a support and an active metal component and a metal promoter supported on the support, characterized in that the active metal component is cobalt and / or nickel; the metal promoter is a combination of at least one group VIIB metal and at least one group IB metal.

[0250] B2. The catalyst according to Project B1, wherein the support includes an alumina support, a dopant element and optional other supports, wherein the other supports are selected from silicon oxide and / or molecular sieves; the ammonia adsorption capacity of the support is 0.3-0.6 mmol / g; and the percentage of the pore volume of the support with a pore size in the range of 7-27 nm to the pore volume of the support is greater than or equal to 70%.

[0251] B3. The catalyst according to Project B1 or B2, wherein the content of alumina support in the carrier accounts for more than 75% by weight of the total amount of alumina support and other supports, preferably 80-100% by weight.

[0252] and / or, the content of the dopant element is 0.05-6% by weight of the matrix, preferably 0.08-4% by weight;

[0253] and / or, the doping element in the support is a non-metallic element, preferably doped during the preparation of the support in the manner of at least one of borate ions, fluoride ions, phosphate ions, sulfate ions and selenate ions;

[0254] and / or, the ammonia adsorption capacity of the carrier is 0.3-0.56 mmol / g;

[0255] and / or, the percentage of pore volume in the carrier with a pore size in the range of 7-27 nm is 70-90% of the total pore volume of the carrier, and the percentage of pore volume with a pore size less than 7 nm is 0-8% of the total pore volume of the carrier;

[0256] and / or, the specific surface area of ​​the carrier is 125-200 m2 / g;

[0257] and / or, the pore volume of the carrier is 0.45-1.1 ml / g;

[0258] and / or, the content of the active metal component is 8-45 g relative to every 100 g of matrix;

[0259] and / or, the content of the metal additive is 0.1-10 g relative to every 100 g of matrix;

[0260] and / or, the weight ratio of Group VIIB metals to Group IB metals in the metal additive is 0.05-15:1, preferably 0.1-12:1;

[0261] and / or, the Group VIIB metal is selected from manganese and / or rhenium;

[0262] and / or, the Group IB metal is selected from at least one of copper, silver and gold.

[0263] B4. The catalyst according to any one of B1 to B3, wherein the support is prepared by a method comprising the following steps: sequentially shaping, drying and calcining a mixture containing an alumina precursor, a dopant element and optionally other support precursors, wherein the other support precursors are selected from silicon oxide precursors and / or molecular sieve precursors, and the dopant element is provided by a support modifier, wherein the support modifier is at least one of inorganic acids.

[0264] B5. The catalyst according to Project B4, wherein the inorganic acid is selected from at least one of inorganic acids containing non-metallic acid radicals, preferably at least one of boric acid, hydrofluoric acid, phosphoric acid, sulfuric acid and selenic acid.

[0265] B6. The catalyst according to Project B4 or B5, wherein the alumina precursor is boehmite, the specific surface area of ​​the boehmite is 260-380 m2 / g, and the pore volume is 0.78-1.2 ml / g.

[0266] B7. The catalyst according to any one of B4 to B6, wherein the drying conditions include: a temperature of 80-150°C and a time of 6-20 h;

[0267] and / or, the calcination conditions include: a temperature of 550-1050℃ and a time of 2-20 h.

[0268] B8. A method for preparing the catalyst according to any one of items B1 to B7, the method comprising: loading an active metal component and a metal promoter onto a support.

[0269] B9, The carrier defined by any one of items B2 to B7 of the project.

[0270] B10. The application of the catalyst described in any one of items B1 to B7, the method described in item B8, or the support described in item B9 in the amination to produce organic amines.

[0271] B11. A method for preparing organic amines, characterized in that the method comprises: in the presence of hydrogen, contacting the amination raw material, the amination reagent, and the catalyst described in any one of items B1 to B7 to carry out an amination reaction;

[0272] Alternatively, the method includes: screening a catalyst comprising a support defined in any one of items B1 to B7, and contacting the amination feedstock, the amination reagent, and the screened catalyst in the presence of hydrogen to carry out an amination reaction.

[0273] B12. According to the method described in Project B11, the conditions for the amination reaction include: the molar ratio of hydrogen, amination reagent and amination raw material is 1-5 : 2-33 : 1, the temperature is 110-220℃, the pressure is 0.8-25 MPa, and the liquid hourly space velocity of the amination raw material is 0.06-1 m3 / (m3·h);

[0274] and / or, the amination raw material is selected from at least one of C2-20 alcohols, C3-20 ketones, C2-20 alkanolamines, and C2-20 aldehydes, preferably ethanol, acetaldehyde, n-propanol, propionaldehyde, isopropanol, n-butanol, butyraldehyde, isobutanol, isobutyraldehyde, 2-ethylhexanol, 2-ethylhexanaldehyde, octanol, octanaldehyde, dodecanool, dodecaldehyde, hexadecanool, hexadecaldehyde, cyclopentanol, cyclohexanol, cyclooctanol, cyclododecanool, At least one of benzyl alcohol, benzaldehyde, phenylethanol, phenylacetaldehyde, 1,4-butanediol, 1,4-butanedialdehyde, 1,5-pentanediol, 1,5-pentanedialdehyde, 1,6-hexanediol, 1,6-hexanedialdehyde, 1,8-octanediol, 1,8-octanedialdehyde, ethanolamine, propanolamine, isopropanolamine, 6-aminohexanol, diethanolamine, diisopropanolamine, dimethylethanolamine, acetone, ethylene glycol, 1,3-propanediol, and 1,12-dodecanediol;

[0275] and / or, the amination agent is selected from at least one of ammonia, a C1-12 primary amine and a C1-12 secondary amine, preferably at least one of ammonia, monomethylamine, dimethylamine, methylethylamine, monoethylamine and diethylamine.

[0276] B13. According to the method described in Project B12, when the amination raw material is a monohydric alcohol, the conditions for the amination reaction include: the molar ratio of hydrogen, amination reagent and amination raw material is 1-4 : 2-10 : 1, the temperature is 130-210℃, the pressure is 1-3.5 MPa, and the liquid hourly space velocity of the amination raw material is 0.1-0.8 m3 / (m3·h);

[0277] Or, when the amination raw material is a ketone or aldehyde, the conditions for the amination reaction include: a molar ratio of hydrogen, amination reagent and amination raw material of 1-4 : 2-5 : 1, a temperature of 110-170℃, a pressure of 0.8-2.5 MPa, and a liquid hourly space velocity of the amination raw material of 0.1-1 m3 / (m3·h);

[0278] Or, when the amination raw material is an alcoholamine, the conditions for the amination reaction include: the molar ratio of hydrogen, amination reagent and amination raw material is 1-4 : 3-25 : 1, the temperature is 130-200℃, the pressure is 1-18 MPa, and the liquid hourly space velocity of the amination raw material is 0.06-0.8 m3 / (m3·h);

[0279] Alternatively, when the amination feedstock is a mixture or diol of 1,6-hexanediol, cycloheximine and 6-amino-1-hexanol, the conditions for the amination reaction include: a molar ratio of hydrogen, amination reagent and amination feedstock of 1-4 : 3-33 : 1, a temperature of 130-220℃, a pressure of 4-25 MPa, and a liquid hourly space velocity of the amination feedstock of 0.06-0.8 m3 / (m3·h).

[0280] C1. A catalyst having the function of catalyzing the hydroamination of alcohols, the catalyst comprising a support and a metal active component and a metal promoter supported on the support, characterized in that the metal active component is cobalt and / or nickel; the metal promoter is a combination of at least one group VIIB metal and at least one group IIB metal.

[0281] C2. The catalyst according to Project C1, wherein the support comprises an alumina support, a dopant element, and optional other supports, wherein the other supports are selected from at least one of silica, molecular sieves, and diatomaceous earth; the ammonia adsorption capacity of the support is 0.3-0.7 mmol / g and the carbon dioxide adsorption capacity is 0.05-0.4 mmol / g; and the pore volume of the support with a pore size in the range of 7-27 nm accounts for more than 65% of the total pore volume of the support.

[0282] C3. The catalyst according to Project C1 or C2, wherein the content of alumina support in the carrier accounts for more than 70% by weight of the total amount of alumina support and other supports, preferably 80-100% by weight.

[0283] and / or, the content of the dopant element in the carrier accounts for 0.05-6% by weight of the total weight of the matrix, preferably 0.08-4% by weight;

[0284] and / or, the doping element in the carrier is selected from metallic and non-metallic elements, excluding sodium and chlorine; the metallic element is selected from at least one of Group IA, Group IIA, Group VA and lanthanide elements, preferably at least one of calcium, magnesium, potassium, bismuth, strontium, barium ions and lanthanum; the non-metallic element is from at least one of non-metallic acid anions, preferably from at least one of borate ions, fluoride ions, phosphate ions, sulfate ions and selenate ions;

[0285] and / or, the ammonia adsorption capacity of the carrier is 0.3-0.6 mmol / g, and the carbon dioxide adsorption capacity is 0.05-0.3 mmol / g;

[0286] and / or, the percentage of pore volume in the carrier with a pore size in the range of 7-27 nm is 70-90% of the total pore volume of the carrier, and the percentage of pore volume with a pore size less than 7 nm is 0-10% of the total pore volume of the carrier;

[0287] and / or, the specific surface area of ​​the carrier is 120-205 m2 / g;

[0288] and / or, the pore volume of the carrier is 0.45-1.2 ml / g;

[0289] and / or, the content of the metal active component is 14-46 g relative to every 100 g of matrix;

[0290] and / or, the content of the metal additive is 0.1-10 g relative to every 100 g of matrix;

[0291] and / or, the weight ratio of Group VIIB metals to Group IIB metals in the metal additive is 0.2-20:1, preferably 0.3-6:1;

[0292] and / or, the Group VIIB metal is selected from manganese and / or rhenium;

[0293] and / or, the Group IIB metal is selected from zinc.

[0294] C4. The catalyst according to any one of C1 to C3, wherein the support is prepared by a method comprising the following steps: sequentially shaping, drying and calcining a mixture containing a dopant element, an alumina precursor and optionally other support precursors, wherein the other support precursors are selected from at least one of silica precursors, molecular sieve precursors and diatomaceous earth precursors.

[0295] C5. The catalyst according to Project C4, wherein the dopant element is provided by a carrier modifier selected from at least one of boric acid, nickel borate, cobalt borate, potassium borate, hydrofluoric acid, potassium fluoride, cobalt fluoride, nickel fluoride, phosphoric acid, aluminum phosphate, potassium phosphate, potassium dihydrogen phosphate, potassium hydrogen phosphate, magnesium phosphate, calcium phosphate, sulfuric acid, cobalt sulfate, nickel sulfate, aluminum sulfate, calcium sulfate, bismuth nitrate, potassium nitrate, potassium sulfate, potassium carbonate, magnesium nitrate, magnesium sulfate, basic magnesium carbonate, calcium nitrate, basic calcium carbonate, strontium nitrate, strontium phosphate, strontium sulfate, barium nitrate, lanthanum nitrate, and selenic acid.

[0296] C6. The catalyst according to project C4 or C5, wherein the alumina precursor is boehmite, the specific surface area of ​​the boehmite is 265-410 m2 / g, and the pore volume is 0.7-1.2 ml / g.

[0297] C7. The catalyst according to any one of C4 to C6, wherein the drying conditions include: a temperature of 80-150°C and a time of 6-20 h;

[0298] and / or, the calcination conditions include: a temperature of 500-1100℃ and a time of 2-20 h.

[0299] C8. A method for preparing the catalyst according to any one of items C1 to C7, the method comprising: loading a metal active component and a metal promoter onto a support.

[0300] C9, The carrier defined by any one of items C2 to C7 in the project.

[0301] The application of the catalyst described in any one of items C1 to C7, the method described in item C8, or the support described in item C9 in the amination to produce organic amines.

[0302] C11. A method for preparing organic amines, characterized in that the method comprises: in the presence of hydrogen, contacting the amination raw material, the amination reagent, and the catalyst described in any one of items C1 to C7 to carry out an amination reaction;

[0303] Alternatively, the method includes: screening a catalyst with a support defined by any one of items C1 to C7, and contacting the amination feedstock, the amination reagent, and the screened catalyst in the presence of hydrogen to carry out an amination reaction.

[0304] C11. According to the method described in Project C11, the conditions for the amination reaction include: the molar ratio of hydrogen, amination reagent and amination raw material is 1-5 : 2-30 : 1, the temperature is 110-220℃, the pressure is 0.8-25 MPa, and the liquid hourly space velocity of the amination raw material is 0.06-1 m3 / (m3·h);

[0305] and / or, the amination raw material is selected from at least one of C2-20 alcohols, C3-20 ketones, C2-20 alkanolamines, and C2-20 aldehydes, preferably ethanol, acetaldehyde, n-propanol, propionaldehyde, isopropanol, n-butanol, butyraldehyde, isobutanol, isobutyraldehyde, 2-ethylhexanol, 2-ethylhexanaldehyde, octanol, octanaldehyde, dodecanool, dodecaldehyde, hexadecanool, hexadecaldehyde, cyclopentanol, cyclohexanol, cyclooctanol, cyclododecanool At least one of the following: alkanols, benzyl alcohol, benzaldehyde, phenethyl alcohol, phenylacetaldehyde, 1,4-butanediol, 1,4-butanedialdehyde, 1,5-pentanediol, 1,5-pentanedialdehyde, 1,6-hexanediol, 1,6-hexanedialdehyde, 1,8-octanediol, 1,8-octanedialdehyde, ethanolamine, propanolamine, isopropanolamine, 6-aminohexanol, diethanolamine, dimethylethanolamine, acetone, ethylene glycol, 1,3-propanediol, and 1,12-dodecanediol;

[0306] and / or, the amination agent is selected from at least one of ammonia, a C1-12 primary amine and a C1-12 secondary amine, preferably at least one of ammonia, monomethylamine, dimethylamine, methylethylamine, monoethylamine and diethylamine.

[0307] C13. According to the method described in Project C12, when the amination raw material is a monohydric alcohol, the conditions for the amination reaction include: the molar ratio of hydrogen, amination reagent and amination raw material is 1-4 : 2-9 : 1, the temperature is 130-200℃, the pressure is 1-2.5 MPa, and the liquid hourly space velocity of the amination raw material is 0.1-0.8 m3 / (m3·h);

[0308] Or, when the amination raw material is a ketone or aldehyde, the conditions for the amination reaction include: a molar ratio of hydrogen, amination reagent and amination raw material of 1-4 : 2-6 : 1, a temperature of 110-180℃, a pressure of 0.8-2.5 MPa, and a liquid hourly space velocity of the amination raw material of 0.1-0.8 m3 / (m3·h);

[0309] Or, when the amination raw material is an alcoholamine, the conditions for the amination reaction include: the molar ratio of hydrogen, amination reagent and amination raw material is 1-4 : 3-20 : 1, the temperature is 130-200℃, the pressure is 1-15 MPa, and the liquid hourly space velocity of the amination raw material is 0.06-0.8 m3 / (m3·h);

[0310] Alternatively, when the amination feedstock is a mixture or diol of 1,6-hexanediol, cycloheximine and 6-amino-1-hexanol, the conditions for the amination reaction include: a molar ratio of hydrogen, amination reagent and amination feedstock of 1-4 : 3-30 : 1, a temperature of 130-220℃, a pressure of 1-25 MPa, and a liquid hourly space velocity of the amination feedstock of 0.1-0.8 m3 / (m3·h).

[0311] D1. A catalyst with catalytic alcohol amination function, the catalyst comprising a support and an active metal component and a metal promoter supported on the support, characterized in that the active metal component is cobalt and / or nickel; the metal promoter is a combination of at least one group VIB metal, at least one group IB metal and at least one group IIB metal.

[0312] D2. The catalyst according to Project D1, wherein the support includes an alumina support, a dopant element and other supports, wherein the other supports are selected from silicon oxide and / or molecular sieves; the ammonia adsorption capacity of the support is 0.25-0.6 mmol / g; and the percentage of the pore volume of the support with a pore size in the range of 7-27 nm to the pore volume of the support is greater than 65%.

[0313] D3. The catalyst according to Project D1 or D2, wherein the content of alumina support in the carrier accounts for more than 70% by weight of the total amount of alumina support and other supports, preferably 80-97% by weight;

[0314] and / or, the content of the dopant element is 0.05-5% by weight of the carrier, preferably 0.08-3% by weight;

[0315] and / or, the doping element in the carrier is a non-metallic element, preferably doped in the manner of at least one of borate ions, fluoride ions, phosphate ions, sulfate ions and selenate ions.

[0316] and / or, the ammonia adsorption capacity of the carrier is 0.3-0.6 mmol / g;

[0317] and / or, the percentage of pore volume in the carrier with a pore size in the range of 7-27 nm is 70-90% of the total pore volume of the carrier, and the percentage of pore volume with a pore size less than 7 nm is 0-8% of the total pore volume of the carrier;

[0318] and / or, the specific surface area of ​​the carrier is 120-210 m2 / g;

[0319] and / or, the pore volume of the carrier is 0.45-1.1 ml / g;

[0320] and / or, relative to every 100 g of carrier, the content of the active metal component is 10-46 g, preferably 18-38 g;

[0321] and / or, relative to every 100 grams of carrier, the content of the metal additive is 0.1-10 g, preferably 0.5-6 g;

[0322] and / or, the weight ratio of Group VIB metals, Group IB metals and Group IIB metals in the metal additive is 0.1-10:0.1-10:1, preferably 0.2-8:0.2-8:1;

[0323] and / or, the group VIB metal is selected from molybdenum and / or tungsten;

[0324] and / or, the Group IB metal is selected from at least one of copper, silver and gold;

[0325] and / or, the Group IIB metal is selected from zinc.

[0326] D4. The catalyst according to any one of D1 to D3, wherein the support is prepared by a method comprising the following steps: sequentially shaping, drying and calcining a mixture containing an alumina precursor, a dopant element and other support precursors, wherein the other support precursors are selected from silicon oxide precursors and / or molecular sieve precursors.

[0327] D5. The catalyst according to Project D4, wherein the dopant element is provided by at least one of boric acid, hydrofluoric acid, phosphoric acid, sulfuric acid and selenic acid.

[0328] D6. The catalyst according to Project D4 or D5, wherein the alumina precursor is boehmite, and the specific surface area of ​​the boehmite is 260-400 m2 / g, and the pore volume is 0.8-1.2 ml / g.

[0329] D7. The catalyst according to any one of D4 to D6 of the project, wherein the drying conditions include: a temperature of 80-150°C and a time of 6-20 h;

[0330] and / or, the calcination conditions include: a temperature of 500-1100℃ and a time of 2-20 h.

[0331] D8. A method for preparing the catalyst described in any one of items D1 to D7, the method comprising: loading an active metal component and a metal promoter onto a support.

[0332] D9, the carrier defined by any one of items D2 to D7.

[0333] The application of the catalyst described in any one of items D1 to D7, the method described in item D8, or the support described in item D9 in the amination to produce organic amines.

[0334] D11. A method for preparing organic amines, characterized in that the method comprises: in the presence of hydrogen, contacting the amination raw material, the amination reagent, and the catalyst described in any one of items D1 to D7 to carry out an amination reaction.

