Amination catalysts, and preparation and use thereof

Abstract

A catalyst suitable for producing organic amines by catalytic amination, its preparation, and its use are disclosed. The catalyst comprises an inorganic porous support containing aluminum and / or silicon and an active metal component supported on the support. The active metal component comprises at least one metal selected from the group consisting