[0335] D12. According to the method described in Project D11, the conditions for the amination reaction include: the molar ratio of hydrogen, amination reagent and amination raw material is 1-5 : 2-35 : 1, the temperature is 105-220℃, the pressure is 0.7-25 MPa, and the liquid hourly space velocity of the amination raw material is 0.06-1 m3 / (m3·h);

[0336] and / or, the amination raw material is selected from at least one of C2-20 alcohols, C3-20 ketones, C2-20 alkanolamines, and C2-20 aldehydes, preferably ethanol, acetaldehyde, n-propanol, propionaldehyde, isopropanol, n-butanol, butyraldehyde, isobutanol, isobutyraldehyde, 2-ethylhexanol, 2-ethylhexanaldehyde, octanol, octanaldehyde, dodecanool, dodecanoaldehyde, hexadecanool, hexadecanoaldehyde, cyclopentanol, cyclohexanol, cyclooctanol, cyclododecanoaldehyde. At least one of the following: alkanols, benzyl alcohol, benzaldehyde, phenethyl alcohol, phenylacetaldehyde, 1,4-butanediol, 1,4-butanedialdehyde, 1,5-pentanediol, 1,5-pentanedialdehyde, 1,6-hexanediol, 1,6-hexanedialdehyde, 1,8-octanediol, 1,8-octanedialdehyde, ethanolamine, propanolamine, isopropanolamine, 6-aminohexanol, diethanolamine, dimethylethanolamine, acetone, ethylene glycol, 1,3-propanediol, and 1,12-dodecanediol;

[0337] and / or, the amination agent is selected from at least one of ammonia, a C1-12 primary amine and a C1-12 secondary amine, preferably at least one of ammonia, monomethylamine, dimethylamine, methylethylamine, monoethylamine and diethylamine.

[0338] D13. According to the method described in Project D12, when the amination raw material is a monohydric alcohol, the conditions for the amination reaction include: the molar ratio of hydrogen, amination reagent and amination raw material is 1-4 : 2-8 : 1, the temperature is 130-200℃, the pressure is 1-2.5 MPa, and the liquid hourly space velocity of the amination raw material is 0.1-0.8 m3 / (m3·h);

[0339] Or, when the amination raw material is a ketone or aldehyde, the conditions for the amination reaction include: a molar ratio of hydrogen, amination reagent and amination raw material of 1-4 : 2-5 : 1, a temperature of 105-180℃, a pressure of 0.7-2.5 MPa, and a liquid hourly space velocity of the amination raw material of 0.1-0.8 m3 / (m3·h);

[0340] Or, when the amination raw material is an alcoholic amine, the conditions for the amination reaction include: the molar ratio of hydrogen, amination reagent and amination raw material is 1-4 : 3-25 : 1, the temperature is 130-200℃, the pressure is 5-18 MPa, and the liquid hourly space velocity of the amination raw material is 0.06-0.8 m3 / (m3·h);

[0341] Alternatively, when the amination feedstock is a mixture or diol of 1,6-hexanediol, cycloheximine and 6-amino-1-hexanol, the conditions for the amination reaction include: a molar ratio of hydrogen, amination reagent and amination feedstock of 1-4 : 3-35 : 1, a temperature of 130-220℃, a pressure of 2-25 MPa, and a liquid hourly space velocity of the amination feedstock of 0.1-0.8 m3 / (m3·h).

[0342] E1. A titanium-containing catalyst with amination function, the catalyst containing a support and an active metal component supported on the support and an optional metal additive, characterized in that the support comprises alumina and titanium dioxide in a weight ratio of 1.5-5:1, and the active metal component is cobalt and / or nickel.

[0343] E2. The titanium-containing catalyst according to Project E1, wherein the weight ratio of alumina to titanium dioxide is 2-4.5:1;

[0344] and / or, relative to every 100 grams of carrier, the content of the active metal component is 13-40 g, preferably 20-36 g;

[0345] and / or, relative to each 100 g of carrier, the content of the metal additive is 0-10 g, preferably 2.5-8 g;

[0346] and / or, the metal additive is selected from at least one of Group VIB, Group VIIB, Group IB, Group IIB and lanthanides, preferably at least one of Cr, Mo, W, Mn, Re, Cu, Ag, Au, Zn, La and Ce.

[0347] E4. The titanium-containing catalyst according to any one of E1 to E3, wherein the titanium-containing catalyst has an ammonia adsorption capacity of 0.3-0.4 mmol / g, a carbon dioxide adsorption capacity of 0.07-0.2 mmol / g, a specific surface area of ​​130-180 m2 / g, a pore volume of 0.55-0.75 ml / g, and the percentage of pore volume with a pore radius less than 4 nm to the total pore volume is less than 20%, and the percentage of pore volume with a pore radius greater than 10 nm to the total pore volume is less than 15%.

[0348] and / or, the carrier is doped with sulfur, and the sulfur content is 0.1-0.5 g, preferably 0.15-0.4 g, relative to 100 g of alumina and titanium dioxide.

[0349] E5. A method for preparing a titanium-containing catalyst with amination function, characterized in that the method comprises:

[0350] (1) The pseudoboehmite and titanium dioxide are mixed, shaped and calcined to obtain a carrier, wherein the amount of pseudoboehmite and titanium dioxide is such that the weight ratio of alumina and titanium dioxide in the obtained carrier is 2-5:1.

[0351] (2) Loading an active metal component and an optional metal additive onto the resulting carrier, wherein the active metal component includes cobalt and / or nickel.

[0352] E6. According to the method described in Project E4, the amount of the pseudoboehmite and the titanium dioxide is such that the weight ratio of the alumina and titanium dioxide in the resulting carrier is 2-4.5:1;

[0353] and / or, the pseudoboehmite is prepared by at least one of the carbonization method, organoaluminum hydrolysis method, aluminum sulfate method and nitric acid method, preferably by the carbonization method or aluminum sulfate method;

[0354] and / or, the titanium dioxide is prepared by precipitation method and / or sol-gel method, preferably titanium dioxide prepared by titanium oxysulfate as raw material.

[0355] E7. According to the method described in Project E5, the content of sulfate in the titanium dioxide is 0.2-3 wt%.

[0356] E8. The method according to any one of E4 to E6, wherein the amount of the active metal component is such that the content of the active metal component is 13-40 g, preferably 20-36 g, relative to 100 g of carrier.

[0357] and / or, the amount of the metal additive is such that the content of the metal additive is 0-10 g, preferably 2.5-8 g, relative to 100 g of carrier;

[0358] and / or, the metal additive is selected from at least one of Group VIB, Group VIIB, Group IB, Group IIB and lanthanides, preferably at least one of Cr, Mo, W, Mn, Re, Cu, Ag, Au, Zn, La and Ce.

[0359] E8. A titanium-containing catalyst prepared by the method described in any one of projects E4 to E7.

[0360] E9. Application of the titanium-containing catalyst described in any one of items E1 to E3 or E8, or the method described in any one of items E4 to E7, in the amination of alcohols.

[0361] E10. A method for preparing an organic amine, characterized in that the method comprises: contacting ammonia and / or an organic amine with an alcohol in the presence of a titanium-containing catalyst as described in any one of items E1 to E3 or E8 to carry out an amination reaction;

[0362] Alternatively, a titanium-containing catalyst may be prepared according to any one of the methods described in Projects E4 to E7, and then ammonia and / or organic amines may be contacted with alcohols in the presence of the obtained titanium-containing catalyst to carry out an amination reaction.

[0363] Example

[0364] The present application will be described in detail below through embodiments, but the present application is not limited thereto.

[0365] In the following examples and comparative examples, unless otherwise specified, all materials and reagents used are commercially available products with analytical purity.

[0366] The testing instruments and methods used in the following embodiments are as follows:

[0367] 1) NH3-TPD test

[0368] Testing instrument: Automated Catalyst Characterization System (Autochem 2920), a product of Micrometers, Inc., USA;

[0369] Test conditions: Accurately weigh approximately 0.1 g of sample and place it in a sample tube. Under He purging conditions, raise the temperature to 600℃ at 10℃ / min, hold for 1 h, lower the temperature to 120℃, then change the gas to a 10% NH3-He mixture, adsorb for 60 min, then change back to He purging for 1 h. After the baseline stabilizes, start counting, raise the temperature to 600℃ at 10℃ / min, hold for 30 min, stop recording, and complete the experiment. Integrate the peak area to calculate the NH3 desorption amount, and use this desorption amount to characterize the ammonia adsorption amount of the sample.

[0370] 2) CO2-TPD test

[0371] Testing instrument: Automated Catalyst Characterization System (Autochem 2920), a product of Microlithics, Inc., USA;

[0372] Test conditions: Accurately weigh approximately 0.1 g of sample and place it in a sample tube. Under He purging conditions, raise the temperature to 600℃ at 10℃ / min, hold for 1 h, lower the temperature to 120℃, then change the gas to a 10% CO2-He mixture, adsorb for 60 min, then change back to He purging for 1 h. After the baseline stabilizes, start counting, raise the temperature to 600℃ at 10℃ / min, hold for 30 min, stop recording, and complete the experiment. Integrate the peak area to calculate the CO2 desorption amount, and use this desorption amount to characterize the CO2 adsorption amount of the sample.

[0373] 3) BET Test

[0374] Testing instrument: Automatic Micropore & Chemisorption Analyzer; Instrument model: ASAP2420, MICROMERITICS, USA;

[0375] Test conditions: Experimental gas: N2 (purity 99.999%); Degassing conditions: temperature increased to 350℃ at 10℃ / min, vacuumed for 4 h; Analytical conditions: full analysis of mesoporous isotherms to obtain specific surface area and pore volume.

[0376] 4) XRD Analysis

[0377] Testing instrument: Panaco Empyrean X-ray diffractometer, Cu target anode, Pixcel 3D detector;

[0378] Test conditions: tube voltage 40KV, tube current 40 mA, divergence slit 1 / 4°, anti-scattering slit 1 / 2°, receiving slit height 7.5 mm, scanning speed 0.013° / step, scanning range 5°-90°.

[0379] The grain size of the active metal component and any possible metal additives was calculated using the Scherrer formula.

[0380] Example I Series

[0381] The first type of implementation of this application will be described in detail below through a series of Examples I. In the following Series I examples, the dry basis (Al2O3) content of the pseudoboehmite powder is 72% by weight.

[0382] Example I-1

[0383] Pseudoboehmite powder (specific surface area 298 m2 / g, pore volume 1.21 ml / g) was kneaded by adding calcium nitrate tetrahydrate (analytical grade), nitric acid and phosphoric acid dilute aqueous solution sequentially. After kneading, it was pressed into strips with a diameter of 5 mm, cut into 4 mm lengths, dried at 100℃ for 12 h, and then calcined at 720℃ for 8 h to prepare the required carrier. The amount of calcium nitrate tetrahydrate (analytical grade) used per 100 g of pseudoboehmite powder (calculated as Al2O3) was 2.95 g, the amount of nitric acid was 6.5 g, and the amount of phosphoric acid was 0.63 g.

[0384] 176.4 g of cobalt nitrate hexahydrate (industrial grade, purity 98%) was dissolved in water to make 182 ml of solution. The solution was loaded onto the obtained 100 g support in two separate spray impregnations. After each spray impregnation, the solution was dried at 120 °C for 8 hours, then calcined at 400 °C for 4 hours, and then gradually reduced with hydrogen at a rate of 20 °C / hour. Finally, the solution was reduced at 430 °C for 3 hours to obtain catalyst AI-1.

[0385] Example I-2

[0386] Pseudoboehmite powder (specific surface area 286 m2 / g, pore volume 0.88 ml / g) was kneaded by adding potassium nitrate (analytical grade) aqueous solution, nitric acid and boric acid dilute acid solution in sequence. After kneading, it was pressed into a clover shape with a diameter of 3 mm, dried at 120℃ for 8 h, and then calcined at 690℃ for 10 h to prepare the required carrier. The amount of potassium nitrate (analytical grade) was 0.26 g, the amount of nitric acid was 5.2 g, and the amount of boric acid was 4.57 g, relative to 100 g of pseudoboehmite powder calculated as Al2O3.

[0387] 151.7 g of nickel nitrate hexahydrate (industrial grade, purity 98%) was dissolved in water to make a solution of 168 ml. The solution was loaded onto the obtained 100 g support in two separate spray impregnations. After each spray impregnation, the solution was dried at 120 °C for 4 hours, then calcined at 390 °C for 4 hours, and then gradually reduced with hydrogen at a rate of 20 °C / hour. Finally, the solution was reduced at 440 °C for 3 hours to obtain catalyst Al-2.

[0388] Example I-3

[0389] Pseudoboehmite powder (specific surface area 310 m2 / g, pore volume 0.92 ml / g) was kneaded by adding magnesium nitrate hexahydrate (analytical grade) aqueous solution, nitric acid and sulfuric acid dilute acid water, and then pressed into toothed spheres with a diameter of 4 mm. The mixture was dried at 100℃ for 15 h and then calcined at 780℃ for 10 h to prepare the required carrier. The amount of magnesium nitrate hexahydrate (analytical grade) was 0.84 g, the amount of nitric acid was 6.1 g, and the amount of sulfuric acid was 1.22 g, relative to 100 g of pseudoboehmite powder based on Al2O3.

[0390] 50.4 g of cobalt nitrate hexahydrate (industrial grade, 98% purity) and 32.6 g of 50wt% manganese nitrate aqueous solution were dissolved in water to make 156 ml solution. The solution was loaded onto the obtained 100 g support by spray impregnation in two batches. After each spray impregnation, the solution was dried at 120 °C for 4 hours, then calcined at 400 °C for 4 hours, and then gradually reduced with hydrogen at a rate of 20 °C / hour. Finally, the solution was reduced at 430 °C for 3 hours to obtain catalyst AI-3.

[0391] Example I-4

[0392] Pseudoboehmite powder (specific surface area 321 m2 / g, pore volume 0.93 ml / g) was kneaded by adding bismuth pentahydrate (analytical grade) aqueous solution, nitric acid and phosphoric acid dilute acid water, etc. into strips with a diameter of 5 mm, cut into 4 mm lengths, dried at 80℃ for 20 h, and then calcined at 660℃ for 15 h to prepare the required carrier. The amount of bismuth pentahydrate (analytical grade) was 1.86 g, the amount of nitric acid was 6.5 g, and the amount of phosphoric acid was 1.9 g, relative to 100 g of pseudoboehmite powder based on Al2O3.

[0393] 75.6 g of cobalt nitrate hexahydrate (industrial grade, 98% purity) and 50.6 g of nickel nitrate hexahydrate (industrial grade, 98% purity) were dissolved in water to make a 166 ml solution. The solution was loaded onto the obtained 100 g support in two separate spray impregnations. After each spray impregnation, the solution was dried at 120 °C for 4 hours, then calcined at 400 °C for 4 hours, and then gradually reduced with hydrogen at a rate of 20 °C / hour. Finally, the solution was reduced at 430 °C for 3 hours to obtain catalyst Al-4.

[0394] Example I-5

[0395] Pseudoboehmite powder (specific surface area 275 m2 / g, pore volume 0.85 ml / g) was kneaded by adding barium nitrate (analytical grade) aqueous solution, nitric acid and boric acid dilute acid solution in sequence. After kneading, it was pressed into a clover shape with a diameter of 3 mm, dried at 150℃ for 6 h, and then calcined at 810℃ for 5 h to prepare the required carrier. The amount of barium nitrate (analytical grade) was 0.19 g, the amount of nitric acid was 6.5 g and the amount of boric acid was 2.29 g per 100 g of pseudoboehmite powder based on Al2O3.

[0396] 126.4 g of nickel nitrate hexahydrate (industrial grade, 98% purity) and 2.9 g of ammonium perrhenate (99% purity) were dissolved in water to make a 160 ml solution. The solution was loaded onto the obtained 100 g support by spray impregnation in two batches. After each spray impregnation, the support was dried at 120 °C for 4 hours, then calcined at 390 °C for 4 hours, and then gradually reduced with hydrogen at a rate of 20 °C / hour. Finally, the support was reduced at 440 °C for 3 hours to obtain catalyst Al-5.

[0397] Example I-6

[0398] Pseudoboehmite powder (specific surface area 269 m2 / g, pore volume 0.86 ml / g) was kneaded by adding cesium nitrate (analytical grade) aqueous solution, nitric acid and sulfuric acid dilute acid water in sequence. After kneading, it was pressed into toothed spheres with a diameter of 4 mm, dried at 120℃ for 8 h, and then calcined at 830℃ for 4 h to prepare the required carrier. The amount of cesium nitrate was 0.03 g, the amount of nitric acid was 6.2 g, and the amount of sulfuric acid was 0.09 g per 100 g of pseudoboehmite powder (calculated as Al2O3).

[0399] 201.6 g of cobalt nitrate hexahydrate (industrial grade, 98% purity) was dissolved in water to make 156 ml of solution; 7.4 g of ammonium molybdate tetrahydrate (analytical grade) was dissolved in water to make 78 ml of solution; the cobalt nitrate solution was loaded onto the obtained 100 g support in two separate spray impregnations; the ammonium molybdate solution was then loaded onto the support in one more spray impregnation. After spray impregnation, the solution was dried at 120 °C for 4 hours, then calcined at 400 °C for 4 hours, and then gradually reduced with hydrogen at a rate of 20 °C / hour. Finally, the solution was reduced at 430 °C for 3 hours to obtain catalyst AI-6.

[0400] Example I-7

[0401] Pseudoboehmite powder (specific surface area 259 m2 / g, pore volume 0.88 ml / g) was kneaded by adding lanthanum nitrate hexahydrate (analytical grade) aqueous solution, nitric acid and sulfuric acid in dilute acid water. After kneading, it was pressed into toothed spheres with a diameter of 4 mm, dried at 100℃ for 10 h, and then calcined at 980℃ for 5 h to prepare the required carrier. The amount of lanthanum nitrate hexahydrate (analytical grade) used was 0.47 g, the amount of nitric acid used was 5 g, and the amount of sulfuric acid used was 0.61 g, relative to 100 g of pseudoboehmite powder based on Al2O3.

[0402] 100.8 g of cobalt nitrate hexahydrate (industrial grade, purity 98) and 14.1 g of copper nitrate trihydrate (analytical grade) were dissolved in water to make a solution of 176 ml. The solution was loaded onto the obtained 100 g support in two separate spray impregnations. After each spray impregnation, the support was dried at 120 °C for 4 hours, then calcined at 400 °C for 4 hours, and then gradually reduced with hydrogen at a rate of 20 °C / hour. Finally, the support was reduced at 430 °C for 3 hours to obtain catalyst AI-7.

[0403] Example I-8

[0404] Pseudoboehmite powder (specific surface area 291 m2 / g, pore volume 0.93 ml / g) was kneaded by adding lanthanum nitrate hexahydrate (analytical grade) aqueous solution, nitric acid and hydrofluoric acid dilute acid solution to the powder in sequence during the kneading process, kneaded and pressed into toothed spheres with a diameter of 4 mm, dried at 90℃ for 12 h, and then calcined at 900℃ for 3 h to prepare the required carrier. The amount of lanthanum nitrate hexahydrate (analytical grade) used was 0.62 g, the amount of nitric acid used was 5.5 g, and the amount of hydrofluoric acid used was 0.05 g, relative to 100 g of pseudoboehmite powder based on Al2O3.

[0405] 126 g of cobalt nitrate hexahydrate (industrial grade, 98% purity) and 25.3 g of nickel nitrate hexahydrate (industrial grade, 98% purity) were dissolved in water to make a solution of 177 ml. The solution was loaded onto the obtained 100 g support by spray impregnation in three batches. After each spray impregnation, the solution was dried at 120 °C for 4 hours, then calcined at 400 °C for 4 hours, and then gradually reduced with hydrogen at a rate of 20 °C / hour. Finally, the solution was reduced at 430 °C for 3 hours to obtain catalyst AI-8.

[0406] Example I-9

[0407] Pseudoboehmite powder (specific surface area 312 m2 / g, pore volume 1.02 ml / g) was kneaded by adding calcium nitrate tetrahydrate (analytical grade) aqueous solution, nitric acid and hydrofluoric acid dilute acid solution sequentially. After kneading, it was pressed into a clover shape with a diameter of 4 mm, dried at 100℃ for 8 h, and then calcined at 930℃ for 3 h to prepare the required carrier. The amount of calcium nitrate tetrahydrate (analytical grade) used was 3.54 g, the amount of nitric acid used was 6.5 g, and the amount of hydrofluoric acid used was 0.13 g, relative to 100 g of pseudoboehmite powder based on Al2O3.

[0408] 176.4 g of cobalt nitrate hexahydrate (industrial grade, 98% purity) and 1.3 g of silver nitrate (analytical grade) were dissolved in water to make a solution of 188 ml. The solution was loaded onto the obtained 100 g support in three separate spray impregnations. After each spray impregnation, the solution was dried at 120 °C for 4 hours, then calcined at 390 °C for 4 hours, and then gradually reduced with hydrogen at a rate of 20 °C / hour. Finally, the solution was reduced at 440 °C for 3 hours to obtain catalyst AI-9.

[0409] Example I-10

[0410] Silicone powder (specific surface area 385 m2 / g, pore volume 0.95 ml / g) was used as raw material. Dilute acid water containing magnesium nitrate, nitric acid and sulfuric acid was used to roll the powder into 4 mm toothed spheres. The spheres were dried at 80°C for 15 h and then calcined at 750°C for 8 h to prepare the required carrier. The amount of magnesium nitrate hexahydrate (analytical grade) was 8.44 g, the amount of nitric acid was 6.1 g and the amount of sulfuric acid was 4.28 g, relative to 100 g of silica powder (calculated as SiO2).

[0411] The remaining steps are the same as in Example 3, and catalyst AI-10 is obtained.

[0412] Example I-11

[0413] Pseudoboehmite powder (specific surface area 261 m2 / g, pore volume 0.83 ml / g) was kneaded by adding potassium nitrate (analytical grade) aqueous solution, nitric acid and phosphoric acid dilute acid water in sequence, kneaded and pressed into 4 mm toothed spheres, dried at 100℃ for 10 h, and then calcined at 1030℃ for 5 h to prepare the required carrier. Among them, the amount of potassium nitrate (analytical grade) was 1.29 g, the amount of nitric acid was 6.3 g and the amount of phosphoric acid was 4.9 g per 100 g of pseudoboehmite powder based on Al2O3.

[0414] The remaining steps are the same as in Example 3, and catalyst AI-11 is obtained.

[0415] Example I-12

[0416] ZSM-5 powder (specific surface area 354 m2 / g, pore volume 0.57 ml / g, crystallinity 97.5%, SiO2 / Al2O3=61) was kneaded. During the kneading process, calcium nitrate tetrahydrate (analytical grade) aqueous solution, nitric acid and phosphoric acid dilute acid water were added successively. The mixture was pressed into 3.0 mm toothed spheres, dried at 120℃ for 10 h, and then calcined at 920℃ for 5 h to prepare the required carrier. The amount of calcium nitrate tetrahydrate (analytical grade) used per 100 g of ZSM-5 powder was 1.56 g, the amount of nitric acid was 8.2 g, and the amount of phosphoric acid was 2.9 g.

[0417] The remaining steps are the same as in Example 7, and catalyst AI-12 is prepared.

[0418] Example I-13

[0419] Carrier preparation is the same as in Examples I-7

[0420] 2.56 g palladium chloride (purity 99.5%) and 38.2 g copper nitrate trihydrate (analytical grade) were dissolved in water to make a solution of 171 ml. The solution was loaded onto the obtained 100 g support in two separate spray impregnations. After each spray impregnation, the solution was dried at 120 °C for 4 hours, then calcined at 400 °C for 4 hours, and then gradually reduced with hydrogen at a rate of 20 °C / hour. Finally, the solution was reduced at 230 °C for 3 hours to obtain catalyst AI-13.

[0421] Comparative Example I-1

[0422] The catalyst was prepared according to the method of Example 5, except that the amount of boric acid used was 3.43 g, the amount of barium nitrate (analytical grade) was 4.76 g, and the amount of nitric acid was 6.5 g, relative to 100 g of pseudoboehmite powder based on Al2O3. The prepared catalyst was named DI-1.

[0423] Comparative Example I-2

[0424] The catalyst was prepared according to the method of Example 3, except that only dilute acid water containing nitric acid was added during the kneading process, wherein the amount of nitric acid used was 6.1 g relative to 100 g of pseudoboehmite powder based on Al2O3. The prepared catalyst was named DI-2.

[0425] Comparative Example I-3

[0426] The catalyst was prepared according to the method of Example 3, except that dilute acid water containing nitric acid and phosphoric acid was added during the kneading process. The amount of phosphoric acid used was 15.82 g and the amount of nitric acid used was 6.2 g per 100 g of pseudoboehmite powder based on Al2O3. The prepared catalyst was named DI-3.

[0427] Test Case I-1

[0428] The elemental composition of the support and catalyst was analyzed by plasma emission spectrometry. The content of elements (ions) other than the support was expressed as the weight of 100 g of matrix (i.e., the support based on non-hetero-element components (e.g., Al2O3 when boehmite is the support source)). The supports prepared above were characterized by NH3-TPD, CO2-TPD and BET nitrogen adsorption-desorption methods. The results are shown in Table I-1.

[0429] Table I-1 Properties of the carriers in each embodiment and comparative example Example number Doping elements Active metal components and metal additives Ammonia adsorption capacity, mmol / g CO2 adsorption capacity, mmol / g Specific surface area, m 2 / g Pore ​​volume, ml / g type Relative content, g type Relative content, g Active metal components Content, g Metal additives Content, g Example I-1 Ca 0.5 P 0.2 Co 35 — — 0.35 0.15 215 0.91 Example I-2 K 0.1 B 0.8 Ni 30 — — 0.35 0.13 208 0.84 Example I-3 Mg 0.08 S 0.4 Co 10 Mn 5 0.4 0.13 196 0.78 Example I-4 Bi 0.8 P 0.6 Co+Ni 15+10 — — 0.35 0.12 220 0.83 Example I-5 Ba 0.1 B 0.4 Ni 25 Re 2 0.35 0.13 200 0.8 Example I-6 Cs 0.02 S 0.03 Co 40 Mo 4 0.31 0.13 185 0.78 Example I-7 La 0.15 S 0.2 Co 20 Cu 5 0.43 0.11 138 0.64 Example I-8 La 0.2 F 0.05 Co+Ni 25+5 — — 0.33 0.17 173 0.59 Example I-9 Ca 0.6 F 0.12 Co 35 Ag 0.8 0.27 0.23 188 0.62 Example I-10 Mg 0.8 S 1.4 Co 10 Mn 5 0.46 0.26 192 0.72 Example I-11 K 0.5 P 1.55 Co 10 Mn 5 0.52 0.23 135 0.74 Example I-12 Ca 0.2 P 0.7 Co 20 Cu 5 0.59 0.16 249 0.51 Example I-13 La 0.15 S 0.2 Pd 1.37 Cu 9 0.41 0.15 142 0.62 Comparative Example I-1 Ba 2.5 B 0.6 Ni 25 Re 2 0.22 0.38 203 0.81 Comparative Example I-2 - 0 - 0 Co 10 Mn 5 0.16 0.12 198 0.78 Comparative Example I-3 - 0 P 5 Co 10 Mn 5 0.72 0.07 195 0.77

[0430] Test Case I-2

[0431] This test example is used to illustrate the method for preparing 1,6-hexanediamine by hydroamylation of 1,6-hexanediol using the catalyst of the Type I embodiment of this application.

[0432] 100 mL of the catalyst prepared in the example was measured and placed in a fixed-bed reactor. It was activated with hydrogen at 220°C for 2 hours, then cooled to 165°C. The system pressure was increased to 8.8 MPa with hydrogen. Ammonia was then metered and fed into the reaction system using a metering pump. After being preheated to 100°C, it entered the upper part of the reactor. 1,6-hexanediol, heated and melted, was fed into the upper part of the reactor using a metering pump. Hydrogen was stably fed in through a gas mass flow meter. The molar ratio of hydrogen:ammonia:1,6-hexanediol was 3:14:1, and the liquid hourly space velocity of 1,6-hexanediol was 0.42 h⁻¹. Catalytic amination reaction was carried out in the reactor at a reaction temperature of 185°C and a reaction pressure of 8.8 MPa. After the reaction stabilized (i.e., after 360 h), the reaction solution was sampled and analyzed. The analysis results are listed in Table I-2.

[0433] The sampling and analysis method is gas chromatography, and calibration is performed by using the correction factor of the prepared standard sample;

[0434] The conversion rate and selectivity are calculated based on the mole content of each component in the reaction solution.

[0435] To calculate the selectivity of cyclohexylimine, replace the molecule in the hexamethylenediamine selectivity formula with the molar content of cyclohexylimine. To calculate the selectivity of aminohexanol, replace the molecule in the hexamethylenediamine selectivity formula with the molar content of aminohexanol. And so on. To calculate the selectivity of the “other” components, replace the molecule in the hexamethylenediamine selectivity formula with the molar content of amine dimer × 2. Amine dimer refers to the dimer of 1,6-hexamethylenediamine (bis(hexamethylenediamine), also known as N-(6-aminohexyl)-1,6-hexamethylenediamine) and the dimer of 1,6-hexamethylenediamine and cyclohexylimine (N-(6-aminohexyl)cyclohexylimine).

[0436] Table I-2 Test results of catalysts in each example and control example catalyst Catalyst composition Conversion rate, % Selectivity, % Hexamethylenediamine Cycloheximine aminohexanol other AI-1 Co / Al2O3 88 48.8 20.6 26.7 3.9 AI-2 Ni / Al2O3 90 48.3 19.5 28.4 3.8 AI-3 Co-Mn / Al2O3 92 51 19.2 26.5 3.3 AI-4 Co-Ni / Al2O3 87 47.5 21.0 27.4 4.1 AI-5 Ni-Re / Al2O3 91 50.1 20.9 25.9 3.1 AI-6 Co-Mo / Al2O3 86 48.7 17.6 30.2 3.5 AI-7 Co-Cu / Al2O3 90 49.3 20.3 27.2 3.2 AI-8 Co-Ni / Al2O3 91 48.8 20.2 27.3 3.7 AI-9 Co-Ag / Al2O3 82 46.8 19.6 30.3 3.3 AI-10 Co-Mn / SiO2 78 45.5 20.1 29.6 4.8 AI-11 Co-Mn / Al2O3 79 44.9 22.3 28.3 4.5 AI-12 Co-Cu / ZSM-5 93 50.7 23.1 22.4 3.8 AI-13 Pd-Cu / Al2O3 90 50.1 21.9 25.0 3.0 DI-1 Ni-Re / Al2O3 64 32.9 22.6 34.3 10.2 DI-2 Co-Mn / Al2O3 56 33.1 23.7 35.8 7.4 DI-3 Co-Mn / Al2O3 62 36.7 27.9 25.6 9.8

[0437] As can be seen from the data in Table I-2, the conversion rate of the catalyst in this application is higher than that of the control catalyst, and the activity is higher, indicating that the catalyst in this application has a faster reaction rate.

[0438] The above catalysts were tested for 360 hours and then removed for characterization. It was found that the specific surface area and pore volume of the catalysts DI-1, DI-2 and DI-3 prepared in the control example were significantly reduced, and the carbon deposition was 11 wt%, 9.1 wt% and 8.9 wt% respectively. However, the specific surface area and pore volume of the catalysts prepared in the present application embodiment did not change significantly, and the carbon deposition was less than 2 wt%.

[0439] Furthermore, when catalysts AI-1 to AI-11 catalyzed the reaction for 1000 h, analysis of the reaction solution revealed no significant changes in conversion rate and selectivity compared to 360 h, i.e., the decrease in conversion rate was no more than 2% and the decrease in selectivity was no more than 1%. However, when DI-1 to DI-3 catalyzed the reaction for 1000 h, both conversion rate and selectivity decreased significantly compared to 360 h, with conversion rates decreasing to 31%, 28%, and 35%, respectively. The selectivity of hexamethylenediamine decreased to 25%, 23%, and 26%, respectively.

[0440] Test Case I-3

[0441] This test example is used to illustrate the method for preparing ethylamine from ethanol by hydroamylation using the catalyst of the Type I embodiment of this application.

[0442] 100 mL of the catalyst AI-3 prepared in Example I-3 was measured and placed in a fixed-bed reactor. It was activated with hydrogen at 220°C for 2 hours, then cooled to 160°C. The system pressure was increased to 1.75 MPa with hydrogen. Ammonia was then metered and fed into the reaction system using a metering pump. After preheating to 110°C, it entered the upper part of the reactor. Ethanol was also metered and fed into the upper part of the reactor. Hydrogen was steadily fed in using a gas mass flow meter. The molar ratio of hydrogen:ammonia:ethanol was 2:5:1, and the liquid hourly space velocity of ethanol was 0.5 h-1. Catalytic amination reaction was carried out in the reactor at a reaction temperature of 175°C and a reaction pressure of 1.75 MPa. After the reaction stabilized, the reaction solution was sampled and analyzed (the analysis conditions and conversion and selectivity calculation methods were similar to those in Test Example I-2). The analysis results are shown in Table I-3.

[0443] Table I-3 Results of Test Case I-3 Ethanol conversion rate (%) Selectivity (%) Monoethylamine Diethylamine Triethylamine 360 h 98.95 27.4 47.3 24.8 1000 h 98.91 27.3 47.4 24.8

[0444] Test Case I-4

[0445] This test example is used to illustrate the method for preparing ethylenediamine from ethanolamine by hydroammoniation using the catalyst of the Type I embodiment of this application.

[0446] 100 mL of the catalyst AI-3 prepared in Example I-3 was measured and placed in a fixed-bed reactor. It was activated with hydrogen at 220°C for 2 hours, then cooled to 180°C. The system pressure was increased to 9.6 MPa with hydrogen. Ammonia was then metered and fed into the reaction system using a metering pump. After being preheated to 100°C, it entered the upper part of the reactor. Ethanolamine was fed into the upper part of the reactor using a metering pump. Hydrogen was stably fed in through a gas mass flow meter. The molar ratio of hydrogen:ammonia:ethanolamine was 3:12:1, and the liquid hourly space velocity of ethanolamine was 0.5 h-1. Catalytic amination reaction was carried out in the reactor at a reaction temperature of 180°C and a reaction pressure of 9.6 MPa. After the reaction stabilized, the reaction liquid was sampled and analyzed (the analysis conditions and conversion and selectivity calculation methods were similar to those in Test Example I-2). The analysis results are shown in Table I-4.

[0447] Table I-4 Results of Test Case I-4 Ethanolamine conversion rate (%) Selectivity (%) ethylenediamine Piper Diethylenetriamine Hydroxyethyl ethylenediamine N-aminoethylpiperazine N-hydroxyethylpiperazine 360 h 90.0 57.6 25.3 7.68 8.31 0.50 0.40 1000 h 90.2 57.7 25.2 7.55 8.32 0.56 0.47

[0448] Test Case I-5

[0449] This test example is used to illustrate the method for preparing hexanediamine from a mixture of 1,6-hexanediol, cycloheximine and aminohexanol using the catalyst of the Type I embodiment of this application.

[0450] 100 mL of the catalyst AI-3 prepared in Example I-3 was measured and placed in a fixed-bed reactor. It was activated with hydrogen at 220°C for 2 hours, then cooled to 170°C. The system pressure was increased to 8.2 MPa with hydrogen. Ammonia was then metered and fed into the reaction system using a metering pump. After preheating to 110°C, the ammonia entered the upper part of the reactor. A mixed solution of 53 wt% 1,6-hexanediol, 30 wt% cycloheximine, and 17 wt% 6-amino-1-hexanol was 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 the sum of the three substances in the mixed solution was 4:15:1. The liquid hourly space velocity (LHSV) of the mixed solution was 0.5 h⁻¹. The catalytic amination reaction was carried out in the reactor at a reaction temperature of 190°C and a reaction pressure of 8.2 MPa. After the reaction stabilized at MPa, the reaction solution was sampled and analyzed (the analysis conditions and conversion and selectivity calculation methods were similar to those in test example I-2). The analysis results are shown in Table I-5.

[0451] Table I-5 Results of Test Case I-5 Hexanediol conversion rate (%) Selectivity (%) Hexamethylenediamine Cycloheximine aminohexanol 360 h 98.0 98.4 0.8 0.2 1000 h 98.1 98.5 0.7 0.2

[0452] Example II Series

[0453] The second type of embodiments of this application will be described in detail below through a series of examples II. In the following examples of the second series, the pseudoboehmite powder is produced by the aluminum sulfate method, and its dry basis (Al2O3) content is 72% by weight; the silica sol is purchased from Qingdao Ocean Chemical Co., Ltd., model JN-40.

[0454] Example II-1

[0455] The pseudoboehmite powder (specific surface area 346 m2 / g, pore volume 1.13 ml / g, phosphorus content 0.22 g relative to 100 g of Al2O3 powder) was kneaded with dilute acid water containing 15 vol% nitric acid, pressed into strips with a diameter of 5 mm, dried at 120 °C for 12 h, and then calcined at 800 °C for 5 h to prepare a carrier. The specific parameters of the carrier are shown in Table II-1.

[0456] 186.5 g of cobalt nitrate hexahydrate (industrial grade, 98% purity), 19.5 g of 50 wt% manganese nitrate aqueous solution, and 14.13 g of copper nitrate trihydrate were dissolved in water to prepare a 132 ml solution. This solution was then loaded onto a 100 g support using a spray-dip method in two separate applications. After each spray-dip, the support was dried at 120 °C for 4 hours and then calcined at 400 °C for 2 hours. The support was then gradually reduced with hydrogen at a reduction rate of 20 °C / hour, and finally reduced at 480 °C for 2 hours to obtain catalyst A-II-1.

[0457] Example II-2

[0458] The pseudoboehmite powder (specific surface area 333 m2 / g, pore volume 1.04 ml / g, boron content 0.53 g relative to 100 g of Al2O3 powder) was kneaded and pressed into clover shape with 10 vol% nitric acid water, dried at 150 °C for 6 h, and then calcined at 820 °C for 4 h to prepare a carrier. The specific parameters of the carrier are shown in Table II-1.

[0459] 151.7 g of nickel nitrate hexahydrate (industrial grade, 98% purity), 13.0 g of 50wt% manganese nitrate aqueous solution, and 8.48 g of copper nitrate trihydrate were dissolved in water to prepare a 148 ml solution. This solution was then loaded onto a 100 g support using a spray-dip method in two separate applications. After each spray-dip, the support was dried at 120°C for 4 hours and then calcined at 400°C for 4 hours. 1.12 g of ammonium perrhenate was dissolved in water to prepare a 78 ml solution, which was then sprayed onto the semi-finished product obtained above. The semi-finished product was dried at 120°C for 4 hours and then calcined at 370°C for 4 hours. The product was then gradually reduced with hydrogen at a reduction rate of 20°C / hour, and finally reduced at 450°C for 3 hours to obtain catalyst A-II-2.

[0460] Example II-3

[0461] The pseudoboehmite powder (specific surface area 369 m2 / g, pore volume 0.99 ml / g, sulfur content 2.88 g relative to 100 g of Al2O3 powder) and silica sol were mixed and kneaded with dilute acid water containing 15 vol% nitric acid, pressed into toothed spheres with a diameter of 4 mm, dried at 100 °C for 20 h, and then calcined at 840 °C for 5 h to prepare a carrier. The specific parameters of the carrier are shown in Table II-1.

[0462] 45.4 g of cobalt nitrate hexahydrate (industrial grade, 98% purity) and 1.57 g of silver nitrate were dissolved in water to make a 102 ml solution. This solution was then loaded onto a 100 g support using a spray-dip method in two separate applications. After each spray-dip, the support was dried at 120 °C for 4 hours and then calcined at 400 °C for 4 hours. 1.50 g of ammonium perrhenate was dissolved in water to make a 70 ml solution. This solution was sprayed onto the semi-finished product obtained above, dried at 120 °C for 4 hours, and then calcined at 390 °C for 4 hours. Then, the product was gradually reduced with hydrogen at a reduction rate of 20 °C / hour, and finally reduced at 420 °C for 4 hours to obtain catalyst A-II-3.

[0463] Example II-4

[0464] The pseudoboehmite powder (specific surface area 375 m2 / g, pore volume 1.15 ml / g, fluorine content 0.08 g relative to 100 g of Al2O3 powder) and ZSM-5 (commercially available, produced by Nankai University, SiO2 / Al2O3=45 (MoR ratio)) were mixed and kneaded with dilute acid water containing 12 vol% nitric acid, pressed into cylindrical strips with a diameter of 4 mm, dried at 120℃ for 8 h, and then calcined at 810℃ for 4 h to prepare the carrier. The specific parameters of the carrier are shown in Table II-1.

[0465] 126.0 g of cobalt nitrate hexahydrate (industrial grade, 98% purity) and 0.79 g of silver nitrate were dissolved in water to make a 192 ml solution. This solution was then applied to a 100 g support using a spray-dip method in two separate applications. After each spray-dip, the support was dried at 120 °C for 4 hours and then calcined at 380 °C for 4 hours. 8.70 g of ammonium perrhenate was dissolved in water to make an 81 ml solution. This solution was sprayed onto the semi-finished product obtained above, dried at 120 °C for 4 hours, and then calcined at 400 °C for 3 hours. The product was then gradually reduced with hydrogen at a reduction rate of 20 °C / hour, and finally reduced at 420 °C for 4 hours to obtain catalyst A-II-4.

[0466] Example II-5

[0467] The pseudoboehmite powder (specific surface area 298 m2 / g, pore volume 0.85 ml / g, phosphorus content 0.18 g relative to 100 g of Al2O3 powder) was kneaded with dilute acid water containing 15 vol% nitric acid, pressed into cylindrical strips with a diameter of 2.5 mm, dried at 110 °C for 14 h, and then calcined at 890 °C for 4 h to prepare a carrier. The specific parameters of the carrier are shown in Table II-1.

[0468] 75.6 g of cobalt nitrate hexahydrate (industrial grade, 98% purity), 13.0 g of 50wt% manganese nitrate aqueous solution, and 3.15 g of silver nitrate were dissolved in water to make a 112 ml solution. This solution was then loaded onto a 100 g support using a spray-dip method in two separate applications. After each spray-dip, the support was dried at 120°C for 4 hours and then calcined at 380°C for 4 hours. 2.90 g of ammonium perrhenate was dissolved in water to make a 70 ml solution, which was then sprayed onto the semi-finished product obtained above. The semi-finished product was dried at 120°C for 4 hours and then calcined at 400°C for 2 hours. The product was then gradually reduced with hydrogen at a reduction rate of 20°C / hour, and finally reduced at 450°C for 3 hours to obtain catalyst A-II-5.

[0469] Example II-6

[0470] The pseudoboehmite powder (specific surface area 348 m2 / g, pore volume 1.09 ml / g, boron content 3.66 g relative to 100 g of Al2O3 powder) and silica sol were mixed and kneaded with dilute acid water containing 15 vol% nitric acid, pressed into cylindrical strips with a diameter of 4 mm, dried at 120 °C for 7 h, and then calcined at 810 °C for 6 h to prepare the carrier. The specific parameters of the carrier are shown in Table II-1.

[0471] 126.4 g of nickel nitrate hexahydrate (industrial grade, 98% purity), 26.1 g of 50 wt% manganese nitrate aqueous solution, and 1.57 g of silver nitrate were dissolved in water to make a 146 ml solution. This solution was then loaded onto a 100 g support using a spray-dip method in two separate applications. After each spray-dip, the support was dried at 120 °C for 4 hours and then calcined at 380 °C for 4 hours. 4.40 g of ammonium perrhenate was dissolved in water to make a 74 ml solution, which was then sprayed onto the semi-finished product obtained above. The semi-finished product was dried at 120 °C for 4 hours and then calcined at 350 °C for 6 hours. The product was then gradually reduced with hydrogen at a reduction rate of 20 °C / hour, and finally reduced at 440 °C for 3 hours to obtain catalyst A-II-6.

[0472] Example II-7

[0473] The pseudoboehmite powder (specific surface area 374 m2 / g, pore volume 1.18 ml / g, sulfur content 0.81 g relative to 100 g of Al2O3 powder) and silica sol were mixed and kneaded with dilute acid water containing 10 vol% nitric acid, pressed into cylindrical strips with a diameter of 4 mm, dried at 120 °C for 7 h, and then calcined at 750 °C for 6 h to prepare a carrier. The specific parameters of the carrier are shown in Table II-1.

[0474] 201.6 g of cobalt nitrate hexahydrate (industrial grade, 98% purity), 11.30 g of copper nitrate trihydrate, and 9.80 g of 50wt% manganese nitrate aqueous solution were dissolved in water to prepare a 132 ml solution. This solution was then loaded onto a 100 g support using a spray-dip method in two separate applications. After each spray-dip, the support was dried at 120°C for 4 hours and then calcined at 380°C for 4 hours. 4.70 g of ammonium perrhenate was dissolved in water to prepare a 74 ml solution, which was then sprayed onto the semi-finished product obtained above. The semi-finished product was dried at 120°C for 4 hours and then calcined at 400°C for 2 hours. The product was then gradually reduced with hydrogen at a reduction rate of 20°C / hour, and finally reduced at 460°C for 2 hours to obtain catalyst A-II-7.

[0475] Example II-8

[0476] The pseudoboehmite powder (specific surface area 355 m2 / g, pore volume 1.05 ml / g, sulfur content 0.88 g relative to 100 g of Al2O3 powder) and silica sol were mixed and kneaded with dilute acid water containing 10 vol% nitric acid, pressed into cylindrical strips with a diameter of 4 mm, dried at 120 °C for 7 h, and then calcined at 810 °C for 6 h to prepare the carrier. The specific parameters of the carrier are shown in Table II-1.

[0477] 100.8 g of cobalt nitrate hexahydrate (industrial grade, 98% purity), 14.30 g of copper nitrate trihydrate, and 1.57 g of silver nitrate were dissolved in water to make a 116 ml solution. The solution was loaded onto a 100 g support in two separate spray impregnation operations. After each spray impregnation, the support was dried at 120 °C for 4 hours and then calcined at 360 °C for 4 hours. The support was then gradually reduced with hydrogen at a rate of 20 °C / hour, and finally reduced at 420 °C for 5 hours to obtain catalyst A-II-8.

[0478] Example II-9

[0479] The pseudoboehmite powder (specific surface area 380 m2 / g, pore volume 1.01 ml / g, fluorine content 0.82 g relative to 100 g of Al2O3 powder) and silica sol were mixed and kneaded with dilute acid water containing 15 vol% nitric acid, pressed into cylindrical strips with a diameter of 4 mm, dried at 120 °C for 7 h, and then calcined at 810 °C for 6 h to prepare the carrier. The specific parameters of the carrier are shown in Table II-1.

[0480] 176.4 g of cobalt nitrate hexahydrate (industrial grade, 98% purity), 13.0 g of 50wt% manganese nitrate aqueous solution, and 1.57 g of silver nitrate were dissolved in water to make a 154 ml solution. This solution was then loaded onto a 100 g support using a spray-dip method in two separate applications. After each spray-dip, the support was dried at 120°C for 4 hours and then calcined at 380°C for 4 hours. 1.50 g of ammonium perrhenate was dissolved in water to make a 74 ml solution, which was then sprayed onto the semi-finished product obtained above. The semi-finished product was dried at 120°C for 4 hours and then calcined at 380°C for 3 hours. The product was then gradually reduced with hydrogen at a reduction rate of 20°C / hour, and finally reduced at 450°C for 3 hours to obtain catalyst A-II-9.

[0481] Example II-10

[0482] The pseudoboehmite powder (specific surface area 328 m2 / g, pore volume 0.97 ml / g, sulfur content 0.95 g relative to 100 g of Al2O3 powder) was kneaded with dilute acid water containing 5 vol% nitric acid, pressed into cylindrical strips with a diameter of 4 mm, dried at 120 °C for 7 h, and then calcined at 810 °C for 6 h to prepare a carrier. The specific parameters of the carrier are shown in Table II-1.

[0483] 226.8 g of cobalt nitrate hexahydrate (industrial grade, 98% purity), 26.1 g of 50wt% manganese nitrate aqueous solution, and 0.79 g of silver nitrate were dissolved in water to make a 162 ml solution. This solution was loaded onto a 100 g support using a spray-dip method in two separate applications. After each spray-dip, the support was dried at 120°C for 4 hours and then calcined at 380°C for 4 hours. 0.7 g of ammonium perrhenate was dissolved in water to make a 74 ml solution. This solution was sprayed onto the semi-finished product obtained above, dried at 120°C for 4 hours, and then calcined at 420°C for 2 hours. Then, hydrogen was gradually introduced for reduction at a rate of 20°C / hour, and finally, reduction was carried out at 430°C for 4 hours to obtain catalyst A-II-10.

[0484] Example II-11

[0485] The pseudoboehmite powder (specific surface area 304 m2 / g, pore volume 1.06 ml / g, phosphorus content 4.6 g relative to 100 g of Al2O3 powder) and silica sol were mixed and kneaded with dilute acid water containing 5 vol% nitric acid, pressed into cylindrical strips with a diameter of 4 mm, dried at 120 °C for 7 h, and then calcined at 810 °C for 6 h to prepare the carrier. The specific parameters of the carrier are shown in Table II-1.

[0486] 141.1 g of cobalt nitrate hexahydrate (industrial grade, 98% purity), 13.0 g of 50wt% manganese nitrate aqueous solution, and 0.79 g of silver nitrate were dissolved in water to make a 152 ml solution. This solution was then loaded onto a 100 g support using a spray-dip method in two separate applications. After each spray-dip, the support was dried at 120°C for 4 hours and then calcined at 380°C for 4 hours. 2.90 g of ammonium perrhenate was dissolved in water to make a 74 ml solution, which was then sprayed onto the semi-finished product obtained above. The semi-finished product was dried at 120°C for 4 hours and then calcined at 400°C for 4 hours. The product was then gradually reduced with hydrogen at a reduction rate of 20°C / hour, and finally reduced at 460°C for 2 hours to obtain catalyst A-II-11.

[0487] Example II-12

[0488] The catalyst was prepared according to the method of Example II-3, except that the pseudoboehmite powder used did not contain impurities and had a specific surface area of ​​298 m2 / g and a pore volume of 1.08 ml / g. The prepared catalyst was named A-II-12.

[0489] Comparative Example II-1

[0490] After mixing the pseudoboehmite powder (specific surface area 376 m2 / g, pore volume 1.01 ml / g, sulfur-free) with silica sol, knead it with dilute acid water containing 10 vol% nitric acid, press it into 4 mm toothed spheres, dry it at 120℃ for 5 h, and then calcine it at 860℃ for 6 h to prepare the carrier. The specific parameters of the carrier are shown in Table II-1.

[0491] The remaining steps are the same as in Example 8, and catalyst D-II-1 is prepared.

[0492] Comparative Example II-2

[0493] After mixing the pseudoboehmite powder (specific surface area 358 m2 / g, pore volume 1.15 ml / g, sulfur-free) with silica sol, knead it with dilute acid water containing 10 vol% nitric acid, press it into 4 mm toothed spheres, dry it at 100℃ for 12 h, and then calcine it at 890℃ for 6 h to prepare the carrier. The specific parameters of the carrier are shown in Table II-1.

[0494] 226.8 g of cobalt nitrate hexahydrate (industrial grade, 98% purity) and 0.79 g of silver nitrate were dissolved in water to make a 162 ml solution. The solution was loaded onto a 100 g support in two separate spray impregnation operations. After each spray impregnation, the support was dried at 120 °C for 4 hours and then calcined at 380 °C for 4 hours. Then, the support was gradually reduced with hydrogen at a rate of 20 °C / hour, and finally reduced at 450 °C for 4 hours to obtain catalyst D-II-2.

[0495] Test Case II-1

[0496] The elemental composition of the support and catalyst was analyzed by plasma emission spectrometry. The contents of dopants, active metal components and metal additives were expressed as the weight of 100 g of matrix. The supports prepared above were characterized by NH3-TPD and BET nitrogen adsorption-desorption methods. The results are shown in Table II-1.

[0497] Table II-1 Properties of the carriers in each embodiment and comparative example Example serial number Active metal components and content, g Metal additives and their content, g Matrix and its composition (wt%) Specific surface area, m 2 / g Pore ​​volume, ml / g Ammonia adsorption capacity mmol / g 7-27nm pore size distribution <7nm pore size distribution Doping elements and their content, g Example II-1 Co 37 Mn 2 / Cu 5 Al2O3 150 0.71 0.33 0.75 0.03 P 0.22 Example II-2 Ni 30 Mn2 / Cu3 Al2O3 158 0.79 0.35 0.72 0.07 B 0.53 Example II-3 Co 9 Re 1 / Ag 1 Al2O378 / SiO222 144 0.56 0.56 0.71 0.06 S 2.25 Example II-4 Co 25 Re 6 / Ag 0.5 Al2O385 / ZSM-5 15 180 1.01 0.38 0.76 0.04 F 0.07 Example II-5 Co 15 Mn² / Re² / Ag² Al2O3 132 0.61 0.32 0.73 0.05 P 0.18 Example II-6 Ni 25 Mn 4 / Re 3 / Ag 1 Al2O380 / SiO220 188 0.78 0.46 0.7 0.02 B 2.93 Example II-7 Co 40 Mn 1.5 / Re 3.2 / Cu 4 Al2O382 / SiO218 171 0.71 0.45 0.72 0.08 S 0.66 Example II-8 Co 20 Mn 3 / Cu 5 / Ag 1 Al2O386 / SiO214 165 0.63 0.48 0.76 0.06 S 0.76 Example II-9 Co 35 Mn 2 / Re 1 / Ag 1 Al2O389 / SiO211 181 0.82 0.55 0.74 0.05 F 0.73 Example II-10 Co 45 Mn 4 / Re 0.5 / Ag 0.5 Al2O3 178 0.86 0.52 0.71 0.04 S 0.95 Example II-11 Co 28 Mn² / Re² / Ag 0.5 Al2O395 / SiO25 176 0.81 0.46 0.73 0.07 P 4.37 Example II-12 Co 9 Re 1 / Ag 1 Al2O378 / SiO222 135 0.59 0.28 0.82 0.06 - Comparative Example II-1 Co 20 Mn 3 / Cu 5 / Ag 1 Al2O392 / SiO28 178 0.75 0.23 0.65 0.12 - Comparative Example II-2 Co 45 Ag 0.5 Al2O396 / SiO24 162 0.62 0.20 0.69 0.04 -

[0498] Test Case II-2

[0499] This test example is used to illustrate the method for preparing 1,6-hexanediamine by hydroamylation of 1,6-hexanediol using the catalyst of the Type II embodiment of this application.

[0500] 100 mL of the catalysts prepared in the examples and the control example were respectively placed in a fixed-bed reactor. The catalysts were activated with hydrogen at 220°C for 2 hours, then cooled to 168°C. The system pressure was increased to 9.5 MPa with hydrogen. Ammonia was then metered and fed into the reaction system using a metering pump. After preheating to 155°C, the ammonia was fed into the upper part of the reactor. Melted 1,6-hexanediol was fed into the upper part of the reactor using a metering pump. Hydrogen was steadily fed in using a gas mass flow meter. The molar ratio of hydrogen:ammonia:1,6-hexanediol was 3:8:1, and the liquid hourly space velocity of 1,6-hexanediol was 0.5 h⁻¹. Catalytic amination reaction was carried out in the reactor at a reaction temperature of 200°C and a reaction pressure of 11 MPa. After the reaction stabilized (i.e., after 500 h), the reaction solution was sampled and analyzed. The analysis results are listed in Table II-2.

[0501] The sampling and analysis method is gas chromatography analysis, and calibration is performed by using the correction factor of the prepared standard sample.

[0502] The conversion rate and selectivity are calculated based on the mole content of each component in the reaction solution. The specific calculation method is the same as that in Test Example I-2.

[0503] Table II-2 Test results of catalysts in each example and control example catalyst Catalyst composition Conversion rate, % Selectivity, % Hexamethylenediamine Cycloheximine aminohexanol other A-II-1 Co-Mn-Cu / Al2O3 89.6 49.1 23.2 24.5 3.2 A-II-2 Ni-Mn-Cu / Al2O3 91.3 50.5 24.8 21.6 3.1 A-II-3 Co-Re-Ag / Al2O3-SiO2 89.5 51.2 19.2 26.8 2.8 A-II-4 Co-Re-Ag / Al2O3-ZSM-5 90.4 47.9 21.0 27.4 3.7 A-II-5 Co-Mn-Re-Ag / Al2O3 92.8 45.5 20.1 31.3 3.1 A-II-6 Ni-Mn-Re-Ag / Al2O 3- SiO2 89.6 49.8 19.8 26.9 3.5 A-II-7 Co-Mn-Re-Cu / Al2O3-SiO2 92.3 52 23.1 21.3 3.6 A-II-8 Co-Mn-Cu-Ag / Al2O3-SiO2 85.1 48.8 20.2 27.9 3.1 A-II-9 Co-Mn-Re-Ag / Al2O3-SiO2 84.2 49 22 25.1 3.9 A-II-10 Co-Zn / Al2O3 82.1 46.1 19.9 29.9 4.1 A-II-11 Co-Mn-Re-Ag / Al2O3-SiO2 83.2 45.8 21.8 29.8 2.6 A-II-12 Co-Re-Ag / Al2O3-SiO2 72.3 37.9 25.1 30.5 6.5 D-II-1 Co-Mn-Cu-Ag / Al2O3-SiO2 73.4 36.4 23.1 32.4 8.1 D-II-2 Co-Ag / Al2O3-SiO2 68.5 34.5 24.5 30.6 10.4

[0504] As can be seen from the data in Table II-2, the catalyst of this application has a higher conversion rate and hexamethylenediamine selectivity, indicating that its catalytic activity has been improved compared with the catalyst of non-this application. At the same time, the selectivity of "other", that is, amines with more than 12 carbons, is lower, which indicates that the catalyst of this application has a lower carbon deposition rate and higher stability.

[0505] Long-term stability experiments of 500 h were conducted on the above-mentioned A-II-3 and D-II-2 catalysts, respectively. BET and XRD tests were performed on the catalysts before and after use (results are shown in Table II-3). The results showed that the specific surface area, pore volume, and active metal grain size of the A-II-3 catalyst remained basically unchanged, while the specific surface area and pore volume of the D-II-2 catalyst decreased to varying degrees, and the active metal grain size increased significantly compared to before the reaction. This indicates that the catalyst of this application has better stability and less carbon deposition.

[0506] Table II-3 Changes in the properties of the catalyst before and after the reaction catalyst Specific surface area, m 2 / g Pore ​​volume, ml / g active metal component grain size, nm Before A-II-3 reaction 128 0.63 7.4 After the A-II-3 reaction 125 0.62 7.8 D-II-2 before reaction 129 0.65 8.9 After the D-II-2 reaction 110 0.53 16.7

[0507] Test Case II-3

[0508] 100 mL of catalyst A-II-3 prepared in Example II-3 was measured and placed in a fixed-bed reactor. It was activated with hydrogen at 240°C for 2 hours, then cooled to 168°C. The system pressure was increased to 1.8 MPa with hydrogen. Ammonia was then metered and fed into the reaction system using a metering pump. After preheating to 160°C, it entered the upper part of the reactor. Ethanol was fed into the upper part of the reactor using a metering pump. Hydrogen was stably fed in through a gas mass flow meter. The molar ratio of hydrogen:ammonia:ethanol was 3:5:1, and the liquid hourly space velocity of ethanol was 0.6 h-1. Catalytic amination reaction was carried out in the reactor at a reaction temperature of 185°C and a reaction pressure of 2.8 MPa. After the reaction stabilized, samples were taken for analysis. The analysis results are shown in Table II-4.

[0509] Table II-4 Results of Test Case II-3 Continuous reaction time Ethanol conversion rate / % Selectivity / % Monoethylamine Diethylamine Triethylamine other 500 h 98.4 25.9 50.9 22.9 0.3 1000 h 98.5 26.1 50.8 22.8 0.3

[0510] Test Case II-4

[0511] 100 mL of catalyst A-II-5 prepared in Example II-5 was measured and placed in a fixed-bed reactor. It was activated with hydrogen at 240°C for 2 hours, then cooled to 168°C. The system pressure was increased to 8 MPa with hydrogen. Ammonia was then metered and fed into the reaction system using a metering pump. After preheating to 150°C, it entered the upper part of the reactor. Ethanolamine was fed into the upper part of the reactor using a metering pump. Hydrogen was stably fed in through a gas mass flow meter. The molar ratio of hydrogen:ammonia:ethanolamine was 3:8:1, and the liquid hourly space velocity of ethanolamine was 0.6 h-1. Catalytic amination reaction was carried out in the reactor at a reaction temperature of 195°C and a reaction pressure of 9.5 MPa. After the reaction stabilized, samples were taken for analysis (analytical conditions and conversion and selectivity calculation methods were similar to those in Test Example II-2). The analytical results are shown in Table II-5.

[0512] Table II-5 Results of Test Case II-4 Continuous reaction time ethanolamine conversion rate Selectivity / % ethylenediamine Piper Diethylenetriamine Hydroxyethyl ethylenediamine N-aminoethylpiperazine N-hydroxyethylpiperazine other 500 h 91.5 58.4 25.2 7.99 7.5 0.5 0.3 0.1 1000 h 91.4 58.3 25.3 8.02 7.56 0.42 0.3 0.1

[0513] Example III Series

[0514] The following will describe in detail the third type of implementation of this application through a series of examples III. In the following examples of the third series, the pseudoboehmite powder was produced by the aluminum sulfate method, and its dry basis (Al2O3) content was 72% by weight; the silica sol was purchased from Qingdao Ocean Chemical Co., Ltd., model JN-40.

[0515] Example III-1

[0516] The pseudoboehmite powder (specific surface area 375 m2 / g, pore volume 0.99 ml / g, boron content 3.89 g per 100 g Al2O3) was kneaded and pressed into strips with a diameter of 5 mm using dilute acid water containing 5 vol% nitric acid (containing a quantified amount of calcium nitrate, calcium content 0.11 g per 100 g Al2O3), dried at 120℃ for 12 h, and then calcined at 800℃ for 10 h to prepare a carrier. The specific parameters of the carrier are shown in Table III-1.

[0517] 176.4 g of cobalt nitrate hexahydrate (industrial grade, 98% purity), 26.1 g of 50wt% manganese nitrate aqueous solution, and 6.83 g of zinc nitrate were dissolved in water to make a 138 ml solution. The solution was loaded onto a 100 g support in two separate spray impregnation operations. After each spray impregnation, the support was dried at 120 °C for 4 hours and then calcined at 400 °C for 4 hours. Then, the support was gradually reduced with hydrogen at a rate of 20 °C / hour, and finally reduced at 430 °C for 3 hours to obtain catalyst A-III-1.

[0518] Example III-2

[0519] The pseudoboehmite powder (specific surface area 405 m2 / g, pore volume 1.06 ml / g, sulfur content 0.79 g relative to 100 g Al2O3) was kneaded and pressed into 3 mm thick clover shapes using dilute acid water containing 5 vol% nitric acid (containing quantified magnesium nitrate, magnesium content 0.78 g relative to 100 g Al2O3), dried at 120 °C for 15 h, and then calcined at 840 °C for 4 h to prepare a carrier. The specific parameters of the carrier are shown in Table III-1.

[0520] 161.8 g of nickel nitrate hexahydrate (industrial grade, 98% purity), 39.1 g of 50wt% manganese nitrate aqueous solution, and 6.83 g of zinc nitrate were dissolved in water to form a 146 ml solution. The solution was loaded onto a 100 g support using a spray-dip method in two separate applications. After each spray-dip, the support was dried at 120 °C for 5 hours and then calcined at 390 °C for 4 hours. The support was then gradually reduced with hydrogen at a reduction rate of 20 °C / hour, and finally reduced at 440 °C for 3 hours to obtain catalyst A-III-2.

[0521] Example III-3

[0522] The pseudoboehmite powder (specific surface area 386 m2 / g, pore volume 1.09 ml / g, sulfur content 0.84 g per 100 g Al2O3) and silica sol were mixed and kneaded and pressed into toothed spheres with a diameter of 4 mm using dilute acid water containing 5 vol% nitric acid (containing a quantified amount of potassium nitrate, potassium content 2.1 g per 100 g Al2O3). The mixture was dried at 100 °C for 20 h and then calcined at 850 °C for 6 h to prepare the carrier. The specific parameters of the carrier are shown in Table III-1.

[0523] 50.4 g of cobalt nitrate hexahydrate (industrial grade, 98% purity), 13.0 g of 50wt% manganese nitrate aqueous solution, and 6.83 g of zinc nitrate solution were dissolved in water to make 104 ml of solution. The solution was loaded onto the obtained 100 g support in two separate spray impregnation operations. After each spray impregnation, the support was dried at 120 °C for 4 hours and then calcined at 400 °C for 4 hours. Then, the support was gradually reduced with hydrogen at a reduction rate of 20 °C / hour, and finally reduced at 430 °C for 3 hours to obtain catalyst A-III-3.

[0524] Example III-4

[0525] Pseudoboehmite powder (specific surface area 398 m2 / g, pore volume 0.99 ml / g, fluorine content 0.85 g relative to 100 g Al2O3) and ZSM-5 (commercially available, produced by Nankai University, SiO2 / Al2O3=45 (Mor ratio)) were mixed and kneaded and pressed into toothed spheres with a diameter of 4 mm using dilute acid water containing 5 vol% nitric acid (containing a quantified amount of bismuth nitrate, with a bismuth content of 1.8 g relative to 100 g of pseudoboehmite powder based on Al2O3). The mixture was dried at 140℃ for 10 h and then calcined at 750℃ for 10 h to prepare a carrier. The specific parameters of the carrier are shown in Table III-1.

[0526] 100.8 g of cobalt nitrate hexahydrate (industrial grade, 98% purity), 3.3 g of 50wt% manganese nitrate aqueous solution, and 4.55 g of zinc nitrate solution were dissolved in water to make 188 ml of solution. The solution was loaded onto the obtained 100 g support in two separate spray impregnation operations. After each spray impregnation, the support was dried at 120 °C for 4 hours and then calcined at 400 °C for 4 hours. Then, the support was gradually reduced with hydrogen at a reduction rate of 20 °C / hour, and finally reduced at 430 °C for 3 hours to obtain catalyst A-III-4.

[0527] Example III-5

[0528] The pseudoboehmite powder (specific surface area 375 m2 / g, pore volume 1.15 ml / g, phosphorus content 0.33 g per 100 g Al2O3) was kneaded and pressed into toothed spheres with a diameter of 4 mm using dilute acid water containing 5 vol% nitric acid (containing a quantified amount of barium nitrate, barium content 1.7 g per 100 g Al2O3). The spheres were dried at 150 °C for 6 h and then calcined at 950 °C for 3 h to prepare a carrier. The specific parameters of the carrier are shown in Table III-1.

[0529] 75.6 g of cobalt nitrate hexahydrate (industrial grade, 98% purity) and 4.55 g of zinc nitrate solution were dissolved in water to make 104 ml of solution. The solution was loaded onto the obtained 100 g support in two separate spray impregnation operations. After each spray impregnation, the solution was dried at 120 °C for 4 hours and then calcined at 380 °C for 4 hours. 2.9 g of ammonium perrhenate was dissolved in water to make 45 ml of solution. This solution was sprayed onto the semi-finished product obtained above, dried at 120 °C for 4 hours, and then calcined at 380 °C for 4 hours. Then, reduction was carried out by gradually increasing the temperature with hydrogen at a reduction rate of 30 °C / hour, and finally reduced at 450 °C for 4 hours to obtain catalyst A-III-5.

[0530] Example III-6

[0531] The pseudoboehmite powder (specific surface area 320 m2 / g, pore volume 1.03 ml / g, boron content 0.24 g relative to 100 g Al2O3) and silica sol were mixed and kneaded with dilute acid water containing 5 vol% nitric acid (containing a measured amount of calcium nitrate, with a calcium content of 1.20 g relative to 100 g Al2O3 carrier), pressed into strips with a diameter of 5 mm, cut into 4 mm lengths, dried at 110 °C for 16 h, and then calcined at 880 °C for 5 h to prepare the carrier. The specific parameters of the carrier are shown in Table III-1.

[0532] 126.4 g of nickel nitrate hexahydrate (industrial grade, 98% purity) and 22.75 g of zinc nitrate were dissolved in water to make a 150 ml solution. The solution was loaded onto a 100 g support in two separate spray impregnation operations. After each spray impregnation, the support was dried at 120 °C for 8 hours and then calcined at 360 °C for 6 hours. 4.30 g of ammonium perrhenate was dissolved in water to make a 67 ml solution. This solution was sprayed onto the semi-finished product obtained above, dried at 120 °C for 4 hours, and then calcined at 400 °C for 4 hours. Then, hydrogen was gradually introduced for reduction at a rate of 20 °C / hour, and finally reduced at 430 °C for 3 hours to obtain catalyst A-III-6.

[0533] Example III-7

[0534] The pseudoboehmite powder (specific surface area 355 m2 / g, pore volume 0.99 ml / g, sulfur content 2.65 g relative to 100 g Al2O3) and silica sol were mixed and kneaded with dilute acid water containing 5 vol% nitric acid (containing a measured amount of magnesium nitrate, magnesium content 1.4 g relative to 100 g Al2O3), pressed into strips with a diameter of 5 mm, dried at 120 °C for 15 h, and then calcined at 550 °C for 20 h to prepare the carrier. The specific parameters of the carrier are shown in Table III-1.

[0535] 201.6 g of cobalt nitrate hexahydrate (industrial grade, 98% purity) and 2.28 g of zinc nitrate were dissolved in water to make a 136 ml solution. The solution was loaded onto a 100 g support using a spray-dip method in two separate applications. After each spray-dip, the solution was dried at 120 °C for 4 hours and then calcined at 400 °C for 4 hours. 1.40 g of ammonium perrhenate was dissolved in water to make a 62 ml solution. This solution was sprayed onto the semi-finished product obtained above, dried at 120 °C for 4 hours, and then calcined at 400 °C for 4 hours. Then, reduction was carried out with hydrogen at a gradual heating rate of 20 °C / hour, and finally reduced at 480 °C for 2 hours to obtain catalyst A-III-7.

[0536] Example III-8

[0537] Pseudoboehmite powder (specific surface area 275 m2 / g, pore volume 0.99 ml / g, fluorine content 0.08 g per 100 g Al2O3) was kneaded and pressed into strips with a diameter of 5 mm using dilute acid water containing 5 vol% nitric acid (containing a measured amount of calcium nitrate, calcium content 0.80 g per 100 g Al2O3), dried at 150℃ for 8 h, and then calcined at 800℃ for 8 h to prepare a carrier. The specific parameters of the carrier are shown in Table III-1.

[0538] 100.8 g of cobalt nitrate hexahydrate (industrial grade, 98% purity) and 13.65 g of zinc nitrate were dissolved in water to make a 122 ml solution. The solution was loaded onto a 100 g support in two separate spray impregnation operations. After each spray impregnation, the support was dried at 120 °C for 4 hours and then calcined at 400 °C for 4 hours. 1.40 g of ammonium perrhenate was dissolved in water to make a 55 ml solution. This solution was sprayed onto the semi-finished product obtained above, dried at 120 °C for 4 hours, and then calcined at 400 °C for 4 hours. Then, the product was gradually reduced with hydrogen at a reduction rate of 20 °C / hour, and finally reduced at 450 °C for 3 hours to obtain catalyst A-III-8.

[0539] Example III-9

[0540] Phyllite powder (specific surface area 379 m2 / g, pore volume 0.99 ml / g, phosphorus content 0.2 g per 100 g Al2O3) was kneaded and pressed into cylindrical shapes with a diameter of 5 mm using dilute acid water containing 5 vol% nitric acid (containing a measured amount of calcium nitrate, calcium content 1.30 g per 100 g Al2O3). The mixture was dried at 100 °C for 18 h and then calcined at 880 °C for 4 h to prepare a carrier. The specific parameters of the carrier are shown in Table III-1.

[0541] 176.4 g of cobalt nitrate hexahydrate (industrial grade, 98% purity), 19.5 g of 50 wt% manganese nitrate aqueous solution, and 19.36 g of zinc nitrate were dissolved in water to make a 152 ml solution. The solution was loaded onto a 100 g support using a spray-dip method in two separate applications. After each spray-dip, the solution was dried at 120 °C for 4 hours and then calcined at 380 °C for 4 hours. 1.44 g of ammonium perrhenate was dissolved in water to make a 70 ml solution. This solution was sprayed onto the semi-finished product obtained above, dried at 120 °C for 4 hours, and then calcined at 420 °C for 3 hours. Then, it was gradually reduced with hydrogen at a reduction rate of 20 °C / hour, and finally reduced at 420 °C for 6 hours to obtain catalyst A-III-9.

[0542] Example III-10

[0543] The pseudoboehmite powder (specific surface area 392 m2 / g, pore volume 0.99 ml / g, sulfur content 0.97 g per 100 g Al2O3) was kneaded and pressed into strips with a diameter of 5 mm using dilute acid water containing 5 vol% nitric acid (containing a measured amount of calcium nitrate, calcium content 0.05 g per 100 g Al2O3), dried at 80 °C for 20 h, and then calcined at 700 °C for 10 h to prepare a carrier. The specific parameters of the carrier are shown in Table III-1.

[0544] 226.8 g of cobalt nitrate hexahydrate (industrial grade, 98% purity), 26.1 g of 50wt% manganese nitrate, and 2.28 g of zinc nitrate were dissolved in water to prepare a 162 ml solution. This solution was then applied to a 100 g support using a spray-dip method in two separate applications. After each spray-dip, the support was dried at 120°C for 6 hours and then calcined at 400°C for 4 hours. 2.88 g of ammonium perrhenate was dissolved in water to prepare a 75 ml solution, which was then sprayed onto the semi-finished product obtained above. The semi-finished product was dried at 120°C for 4 hours and then calcined at 400°C for 4 hours. The product was then gradually reduced with hydrogen at a reduction rate of 20°C / hour, and finally reduced at 440°C for 4 hours to obtain catalyst A-III-10.

[0545] Example III-11

[0546] The pseudoboehmite powder (specific surface area 315 m2 / g, pore volume 0.99 ml / g, phosphorus content 4.64 g per 100 g Al2O3) was kneaded and pressed into clover shape with a diameter of 3 mm using dilute acid water containing 5 vol% nitric acid (containing a measured amount of calcium nitrate, calcium content 1.25 g per 100 g Al2O3). It was dried at 120℃ for 8 h and then calcined at 750℃ for 8 h to prepare a carrier. The specific parameters of the carrier are shown in Table III-1.

[0547] 141.1 g of cobalt nitrate hexahydrate (industrial grade, 98% purity), 32.6 g of 50wt% manganese nitrate aqueous solution, and 2.28 g of zinc nitrate were dissolved in water to make a 154 ml solution. The solution was loaded onto a 100 g support using a spray-dip method in two separate applications. After each spray-dip, the support was dried at 120 °C for 4 hours and then calcined at 400 °C for 4 hours. 5.76 g of ammonium perrhenate was dissolved in water to make a 71 ml solution, which was then sprayed onto the semi-finished product obtained above. The semi-finished product was dried at 120 °C for 4 hours and then calcined at 390 °C for 6 hours. Then, the product was gradually reduced with hydrogen at a reduction rate of 20 °C / hour, and finally reduced at 450 °C for 3 hours to obtain catalyst A-III-11.

[0548] Example III-12

[0549] The catalyst was prepared according to the method of Example III-6, except that the pseudoboehmite powder used did not contain impurities and had a specific surface area of ​​366 m2 / g and a pore volume of 1.05 ml / g, thus obtaining catalyst A-III-12.

[0550] Comparative Example III-1

[0551] The catalyst was prepared according to the method of Example III-6, except that the pseudoboehmite powder used was free of impurities and had a specific surface area of ​​325 m2 / g and a pore volume of 0.95 ml / g. Zinc nitrate was replaced with 15.2 g of nickel nitrate hexahydrate (industrial grade, purity 98%) to obtain catalyst D-III-1.

[0552] Comparative Example III-2

[0553] The catalyst was prepared according to the method of Example III-9, except that the pseudoboehmite powder used was free of impurities and had a specific surface area of ​​349 m2 / g and a pore volume of 1.13 ml / g. The manganese nitrate and ammonium perrhenate were replaced with 20.1 g of cobalt nitrate hexahydrate (industrial grade, 98% purity) to obtain catalyst D-III-3.

[0554] Comparative Example III-3

[0555] The catalyst was prepared according to the method of Example III-2, except that the pseudoboehmite powder used (specific surface area 396 m2 / g, pore volume 1.21 ml / g, sulfur content 4.25 g relative to 100 g Al2O3) was replaced with 5.79 g of ferric nitrate nonahydrate. Catalyst D-III-3 was obtained.

[0556] Test Case III-1

[0557] The elemental composition of the support and catalyst was analyzed by plasma emission spectrometry. The contents of dopants, active metal components and metal additives were expressed as the weight of 100 g of matrix. The supports prepared above were characterized by NH3-TPD, CO2-TPD and BET nitrogen adsorption-desorption methods. The results are shown in Table III-1.

[0558] Table III-1 Properties of the carriers in each embodiment and comparative example Example serial number Metal active components and composition, g Metallic additives and their composition, g Matrix and composition (wt%) Carrier specific surface area, m 2 / g Carrier pore volume, ml / g Ammonia adsorption capacity, mmol / g CO2 adsorption capacity, mmol / g pore volume percentage of 7-27nm pores <7nm pore volume percentage Doping elements and their content Example III-1 Co 35 Mn 4 / Zn 1.5 Al2O3 165 0.74 0.33 0.08 0.75 0.08 B 3.89 / Ca 0.11 Example III-2 Ni 32 Mn 6 / Zn 1.5 Al2O3 163 0.78 0.34 0.11 0.72 0.05 S 0.79 / Mg 0.78 Example III-3 Co 10 Mn 2 / Zn 1.5 Al2O374 / SiO226 149 0.57 0.52 0.28 0.71 0.07 S 0.62 / K 1.6 Example III-4 Co 20 Mn 0.5 / Zn 1 Al2O385 / ZSM-5 15 181 0.99 0.37 0.22 0.76 0.05 F 0.72 / Bi 1.5 Example III-5 Co 15 Re 2 / Zn 1 Al2O3 139 0.62 0.34 0.18 0.73 0.03 P 0.33 / Ba 1.7 Example III-6 Ni 25 Re 3 / Zn 5 Al2O380 / SiO220 190 0.8 0.44 0.13 0.7 0.02 B 0.19 / Ca 0.96 Example III-7 Co 40 Re 1 / Zn 0.5 Al2O382 / SiO218 175 0.73 0.47 0.16 0.72 0.08 S 2.17 / Mg 1.1 Example III-8 Co 20 Re 1 / Zn 3 Al2O3 168 0.66 0.45 0.1 0.76 0.09 F 0.08 / Ca 0.8 Example III-9 Co 35 Mn 3 / Re 1 / Zn 0.5 Al2O3 191 0.81 0.52 0.14 0.74 0.01 P 0.2 / Ca 1.3 Example III-10 Co 45 Mn 4 / Re 2 / Ag 0.5 Al2O3 182 0.86 0.49 0.07 0.71 0.04 S 0.97 / Ca 0.05 Example III-11 Co 28 Mn 5 / Re 4 / Ag 0.5 Al2O3 185 0.82 0.44 0.23 0.73 0.03 P 4.64 / Ca 1.25 Example III-12 Ni 25 Re 3 / Zn 5 Al2O380 / SiO220 182 0.79 0.28 0.12 0.77 0.04 Ca 0.96 Comparative Example III-1 Ni 28 Re 3 Al2O380 / SiO220 170 0.61 0.23 0.20 0.72 0.05 Ca 0.96 Comparative Example III-2 Co 39 Zn 0.5 Al2O3 183 0.75 0.19 0.26 0.78 0.03 Ca 1.3 Comparative Example III-3 Ni 30 Mn 5 / Fe 0.8 Al2O3 159 0.69 0.71 0.06 0.74 0.05 S 4.25 / Mg 0.78

[0559] Test Case III-2

[0560] This test example is used to illustrate the method for preparing 1,6-hexanediamine by hydroamylation of 1,6-hexanediol using the catalyst of the Type III embodiment of this application.

[0561] 100 mL of the catalysts prepared in the examples and the control example were respectively placed in a fixed-bed reactor. The catalysts were activated with hydrogen at 220°C for 2 hours, then cooled to 168°C. The system pressure was increased to 12 MPa with hydrogen. Ammonia was then metered and fed into the reaction system using a metering pump. After being preheated to 160°C, the ammonia entered the upper part of the reactor. Melted 1,6-hexanediol was fed into the upper part of the reactor using a metering pump. Hydrogen was steadily fed in through a gas mass flow meter. The molar ratio of hydrogen:ammonia:1,6-hexanediol was 3:8:1, and the liquid hourly space velocity of 1,6-hexanediol was 0.6 h⁻¹. Catalytic amination reaction was carried out in the reactor at a reaction temperature of 205°C and a reaction pressure of 13 MPa. After the reaction stabilized (i.e., after 10 h), the reaction solution was sampled and analyzed. The analysis results are listed in Table III-2.

[0562] The sampling and analysis method is gas chromatography analysis, and calibration is performed by using the correction factor of the prepared standard sample.

[0563] The conversion rate and selectivity are calculated based on the mole content of each component in the reaction solution. The specific calculation method is the same as that in Test Example I-2.

[0564] Table III-2 Test results of catalysts in each example and control example catalyst Catalyst composition Conversion rate, % Selectivity, % Hexamethylenediamine Cycloheximine aminohexanol other A-III-1 Co-Mn-Zn / Al2O3 88.4 48.9 21.6 26.7 2.8 A-III-2 Ni-Mn-Zn / Al2O3 91.2 50.1 20.9 26.1 2.9 A-III-3 Co-Mn-Zn / Al2O3-SiO2 88.9 42.3 19.8 35.5 2.4 A-III-4 Co-Mn-Zn / Al2O3-ZSM-5 91.4 48.5 20.7 27.7 3.1 A-III-5 Co-Re-Zn / Al2O3 87.9 46.5 21.2 28.9 3.4 A-III-6 Ni-Re-Zn / Al2O3-SiO2 88.1 47.8 19.7 29.6 2.9 A-III-7 Co-Re-Zn / Al2O3-SiO2 91.8 51.8 22.7 22.4 3.1 A-III-8 Co-Re-Zn / Al2O3 86.5 48.5 21.3 27.3 2.9 A-III-9 Co-Mn-Re-Zn / Al2O3 87.8 48.6 21.9 26.9 2.6 A-III-10 Co-Mn-Re-Zn / Al2O3 84.9 45.8 20.1 31.4 2.7 A-III-11 Co-Mn-Re-Zn / Al2O3 85.9 46.2 22.3 28.9 2.6 A-III-12 Co-Mn-Zn / Al2O3-SiO2 74.2 36.3 20.9 34.6 8.2 D-III-1 Ni-Re / Al2O3-SiO2 65.2 32.3 26.8 31.2 9.7 D-III-2 Co-Zn / Al2O3 64.1 36.1 28.2 25.4 10.3 D-III-3 Ni-Mn-Fe / Al2O3 71.6 35.7 30.6 24.3 9.4

[0565] Using the same process conditions, the above-mentioned catalysts were subjected to long-term stability testing over a period of 500 hours. BET and XRD tests were performed on the catalysts before and after application. The results showed that the specific surface area and pore volume of catalysts A-III-1 to A-III-11 remained essentially unchanged before and after application (decreased by no more than 2%), while the specific surface area and pore volume of catalysts D-III-1 to D-III-3 decreased more significantly after application (all exceeding 8%). This indicates that the catalyst of this application has better stability and less carbon deposition.

[0566] Further testing revealed that after 1000 h of use, the conversion rate of catalyst A-III-2 decreased by no more than 5%, and the specific surface area and pore volume decreased by no more than 5%. This demonstrates that the catalyst of this application has a long lifespan.

[0567] Test Case III-3

[0568] This test example is used to illustrate the method of preparing n-propylamine by hydroamylation of n-propanol using the catalyst of the Type III embodiment of this application.

[0569] 100 mL of catalyst A-III-2 prepared in Example III-3 was measured and placed in a fixed-bed reactor. It was activated with hydrogen at 220°C for 2 hours, then cooled to 172°C. The system pressure was increased to 1.5 MPa with hydrogen. Ammonia was then metered and fed into the reaction system using a metering pump. After being preheated to 150°C, it entered the upper part of the reactor. n-Propanol was fed into the upper part of the reactor using a metering pump. Hydrogen was stably fed in through a gas mass flow meter. The molar ratio of hydrogen:ammonia:n-propanol was 3:5:1, and the liquid hourly space velocity of propanol was 0.75 h-1. Catalytic amination reaction was carried out in the reactor at a reaction temperature of 180°C and a reaction pressure of 2 MPa. After the reaction stabilized, the reaction liquid was sampled and analyzed (the analysis conditions and conversion and selectivity calculation methods were similar to those in Test Example III-2). The analysis results are shown in Table III-3.

[0570] Table III-3 Results of Test Case III-3 Continuous reaction time n-Propanol conversion rate, % Selectivity, % n-Propylamine di-n-propylamine Tri-n-propylamine other 200 h 99.0 27.5 48.6 23.5 0.4 500 h 99.1 26.9 48.3 24.4 0.4

[0571] Example IV Series

[0572] The following will describe in detail the fourth type of embodiments of this application through a series of examples IV. In the following examples IV, the dry basis (Al2O3) content of the pseudoboehmite powder is 72% by weight; the silica sol was purchased from Qingdao Ocean Chemical Co., Ltd., model JN-40.

[0573] Example IV-1

[0574] The pseudoboehmite powder prepared by the aluminum sulfate method (specific surface area 380 m2 / g, pore volume 1.02 ml / g, pseudoboehmite powder contains doped element S, relative to 100 g of pseudoboehmite powder calculated as Al2O3, it contains 2.15 g of S element; during the preparation of pseudoboehmite powder, water glass (sodium silicate aqueous solution) of SiO2 precursor was added at the beginning, so that the mass of SiO2 from SiO2 precursor in the carrier after calcination accounts for 4% of the total mass of the carrier) was kneaded with dilute acid water containing 5 vol% nitric acid, and after kneading, it was pressed into strips with a diameter of 5 mm, cut into 4 mm lengths, dried at 120℃ for 8 h, and then calcined at 650℃ for 5 h to prepare the required carrier.

[0575] 186.5 g of cobalt nitrate hexahydrate (industrial grade, 98% purity), 6.83 g of zinc nitrate hexahydrate (analytical grade), and 5.65 g of copper nitrate trihydrate (analytical grade) were dissolved in water to prepare a 148 ml solution. This solution was loaded onto a 100 g support using a spray-dip method in two separate applications. After each spray-dip, the solution was dried at 120 °C for 4 hours and then calcined at 400 °C for 4 hours. Then, 1.8 g of ammonium molybdate tetrahydrate (analytical grade) was dissolved in water to prepare a 74 ml solution, which was sprayed onto the semi-finished product obtained above. The solution was dried at 120 °C for 4 hours and then calcined at 400 °C for 4 hours. The product was then gradually reduced with hydrogen at a reduction rate of 20 °C / hour, and finally reduced at 430 °C for 3 hours to obtain catalyst A-IV-1.

[0576] Example IV-2

[0577] Pseudoboehmite powder prepared by the aluminum sulfate method (specific surface area 375 m2 / g, pore volume 0.98 ml / g, pseudoboehmite powder contains dopant element B, relative to 100 g of pseudoboehmite powder calculated as Al2O3, it contains 0.53 g of element B; during the preparation of pseudoboehmite powder, water glass (sodium silicate aqueous solution) of SiO2 precursor is added at the beginning, so that the mass of SiO2 from SiO2 precursor in the carrier after calcination accounts for 11% of the total mass of the carrier) is kneaded with dilute acid water containing 5 vol% nitric acid, and after kneading, it is pressed into a clover shape with a diameter of 3 mm, dried at 100℃ for 12 h, and then calcined at 590℃ for 8 h to prepare the required carrier.

[0578] 151.7 g of nickel nitrate hexahydrate (industrial grade, 98% purity), 6.83 g of zinc nitrate hexahydrate (analytical grade), and 5.65 g of copper nitrate trihydrate (analytical grade) were dissolved in water to prepare a 156 ml solution. This solution was loaded onto a 100 g support using a spray-dip method in two separate applications. After each spray-dip, the solution was dried at 120 °C for 4 hours and then calcined at 400 °C for 4 hours. Then, 3.7 g of ammonium molybdate tetrahydrate was dissolved in water to prepare a 78 ml solution, which was sprayed onto the semi-finished product obtained above. The solution was dried at 120 °C for 4 hours and then calcined at 400 °C for 4 hours. The product was then gradually reduced with hydrogen at a reduction rate of 20 °C / hour, and finally reduced at 430 °C for 3 hours to obtain catalyst A-IV-2.

[0579] Example IV-3

[0580] Pseudoboehmite powder prepared by the aluminum sulfate method (specific surface area 380 m2 / g, pore volume 1.02 ml / g, pseudoboehmite powder contains doped element S, relative to 100 g of pseudoboehmite powder calculated as Al2O3, it contains 2.15 g of S element; during the preparation of pseudoboehmite powder, water glass (sodium silicate aqueous solution) of SiO2 precursor was added at the beginning, so that the mass of SiO2 from SiO2 precursor in the carrier after calcination accounts for 4% of the total mass of the carrier) was kneaded with dilute acid water containing 5 vol% nitric acid, and after kneading, it was pressed into strips with a diameter of 5 mm, cut into 4 mm lengths, dried at 120℃ for 8 h, and then calcined at 650℃ for 5 h to prepare the required carrier.

[0581] 55.4 g of cobalt nitrate hexahydrate (industrial grade, 98% purity), 6.83 g of zinc nitrate hexahydrate (analytical grade), and 5.65 g of copper nitrate trihydrate (analytical grade) were dissolved in water to prepare a 144 ml solution. This solution was loaded onto a 100 g support using a spray-dip method in two separate applications. After each spray-dip, the solution was dried at 120 °C for 4 hours and then calcined at 400 °C for 4 hours. Then, 1.8 g of ammonium molybdate tetrahydrate was dissolved in water to prepare a 72 ml solution, which was sprayed onto the semi-finished product obtained above. The solution was dried at 120 °C for 4 hours and then calcined at 400 °C for 4 hours. The product was then gradually reduced with hydrogen at a reduction rate of 20 °C / hour, and finally reduced at 430 °C for 3 hours to obtain catalyst A-IV-3.

[0582] Example IV-4

[0583] Boehmite powder (specific surface area 340 m2 / g, pore volume 1.13 ml / g, containing doped element P, with 0.18 g of P relative to 100 g of boehmite powder based on Al2O3) prepared by the aluminum sulfate method was kneaded with dilute acid water containing 5 vol% nitric acid. The kneaded powder contained doped element P, with 0.18 g of P relative to 100 g of boehmite powder based on Al2O3. During the preparation of boehmite powder, ZSM-5 molecular sieve precursor (ZSM-5 powder, Nankai University Catalyst Factory, SiO2 / Al2O3=45 (MoR ratio), the same below) was added at the beginning, so that after calcination, Al2O3 derived from boehmite powder accounted for 85% of the total mass of the carrier. The mixture was kneaded and pressed into toothed spheres with a diameter of 4 mm, dried at 80 °C for 20 h, and then calcined at 530 °C for 6 h to prepare the required carrier.

[0584] 126 g of cobalt nitrate hexahydrate (industrial grade, 98% purity), 4.55 g of zinc nitrate, and 0.79 g of silver nitrate (analytical grade) were dissolved in water to prepare a 210 ml solution. This solution was loaded onto a 100 g support using a spray-dip method in two separate applications. After each spray-dip, the support was dried at 120 °C for 4 hours and then calcined at 400 °C for 4 hours. Then, 3.7 g of ammonium molybdate tetrahydrate (analytical grade) was dissolved in water to prepare a 105 ml solution, which was sprayed onto the semi-finished product obtained above. The semi-finished product was dried at 120 °C for 4 hours and then calcined at 400 °C for 4 hours. The product was then gradually reduced with hydrogen at a reduction rate of 20 °C / hour, and finally reduced at 430 °C for 3 hours to obtain catalyst A-IV-4.

[0585] Example IV-5

[0586] The carrier was prepared according to the method of Example IV-4, except that ZSM-5 molecular sieve precursor was added at the beginning of the preparation of pseudoboehmite powder, so that Al2O3 derived from pseudoboehmite powder accounted for 85% of the total mass of the carrier after calcination.

[0587] 126 g of cobalt nitrate hexahydrate (industrial grade, 98% purity), 9.1 g of zinc nitrate hexahydrate (analytical grade), and 1.57 g of silver nitrate (analytical grade) were dissolved in water to prepare a 208 ml solution. This solution was loaded onto a 100 g support using a spray-dip method in two separate applications. After each spray-dip, the solution was dried at 120 °C for 4 hours and then calcined at 400 °C for 4 hours. Then, 7.4 g of ammonium molybdate tetrahydrate (analytical grade) was dissolved in water to prepare a 104 ml solution, which was sprayed onto the semi-finished product obtained above. The solution was dried at 120 °C for 4 hours and then calcined at 400 °C for 4 hours. The product was then gradually reduced with hydrogen at a reduction rate of 20 °C / hour, and finally reduced at 430 °C for 3 hours to obtain catalyst A-IV-5.

[0588] Example IV-6

[0589] Boehmite powder (specific surface area 341 m2 / g, pore volume 1.11 ml / g, containing dopant element P, with 4.2 g of P relative to 100 g of boehmite powder calculated as Al2O3. During the preparation of boehmite powder, ZSM-5 molecular sieve precursor was added at the beginning, so that after calcination, Al2O3 derived from boehmite powder accounted for 85% of the total mass of the carrier) was kneaded with dilute acid water containing 5 vol% nitric acid, and then pressed into toothed spheres with a diameter of 4 mm. The spheres were dried at 80 °C for 20 h and then calcined at 530 °C for 6 h to prepare the desired carrier.

[0590] The remaining steps are the same as in Example IV-4 to obtain catalyst A-IV-6.

[0591] Example IV-7

[0592] Boehmite powder prepared by the aluminum sulfate method (specific surface area 288 m2 / g, pore volume 0.93 ml / g, containing dopant element S, with 0.88 g of S element relative to 100 g of boehmite powder calculated as Al2O3. During the preparation of boehmite powder, water glass (sodium silicate aqueous solution) as a SiO2 precursor was added at the beginning, so that the mass of SiO2 derived from the SiO2 precursor in the carrier after calcination accounted for 8% of the total mass of the carrier) was kneaded with dilute acid water containing 5 vol% nitric acid, and then pressed into clover-shaped pieces with a diameter of 4 mm. The pieces were dried at 100°C for 8 h and then calcined at 850°C for 4 h to prepare the desired carrier.

[0593] 201.6 g of cobalt nitrate hexahydrate (industrial grade, 98% purity), 2.28 g of zinc nitrate hexahydrate (analytical grade), and 8.48 g of copper nitrate trihydrate (analytical grade) were dissolved in water to prepare a 146 ml solution. This solution was loaded onto a 100 g support using a spray-dip method in two separate applications. After each spray-dip, the solution was dried at 120 °C for 4 hours and then calcined at 400 °C for 4 hours. Then, 2.7 g of ammonium metatungstate (analytical grade) was dissolved in water to prepare a 73 ml solution, which was sprayed onto the semi-finished product obtained above. The solution was dried at 120 °C for 4 hours and then calcined at 400 °C for 4 hours. The product was then gradually reduced with hydrogen at a reduction rate of 20 °C / hour, and finally reduced at 430 °C for 3 hours to obtain catalyst A-IV-7.

[0594] Example IV-8

[0595] The carrier prepared in Example IV-7 was used.

[0596] 100.8 g of cobalt nitrate hexahydrate (industrial grade, 98% purity), 2.28 g of zinc nitrate hexahydrate (analytical grade), and 8.48 g of copper nitrate trihydrate (analytical grade) were dissolved in water to prepare a 150 ml solution. This solution was loaded onto a 100 g support using a spray-dip method in two separate applications. After each spray-dip, the solution was dried at 120 °C for 4 hours and then calcined at 400 °C for 4 hours. Then, 2.7 g of ammonium metatungstate (analytical grade) was dissolved in water to prepare a 75 ml solution, which was sprayed onto the semi-finished product obtained above. The solution was dried at 120 °C for 4 hours and then calcined at 400 °C for 4 hours. The product was then gradually reduced with hydrogen at a reduction rate of 20 °C / hour, and finally reduced at 430 °C for 3 hours to obtain catalyst A-IV-8.

[0597] Example IV-9

[0598] The pseudoboehmite powder prepared by the aluminum sulfate method (specific surface area 281 m2 / g, pore volume 0.87 ml / g, the pseudoboehmite powder contains dopant element F, and relative to 100 g of pseudoboehmite powder calculated as Al2O3, it contains 0.82 g of F element; during the preparation of pseudoboehmite powder, water glass (sodium silicate aqueous solution) of SiO2 precursor was added at the beginning, so that the mass of SiO2 from SiO2 precursor in the carrier after calcination accounted for 21% of the total mass of the carrier) was kneaded with dilute acid water containing 5 vol% nitric acid, and after kneading, it was pressed into a clover shape with a diameter of 4 mm, dried at 90°C for 18 h, and then calcined at 770°C for 9 h to prepare the required carrier.

[0599] 176.4 g of cobalt nitrate hexahydrate (industrial grade, 98% purity), 2.28 g of zinc nitrate hexahydrate (analytical grade), and 11.3 g of copper nitrate trihydrate (analytical grade) were dissolved in water to prepare a 130 ml solution. This solution was loaded onto a 100 g support using a spray-dip method in two separate applications. After each spray-dip, the solution was dried at 120 °C for 4 hours and then calcined at 400 °C for 4 hours. Then, 2.0 g of ammonium metatungstate (analytical grade) was dissolved in water to prepare a 65 ml solution, which was sprayed onto the semi-finished product obtained above. The solution was dried at 120 °C for 4 hours and then calcined at 400 °C for 4 hours. The product was then gradually reduced with hydrogen at a reduction rate of 20 °C / hour, and finally reduced at 430 °C for 3 hours to obtain catalyst A-IV-9.

[0600] Example IV-10

[0601] The pseudoboehmite powder prepared by the aluminum sulfate method (specific surface area 274 m2 / g, pore volume 0.85 ml / g, pseudoboehmite powder contains doped element S, relative to 100 g of pseudoboehmite powder calculated as Al2O3, it contains 0.95 g of S element; during the preparation of pseudoboehmite powder, water glass (sodium silicate aqueous solution) of SiO2 precursor was added at the beginning, so that the mass of SiO2 from SiO2 precursor in the carrier after calcination accounts for 25% of the total mass of the carrier) was kneaded with dilute acid water containing 5 vol% nitric acid, and after kneading, it was pressed into a clover shape with a diameter of 3.5 mm, dried at 150℃ for 6 h, and then calcined at 930℃ for 6 h to prepare the required carrier.

[0602] 227.5 g of nickel nitrate hexahydrate (industrial grade, 98% purity), 2.28 g of zinc nitrate hexahydrate (analytical grade), and 1.10 g of silver nitrate (analytical grade) were dissolved in water to make a 156 ml solution. This solution was loaded onto a 100 g support using a spray-dip method in three separate applications. After each spray-dip, the solution was dried at 120 °C for 4 hours and then calcined at 400 °C for 4 hours. Then, 5.4 g of ammonium metatungstate (analytical grade) was dissolved in water to make a 52 ml solution, which was sprayed onto the semi-finished product obtained above. The solution was dried at 120 °C for 4 hours and then calcined at 400 °C for 4 hours. The product was then gradually reduced with hydrogen at a reduction rate of 20 °C / hour, and finally reduced at 430 °C for 3 hours to obtain catalyst A-IV-10.

[0603] Example IV-11

[0604] The pseudoboehmite powder prepared by the aluminum sulfate method (specific surface area 265 m2 / g, pore volume 0.81 ml / g, the pseudoboehmite powder contains doped element P, and relative to 100 g of pseudoboehmite powder calculated as Al2O3, it contains 3.1 g of P element; during the preparation of pseudoboehmite powder, water glass (sodium silicate aqueous solution) of SiO2 precursor was added at the beginning, so that the mass of SiO2 from SiO2 precursor in the carrier after calcination accounted for 28% of the total mass of the carrier) was kneaded with dilute acid water containing 5 vol% nitric acid, and after kneading, it was pressed into a clover shape with a diameter of 3 mm, dried at 100℃ for 8 h, and then calcined at 1020℃ for 5 h to prepare the required carrier.

[0605] 141.1 g of cobalt nitrate hexahydrate (industrial grade, 98% purity), 2.28 g of zinc nitrate hexahydrate (analytical grade), and 2.20 g of silver nitrate (analytical grade) were dissolved in water to make a 144 ml solution. This solution was loaded onto a 100 g support using a spray-dip method in three separate applications. After each spray-dip, the solution was dried at 120 °C for 4 hours and then calcined at 400 °C for 4 hours. Then, 5.4 g of ammonium metatungstate (analytical grade) was dissolved in water to make a 48 ml solution, which was sprayed onto the semi-finished product obtained above. The solution was dried at 120 °C for 4 hours and then calcined at 400 °C for 4 hours. The product was then gradually reduced with hydrogen at a reduction rate of 20 °C / hour, and finally reduced at 430 °C for 3 hours to obtain catalyst A-IV-11.

[0606] Example IV-12

[0607] The catalyst was prepared according to the method of Example IV-1, except that the pseudoboehmite powder used contained the dopant element P. Relative to 100 g of pseudoboehmite powder calculated as Al2O3, it contained 1.33 g of P element, with a specific surface area of ​​375 m2 / g and a pore volume of 0.98 ml / g, thus obtaining catalyst A-IV-12;

[0608] Comparative Example IV-1

[0609] The catalyst was prepared according to the method of Example IV-2, except that the pseudoboehmite powder used did not contain any doping elements and had a specific surface area of ​​391 m2 / g and a pore volume of 1.06 ml / g. The solution used in the spray impregnation method did not contain zinc nitrate hexahydrate, thus obtaining catalyst D-IV-1.

[0610] Comparative Example IV-2

[0611] The catalyst was prepared according to the method of Example IV-8, except that the pseudoboehmite powder used did not contain any doping elements and had a specific surface area of ​​349 m2 / g and a pore volume of 1.17 ml / g. The solution used in the spray impregnation method did not contain copper nitrate trihydrate, thus obtaining catalyst D-IV-2.

[0612] Comparative Example IV-3

[0613] The catalyst was prepared according to the method of Example IV-2, except that the pseudoboehmite powder used was free of dopants and had a specific surface area of ​​391 m2 / g and a pore volume of 1.06 ml / g. Zinc nitrate hexahydrate was replaced with 16.03 g of magnesium nitrate hexahydrate (analytical grade). Catalyst D-IV-3 was obtained.

[0614] Comparative Example IV-4

[0615] The catalyst was prepared according to the method of Example IV-2, except that the pseudoboehmite powder used was free of dopants and had a specific surface area of ​​391 m2 / g and a pore volume of 1.06 ml / g. Ammonium molybdate was not added, and zinc nitrate hexahydrate was replaced with 8.84 g of calcium nitrate tetrahydrate. Catalyst D-IV-4 was obtained.

[0616] Test Case IV-1

[0617] The elemental composition of the support and catalyst was analyzed by plasma emission spectrometry. The content of doped elements was expressed as the weight of 100 g of matrix. The content of active metal components and metal additives was also expressed as the weight of 100 g of matrix. The support prepared above was characterized by NH3-TPD and BET nitrogen adsorption-desorption methods. The results are shown in Table IV-1.

[0618] Table IV-1 Properties of the carriers in each embodiment and comparative example Example number Doping elements Relative content, g Ammonia adsorption capacity, mmol / g Percentage of pores <7nm, % Percentage of 7-27 nm pores, % Specific surface area, m 2 / g Pore ​​volume, ml / g type Relative content, g Active metal components Metal additives Example IV-1 S 2.02 37 Mo 1 / Cu 2 / Zn 1.5 0.44 4 75 198 0.74 Example IV-2 B 0.47 30 Mo²⁺ / Cu²⁺ / Zn 1.5 0.34 4 72 191 0.78 Example IV-3 S 2.02 11 Mo 1 / Cu 2 / Zn 1.5 0.44 5 74 196 0.72 Example IV-4 P 0.15 25 Mo 2 / Ag 0.5 / Zn 1 0.32 3 76 181 1.05 Example IV-5 P 0.15 25 Mo 4 / Ag 1 / Zn 2 0.33 2 75 179 1.03 Example IV-6 P 3.45 25 Mo 2 / Ag 0.5 / Zn 1 0.52 3 75 177 1.02 Example IV-7 S 0.80 40 W 2 / Cu 3 / Zn 0.5 0.36 5 72 183 0.73 Example IV-8 S 0.80 20 W 2 / Cu 3 / Zn 0.5 0.37 4 72 185 0.75 Example IV-9 F 0.64 35 W 1.5 / Cu 4 / Zn 0.5 0.36 3 74 152 0.65 Example IV-10 S 0.71 45 W 4 / Ag 0.7 / Zn 0.5 0.41 2 71 135 0.52 Example IV-11 P 2.18 28 W 4 / Ag 1.4 / Zn 0.5 0.48 4 73 128 0.48 Example IV-12 P 1.33 37 Mo 1 / Cu 2 / Zn 1.5 0.29 6 71 165 0.69 Comparative Example IV-1 none 0 30 Mo 2 / Cu 2 0.24 4 70 186 0.77 Comparative Example IV-2 0 0 20 W 2 / Zn 0.5 0.16 4 71 189 0.76 Comparative Example IV-3 none 0 30 Mo²⁺ / Cu²⁺ / Mg 1.5 0.20 4 74 184 0.74 Comparative Example IV-4 none 0 30 Cu 2 / Ca 1.5 0.22 5 70 185 0.79

[0619] Test Case IV-2

[0620] This test example is used to illustrate the method for preparing 1,6-hexanediamine by hydroamylation of 1,6-hexanediol using the catalyst of the Class IV embodiment of this application.

[0621] 100 mL of the catalysts prepared in the examples and the control example were respectively placed in a fixed-bed reactor. The catalysts were activated with hydrogen at 220°C for 2 hours, then cooled to 165°C. The system pressure was increased to 11 MPa with hydrogen. Ammonia was then metered and fed into the reaction system using a metering pump. After being preheated to 125°C, the ammonia entered the upper part of the reactor. 1,6-hexanediol, which was heated and melted, was fed into the upper part of the reactor using a metering pump. Hydrogen was stably fed in using a gas mass flow meter. The molar ratio of hydrogen:ammonia:1,6-hexanediol was 2:12:1. The liquid hourly space velocity of 1,6-hexanediol was 0.35 h⁻¹. Catalytic amination reaction was carried out in the reactor at a reaction temperature of 170°C and a reaction pressure of 11 MPa. After 20 h of reaction, the reaction solution was sampled and analyzed. The analysis results are listed in Table IV-2.

[0622] The sampling and analysis method is gas chromatography analysis, and calibration is performed by using the correction factor of the prepared standard sample.

[0623] The conversion rate and selectivity are calculated based on the mole content of each component in the reaction solution. The specific calculation method is the same as that in Test Example I-2.

[0624] Table IV-2 Test results of catalysts in each example and control example catalyst Catalyst composition Conversion rate, % Selectivity, % Hexamethylenediamine Cycloheximine aminohexanol other A-IV-1 Co-Mo-Cu-Zn / Al2O3-SiO2 95 67.3 15.4 14.9 2.4 A-IV-2 Ni-Mo-Cu-Zn / Al2O3-SiO2 95 67.9 14.3 15.3 2.5 A-IV-3 Co-Mo-Cu-Zn / Al2O3-SiO2 90 64.7 13.9 18.2 3.2 A-IV-4 Co-Mo-Ag-Zn / Al2O3-ZSM-5 94 66.3 16.2 15.1 2.4 A-IV-5 Co-Mo-Ag-Zn / Al2O3-ZSM-5 91 63.1 15.8 18.1 3 A-IV-6 Co-Mo-Ag-Zn / Al2O3-ZSM-5 90 60.7 20.3 15.7 3.3 A-IV-7 Co-W-Cu-Zn / Al2O3-SiO2 91 62.3 20.1 14.2 3.4 A-IV-8 Co-W-Cu-Zn / Al2O3-SiO2 94 65.8 14.8 16.5 2.9 A-IV-9 Co-W-Cu-Zn / Al2O3-SiO2 92 64.3 15.7 17.2 2.8 A-IV-10 Ni-W-Ag-Zn / Al2O3-SiO2 89 62.1 23.8 10.6 3.5 A-IV-11 Co-W-Ag-Zn / Al2O3-SiO2 91 62.7 17.3 17 3 A-IV-12 Co-Mo-Cu-Zn / Al2O3-SiO2 85 56.3 20.2 19.2 4.3 D-IV-1 Ni-Mo-Cu / Al2O3-SiO2 80 48.2 21.3 24.9 5.6 D-IV-2 Co-W-Zn / Al2O3-SiO2 81 46.3 21.8 26.6 5.3 D-IV-3 Ni-Mo-Cu-Mg / Al2O3-SiO2 75 42.3 21.6 29.9 6.2 D-IV-4 Ni-Cu-Ca / Al2O3-SiO2 76 39.2 20.5 32.2 8.1

[0625] Test Case IV-3

[0626] This test example is used to illustrate the method of preparing n-propylamine by hydroamylation of n-propanol using the catalyst of the Class IV embodiment of this application.

[0627] 100 mL of catalysts A-IV-3 prepared in Example IV-3 were respectively placed in a fixed-bed reactor and activated with hydrogen at 220°C for 2 hours. Then the temperature was lowered to 140°C, and the system pressure was increased to 2 MPa with hydrogen. Ammonia was then metered and fed into the reaction system using a metering pump. After being preheated to 110°C, it entered the upper part of the reactor. n-Propanol was fed into the upper part of the reactor using a metering pump. Hydrogen was stably fed in through a gas mass flow meter. The molar ratio of hydrogen:ammonia:n-propanol was 3:6:1, and the liquid hourly space velocity of propanol was 0.5 h-1. Catalytic amination reaction was carried out in the reactor. After the reaction stabilized, the reaction solution was sampled and analyzed (the analysis conditions and conversion and selectivity calculation methods were similar to those in Test Example IV-2). The analysis results are shown in Table IV-3.

[0628] Table 3 Results of Test Case IV-3 Continuous reaction time n-Propanol conversion rate, % Selectivity, % n-Propylamine di-n-propylamine Tri-n-propylamine other 20 h 99.12 25.3 53.1 20.8 0.8 400 h 99.13 25.2 53.2 20.7 0.9

[0629] Test Case IV-4

[0630] Under the same conditions as Test Example IV-2, catalysts A-IV-1, A-IV-4, D-IV-1, D-IV-2, and D-IV-3 were loaded into a fixed-bed reactor, respectively. The only change was that the reaction time was extended, and a 400-h experiment was conducted. The reaction solution after the initial stabilization of the reaction, i.e., after 20 h of reaction (analytical conditions and conversion and selectivity calculation methods were the same as Test Example IV-2), and the reaction solution after 400 h of reaction (analytical conditions and conversion and selectivity calculation methods were the same as Test Example IV-2) were analyzed. The analytical results are shown in Table IV-4.

[0631] Table IV-4 Results of Test Case IV-4 catalyst Catalyst composition Conversion rate, % Selectivity, % Hexamethylenediamine Cycloheximine aminohexanol other After 20 h of reaction A-IV-1 Co-Mo-Cu-Zn / Al2O3-SiO2 95 67.3 15.4 14.9 2.4 A-IV-4 Co-Mo-Ag-Zn / Al2O3-ZSM-5 94 66.3 16.2 15.1 2.4 D-IV-1 Ni-Mo-Cu / Al2O3-SiO2 80 48.2 21.3 24.9 5.6 D-IV-2 Co-W-Zn / Al2O3-SiO2 81 46.3 21.8 26.6 5.3 D-IV-3 Ni-Mo-Cu-Mg / Al2O3-SiO2 75 42.3 21.6 29.9 6.2 D-IV-4 Ni-Cu-Ca / Al2O3-SiO2 76 39.2 20.5 32.2 8.1 400 h time A-IV-1 Co-Mo-Cu-Zn / Al2O3-SiO2 94 66.9 15.3 15.3 2.5 A-IV-4 Co-Mo-Ag-Zn / Al2O3-ZSM-5 94 66.1 16.3 15.1 2.5 D-IV-1 Ni-Mo-Cu / Al2O3-SiO2 75 42.3 25.3 26.2 6.2 D-IV-2 Co-W-Zn / Al2O3-SiO2 71 40.5 24.3 28.7 6.5 D-IV-3 Ni-Mo-Cu-Mg / Al2O3-SiO2 61 30.5 24.9 35.7 8.9 D-IV-4 Ni-Cu-Ca / Al2O3-SiO2 45 30.2 21.3 36.8 11.7

[0632] As can be seen from the table above, after 400 hours of testing, catalysts A-IV-1 and A-IV-4 did not show a significant decrease in activity and selectivity (i.e., the decrease was less than 2%), while catalysts D-IV-1 to D-IV-4 all showed a significant decrease, and the amount of byproducts also increased. This indicates that the catalyst of this application has higher stability.

[0633] Example V Series

[0634] The V-type embodiments of this application will be described in detail below through examples V series. In the following V series examples, the dry basis (Al2O3) content of the pseudoboehmite powder is 70 wt%; the titanium dioxide is produced by the oxytitanium sulfate-ammonia hydrolysis method, with a sulfate content of 2.5 wt% and a TiO2 content of 95 wt%, and is a commercially available product of Shandong Dongjia Chemical Co., Ltd. with the code SA-100.

[0635] Example V-1

[0636] 820 g of pseudoboehmite powder (produced by nitric acid method, specific surface area 380 m2 / g, pore volume 0.96 ml / g) and 300 g of titanium dioxide were mixed evenly in a mixer. The mixture was kneaded and pressed into strips with a diameter of 5 mm using 790 ml of dilute acid water containing 5 vol% nitric acid. The strips were then cut into 4 mm lengths and dried overnight at 120°C. Finally, the mixture was calcined at 800°C for 4 h to prepare the desired carrier.

[0637] 126 g of cobalt nitrate hexahydrate (industrial grade, purity 98%) was dissolved in water to make a 150 ml solution. The resulting solution was loaded onto a 100 g support by spray impregnation in two separate applications. After each spray impregnation, the support was dried at 120 °C for 4 hours, then calcined at 400 °C for 4 hours, and then gradually reduced with hydrogen at a rate of 20 °C / hour. Finally, the support was reduced at 430 °C for 3 hours to obtain catalyst AV-1.

[0638] Example V-2

[0639] 780 g of pseudoboehmite powder (produced by carbonization method, specific surface area 405 m2 / g, pore volume 1.01 ml / g) and 220 g of titanium dioxide were mixed evenly in a mixer, kneaded and pressed into a 3 mm thick clover shape using 775 ml of dilute acid water containing 7 vol% acetic acid, dried at 120°C overnight, and then calcined at 850°C for 3 h to prepare the required carrier.

[0640] 140.4 g of nickel nitrate hexahydrate (industrial grade, purity 98%) was dissolved in water to obtain a solution of 144 ml. The solution was loaded onto a 100 g support by spray impregnation in two separate applications. After each spray impregnation, the support was dried at 120 °C for 4 hours, then calcined at 390 °C for 4 hours, and then gradually reduced with hydrogen at a rate of 20 °C / hour. Finally, the support was reduced at 440 °C for 3 hours to obtain catalyst AV-2.

[0641] Example V-3

[0642] 820 g of pseudoboehmite powder (produced by aluminum sulfate method, specific surface area 380 m2 / g, pore volume 1.26 ml / g) and 180 g of titanium dioxide were mixed evenly in a mixer, kneaded and pressed into toothed balls with a diameter of 4 mm using 785 ml of dilute acid water containing 5 vol% nitric acid, dried at 120°C overnight, and then calcined at 820°C for 3 h to prepare the required carrier.

[0643] 134.4 g of cobalt nitrate hexahydrate (industrial grade, 98% purity) and 43.4 g of 50wt% manganese nitrate solution were dissolved in water to obtain a 155 ml solution. The resulting solution was loaded onto a 100 g support by spray impregnation in two separate applications. After each spray impregnation, the support was dried at 120 °C for 4 hours, then calcined at 400 °C for 4 hours, and then gradually reduced with hydrogen at a heating rate of 20 °C / hour. Finally, the support was reduced at 430 °C for 3 hours to obtain catalyst AV-3.

[0644] Example V-4

[0645] 1000 g of pseudoboehmite powder (produced by nitric acid method, specific surface area 380 m2 / g, pore volume 0.96 ml / g) and 200 g of titanium dioxide were mixed evenly in a mixer, kneaded and pressed into strips with a diameter of 5 mm using 785 ml of dilute acid water containing 5 vol% nitric acid, cut into 4 mm lengths, dried at 120°C overnight, and then calcined at 800°C for 4 h to prepare the required carrier.

[0646] 129.2 g of cobalt nitrate hexahydrate (industrial grade, 98% purity) and 4.0 g of silver nitrate (analytical grade) were dissolved in water to make a 162 ml solution. The resulting solution was loaded onto a 100 g support by spray impregnation in two separate applications. After each spray impregnation, the support was dried at 120 °C for 4 hours, then calcined at 400 °C for 4 hours, and then gradually reduced with hydrogen at a rate of 20 °C / hour. Finally, the support was reduced at 430 °C for 3 hours to obtain catalyst AV-4.

[0647] Example V-5

[0648] 1500 g of pseudoboehmite powder (produced by carbonization method, specific surface area 405 m2 / g, pore volume 1.01 ml / g) and 250 g of titanium dioxide were mixed evenly in a mixer, kneaded and pressed into clover shape with 777 ml of dilute acid water containing 5 vol% nitric acid, dried at 120°C overnight, and then calcined at 820°C for 3.5 h to prepare the required carrier.

[0649] 132.6 g of nickel nitrate hexahydrate (industrial grade, 98% purity) and 7.7 g of ammonium perrhenate were dissolved in water to make a 140 ml solution. The resulting solution was loaded onto a 100 g support by spray impregnation in two separate applications. After each spray impregnation, the support was dried at 120 °C for 4 hours, then calcined at 390 °C for 4 hours, and then gradually reduced with hydrogen at a rate of 20 °C / hour. Finally, the support was reduced at 440 °C for 3 hours to obtain catalyst AV-5.

[0650] Example V-6

[0651] 950 g of pseudoboehmite powder (produced by aluminum sulfate method, specific surface area 380 m2 / g, pore volume 0.96 ml / g) and 320 g of titanium dioxide were mixed evenly in a mixer. The mixture was kneaded and pressed into toothed balls with a diameter of 4 mm using 767 ml of dilute acid water containing 5 vol% nitric acid and 2 vol% sulfuric acid. The balls were dried at 120°C overnight and then calcined at 820°C for 5 h to prepare the desired carrier.

[0652] 182.6 g of cobalt nitrate hexahydrate (industrial grade, 98% purity) was dissolved in water to make 170 ml of solution, and 16 g of ammonium molybdate tetrahydrate (analytical grade) was dissolved in water to make 138 ml of solution. The cobalt nitrate solution was loaded onto the obtained 100 g support in two separate spray impregnations. Then, the ammonium molybdate solution was spray impregnated onto the obtained support in one step. After impregnation, the support was dried at 120 °C for 4 hours, then calcined at 400 °C for 4 hours, and then gradually reduced with hydrogen at a heating rate of 20 °C / hour. Finally, the support was reduced at 430 °C for 3 hours to obtain catalyst AV-6.

[0653] Example V-7

[0654] 1000 g of pseudoboehmite powder (produced by aluminum sulfate method, specific surface area 380 m2 / g, pore volume 0.96 ml / g) and 150 g of titanium dioxide were mixed evenly in a mixer. The mixture was kneaded and pressed into toothed balls with a diameter of 4 mm using 770 ml of dilute acid water containing 5 vol% nitric acid and 2 vol% sulfuric acid. The balls were dried at 120°C overnight and then calcined at 820°C for 3.5 h to prepare the required carrier.

[0655] 177.4 g of cobalt nitrate hexahydrate (industrial grade, purity 98%) and 15.9 g of copper nitrate trihydrate (analytical grade) were dissolved in water to make a 140 ml solution. The resulting solution was loaded onto a 100 g support by spray impregnation in two separate applications. After each spray impregnation, the support was dried at 120 °C for 4 hours, then calcined at 400 °C for 4 hours, and then gradually reduced with hydrogen at a heating rate of 20 °C / hour. Finally, the support was reduced at 430 °C for 3 hours to obtain catalyst AV-7.

[0656] Example V-8

[0657] 780 g of pseudoboehmite powder (produced by aluminum sulfate method, specific surface area 380 m2 / g, pore volume 0.96 ml / g) and 220 g of titanium dioxide were mixed evenly in a mixer. The mixture was kneaded and pressed into toothed balls with a diameter of 4 mm using 782 ml of dilute acid water containing 5 vol% nitric acid, 2 vol% hydrofluoric acid and 0.5 wt% lanthanum nitrate. The balls were dried at 120°C overnight and then calcined at 820°C for 4 h to prepare the desired carrier.

[0658] 134.4 g of cobalt nitrate hexahydrate (industrial grade, 98% purity) and 30.3 g of zinc nitrate hexahydrate (analytical grade) were dissolved in water to make a 160 ml solution. The resulting solution was loaded onto a 100 g support by spray impregnation in two separate applications. After each spray impregnation, the support was dried at 120 °C for 4 hours, then calcined at 400 °C for 4 hours, and then gradually reduced with hydrogen at a rate of 20 °C / hour. Finally, the support was reduced at 430 °C for 3 hours to obtain catalyst AV-8.

[0659] Comparative Example V-1

[0660] The catalyst was prepared according to the method of Example V-3, except that the amount of boehmite powder was 500 g, the amount of titanium dioxide was 500 g, and 12.8 g of KNO3 was added during the kneading process to obtain catalyst DV-1.

[0661] Comparative Example V-2

[0662] The catalyst was prepared according to the method of Example V-2, except that the amount of boehmite powder was 900 g and the amount of titanium dioxide was 100 g, thus obtaining catalyst DV-2.

[0663] Test Case V-1

[0664] The elemental composition of the catalyst was analyzed by plasma emission spectrometry. The results showed that all the sulfur in the titanium dioxide was retained in the support and the content of other elements was basically the same as that of the feed amount. The catalyst prepared above was characterized by NH3-TPD, CO2-TPD and BET nitrogen adsorption-desorption methods. The results are shown in Table V-1.

[0665] Table V-1 Properties of catalysts in each example and comparative example catalyst Catalyst composition ammonia adsorption capacity CO2 adsorption capacity Specific surface area Pore ​​volume <4nm percentage >10 nm proportion Doping elements and their relative content, g mmol / g mmol / g m 2 / g ml / g % % AV-1 Co / Al2O3-TiO2 0.33 0.16 161 0.65 18 8 S 0.83 AV-2 Ni / Al2O3-TiO2 0.35 0.13 159 0.68 15 9.5 S 0.69 AV-3 Co-Mn / Al2O3-TiO2 0.38 0.13 170 0.71 14 10 S 1.54 AV-4 Co-Ag / Al2O3-TiO2 0.37 0.14 172 0.68 12 11 S 0.53 AV-5 Ni-Re / Al2O3-TiO2 0.36 0.16 168 0.66 11 12 S 0.46 AV-6 Co-Mo / Al2O3-TiO2 0.32 0.09 143 0.59 8 14 S 1.75 AV-7 Co-Cu / Al2O3-TiO2 0.32 0.1 139 0.61 17 7 S 1.67 AV-8 Co-Zn / Al2O3-TiO2 0.34 0.12 157 0.68 15 12 S 1.83 / F 0.5 / La 0.6 DV-1 Co-Mn-K / Al2O3-TiO2 0.16 0.11 131 0.57 20 17 K 0.6 DV-2 Co-Mn / Al2O3 0.24 0.07 155 0.75 twenty one 16 without

[0666] Test Case V-2

[0667] 100 mL of each of the prepared catalysts AV-1 to AV-8 and catalysts DV-1 and DV-2 were measured and placed in a fixed-bed reactor. The reactor was activated with hydrogen at 220°C for 2 hours, then cooled to 168°C. The system pressure was increased to 12.5 MPa with hydrogen. Ammonia was then metered and fed into the reaction system using a metering pump. After preheating to 150°C, the ammonia entered the reactor. Molten 1,6-hexanediol was also metered and fed into the reactor. Hydrogen was steadily introduced via a gas mass flow meter. The molar ratio of hydrogen:ammonia:1,6-hexanediol was 3:12:1, and the liquid hourly space velocity (LHSV) of 1,6-hexanediol was 0.4. h-1, a catalytic amination reaction was carried out in the reactor at a reaction temperature of 175℃ and a reaction pressure of 12.5 MPa. After the reaction conditions stabilized for 2 hours, the reaction solution was sampled and analyzed. The analysis results are listed in Table V-2.

[0668] The sampling and analysis method is gas chromatography analysis, and calibration is performed by using the correction factor of the prepared standard sample.

[0669] The conversion rate and selectivity are calculated based on the mole content of each component in the reaction solution. The specific calculation method is the same as that in Test Example I-2.

[0670] Table V-2 Test results of catalysts in each example and comparative example catalyst Conversion rate % Selectivity% Hexamethylenediamine Cycloheximine aminohexanol other AV-1 87 47.5 20.6 28.1 3.8 AV-2 89 47.2 19.1 29.3 4.4 AV-3 93 49.8 20.4 27.1 2.7 AV-4 92 50.9 18.4 27.9 2.8 AV-5 91 49.7 20.6 26.8 2.9 AV-6 91 48.8 16.9 30.7 3.6 AV-7 85 46.7 19.2 29.5 4.6 AV-8 90 49.6 19.6 28.2 2.6 DV-1 78 41.3 23.7 29.1 8.7 DV-2 69 36.5 25.2 36.4 6.5

[0671] As can be seen from the data in the table above, the "other" impurities of catalysts DV-1 and DV-2 are significantly higher than those of other catalysts, and their conversion rates are also much lower.

[0672] After evaluating each catalyst for 196 hours, the catalysts were unloaded for characterization. It was found that the specific surface area and pore volume of catalysts AV-1 to AV-8 did not change significantly, and the amount of carbon deposit was not obvious. However, the specific surface area of ​​catalysts DV-1 and DV-2 decreased by 7% and 9%, respectively, and the pore volume decreased by 7%. The amount of carbon deposit was 5.6 wt% and 6.7 wt%, respectively. This indicates that the catalysts of this application have more stable catalytic performance and can accelerate the reaction rate, reduce carbon deposit, and alleviate pore blockage.

[0673] Test Case V-3

[0674] 100 mL of the prepared catalyst was measured and placed in a fixed-bed reactor. Activation was performed at 220°C for 2 hours using hydrogen, followed by cooling to 168°C. The system pressure was increased to 8 MPa using hydrogen. Ammonia was then metered and fed into the reaction system using a metering pump. After preheating to 150°C, the ammonia entered the upper part of the reactor. A mixture of hexanediol, cycloheximine, and 6-amino-1-hexanol (hexanediol: 50 wt%; cycloheximine: 32 wt%; 6-amino-1-hexanol: 18 wt%) was 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 the mixture was 3:18:1, and the liquid hourly space velocity (LHSV) of the mixture was 0.5 h⁻¹. Catalytic amination was carried out in the reactor at a temperature of 185°C and a pressure of 8 MPa. MPa, after the reaction conditions stabilized for 2 hours, the reaction solution was sampled and analyzed (analysis conditions and conversion and selectivity calculation methods were the same as in test case V-2), and the analysis results are shown in Table V-3.

[0675] Table V-3 Results of Test Case V-3 catalyst Hexanediol conversion rate % Selectivity% Hexamethylenediamine Cycloheximine aminohexanol other AV-1 94.9 92.8 0.8 3.8 2.6 AV-2 94.7 93.6 0.7 2.9 2.8 AV-3 97.7 96.4 0.8 1.8 1 AV-4 97.2 97 0.6 1.7 0.7 AV-5 96.6 96.1 0.6 2.1 1.2 AV-6 96.8 94.5 0.7 2.2 2.6 AV-7 94.6 93.9 0.5 2.5 3.1 AV-8 96.1 95.1 0.6 2.3 2 DV-1 79.5 85.2 1.6 5.6 7.6 DV-2 70.6 86.3 2.9 2.6 8.2

[0676] As can be seen from the data in the table above, compared with catalysts DV-1 and DV-2, the catalyst of this application can achieve higher hexanediol conversion and hexanediamine selectivity.

[0677] The preferred embodiments of this application have been described in detail above. However, this application is not limited to the specific details in the above embodiments. Within the scope of the technical concept of this application, various simple modifications can be made to the technical solution of this application, and these simple modifications all fall within the protection scope of this application.

[0678] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable way without contradiction. In order to avoid unnecessary repetition, this application will not describe the various possible combinations separately.

[0679] Furthermore, various different embodiments of this application can be combined in any way, as long as they do not violate the spirit of this application, they should also be regarded as the content of this application. [Simplified Explanation of the Diagram]

[0017] None

Claims

1. A catalyst suitable for catalytic amination to prepare organic amines, comprising an aluminum- and / or silicon-containing inorganic porous support and an active metal component supported on the support, the active metal component comprising at least one metal selected from Group VIII and Group IB, wherein the ammonia adsorption capacity of the support, as measured by NH3-TPD, is 0.3-0.6 mmol / g, wherein the support comprises a matrix and a dopant element, the matrix comprising a first support component and an optional second support component, wherein the first support component is selected from alumina, silicon oxide, molecular sieves, aluminum silicate, or combinations thereof, the second support component is selected from diatomaceous earth and titanium dioxide, and the dopant element in the support is derived from metal cations and / or anions and excludes sodium and chloride ions; the metal cation is selected from calcium, magnesium, potassium, bismuth, strontium, barium, lanthanum, or combinations thereof; the anion is selected from borate, fluoride, phosphate, sulfate, selenate, or combinations thereof, wherein the pore size of the support is 7-27 mm. The percentage of pore volume in the nm range to the total pore volume of the carrier is 70-90%, and the percentage of pore volume in the carrier with a pore size less than 7 nm is 0-10%.

2. The catalyst as claimed in claim 1, wherein the carbon dioxide adsorption capacity of the support is 0.05-0.3 mmol / g.

3. The catalyst as claimed in claim 1, wherein the content of the dopant element in the support is 0.03-6 by weight, based on the total weight of the matrix.

4. The catalyst as claimed in claim 1, wherein the specific surface area of ​​the support is 120-210 m² / g.

5. The catalyst as claimed in claim 1, wherein the pore volume of the support is 0.45-1.1 ml / g.

6. The catalyst as claimed in claim 1, wherein the content of the active metal component is 10-42 g relative to 100 g of matrix.

7. The catalyst of claim 1 further comprises a metal promoter supported on the support, the metal promoter comprising at least one metal selected from Cr, Mo, W, Mn, Re, Cu, Ag, Au, Zn, La and Ce; and the metal promoter is present in an amount of 0.5-8 g relative to 100 g of matrix.

8. The catalyst as claimed in claim 7, wherein: The metal additive comprises a combination of at least one Group VIIB metal and at least one Group IB metal, wherein the weight ratio of the Group VIIB metal to the Group IB metal is 0.1-12:1 based on the metal elements; or the metal additive comprises a combination of at least one Group VIIB metal and at least one Group IIB metal, wherein the weight ratio of the Group VIIB metal to the Group IIB metal is 0.3-6:1 based on the metal elements; or the metal additive comprises a combination of at least one Group VIB metal, at least one Group IB metal, and at least one Group IIB metal, wherein the weight ratio of the Group VIB metal, Group IB metal, and Group IIB metal is 0.2-8:0.2-8:1 based on the metal elements.

9. The catalyst as claimed in claim 8, wherein: The Group VIIB metals are selected from manganese, rhenium, or combinations thereof; the Group IB metals are selected from copper, silver, gold, or combinations thereof; the Group IIB metal is zinc; and the Group VIB metals are selected from molybdenum, tungsten, or combinations thereof.

10. A method for preparing a catalyst as claimed in any one of claims 1-9, comprising the steps of: 1) providing an inorganic porous support containing aluminum and / or silicon, said support having an ammonia adsorption capacity of 0.3-0.6 mmol / g as determined by NH3-TPD, wherein providing the inorganic porous support containing aluminum and / or silicon comprises sequentially shaping, drying and calcining a mixture containing a dopant element and a matrix or its precursor to obtain said support; 2) loading said active metal component and optionally a metal additive onto said support; and 3) subjecting the material obtained in step 2) to heat treatment and optionally reduction treatment to obtain said catalyst.

11. The method as described in claim 10, wherein, The matrix comprises a first carrier component and an optional second carrier component, wherein the first carrier component is selected from alumina, silica, molecular sieve, aluminum silicate, or combinations thereof, and the second carrier component is selected from diatomaceous earth, titanium dioxide, or combinations thereof. The precursor of the first carrier component is boehmite having a specific surface area of ​​250-410 m² / g and a pore volume of 0.7-1.3 ml / g. The doping element is selected from metallic elements, non-metallic elements, or combinations thereof, excluding sodium and chlorine. The metallic element is selected from calcium, magnesium, potassium, bismuth, strontium, barium, lanthanum, or combinations thereof. The non-metallic element is selected from boron, fluorine, phosphorus, sulfur, selenium, or combinations thereof.

12. The method of claim 11, wherein a carrier modifier is used to provide the dopant element, the carrier modifier comprising at least one compound capable of providing cations and / or anions, wherein, The cation is selected from calcium ion, magnesium ion, potassium ion, bismuth ion, strontium ion, barium ion, lanthanum ion, or a combination thereof; the anion is selected from borate ion, fluoride ion, phosphate ion, sulfate ion, selenate ion, or a combination thereof.

13. The method of claim 10, wherein the loading in step 2) comprises impregnating the carrier with a solution of a precursor comprising the active metal component and optionally a metal auxiliaries.

14. A method for preparing organic amines, comprising: The organic amine is obtained by contacting an amination feedstock, an amination reagent, and a catalyst as described in any one of claims 1-9 in the presence of hydrogen gas. The amination raw material is selected from ethanol, acetaldehyde, n-propanol, propionaldehyde, isopropanol, n-butanol, butyraldehyde, isobutanol, isobutyraldehyde, 2-ethylhexanol, 2-ethylhexanol, octanol, octanol, dodecanol, dodecanol, hexadecanol, hexadecanol, cyclopentanol, cyclohexanol, cyclooctanol, cyclododecanol, benzyl alcohol, benzaldehyde, phenethyl alcohol, phenylacetaldehyde, 1,4-butanediol, 1,4-butanedialdehyde, 1,5-pentanediol, 1,5-pentanedialdehyde, 1,6-hexanediol, 1,6-hexanedialdehyde, 1,8-octanediol, 1,8-octanedialdehyde, 1,12-dodecanediol, 1,12-dodecanedialdehyde, ethanolamine, propanolamine, isopropanolamine, 6-aminohexanol, diethanolamine, diisopropanolamine, dimethylethanolamine, acetone, ethylene glycol, 1,3-propanediol, or combinations thereof. The amination reagent is selected from ammonia, C1-12 primary amines, C2-12 secondary amines, or combinations thereof.

15. The method as described in claim 14, wherein, The conditions for the amination reaction include: a molar ratio of hydrogen, amination reagent, and amination feedstock of 1-5 : 2-35 : 1; a temperature of 105-220℃; a pressure of 0.8-25 MPa; and a liquid hourly space velocity of the amination feedstock of 0.06-1 m3 / (m3·h).

16. The method as described in request item 15, wherein: When the amination feedstock is a monohydric alcohol, the amination reaction conditions include: a molar ratio of hydrogen, amination reagent, and amination feedstock of 1-4:2-8:1, a temperature of 130-210℃, a pressure of 1-4 MPa, and a liquid hourly space velocity (LHSV) of the amination feedstock of 0.1-0.8 m³ / (m³·h); when the amination feedstock is a ketone or aldehyde, the amination reaction conditions include: a molar ratio of hydrogen, amination reagent, and amination feedstock of 1-4:2-6:1, a temperature of 105-180℃, a pressure of 0.7-3.5 MPa, and a LHSV of the amination feedstock of 0.1-1 m³ / (m³·h); when the amination feedstock is an alkanolamine, the amination reaction conditions include: a molar ratio of hydrogen, amination reagent, and amination feedstock of 1-4:3-20:

1.

1. The temperature is 130-200℃, the pressure is 1-18 MPa, and the liquid hourly space velocity (LHSV) of the amination feedstock is 0.06-0.8 m³ / (m³·h); when the amination feedstock is a diol, the conditions for the amination reaction include: a molar ratio of hydrogen, amination reagent, and amination feedstock of 1-4 : 3-35 : 1, a temperature of 130-220℃, a pressure of 4-25 MPa, and a LHSV of the amination feedstock of 0.06-0.8 m³ / (m³·h).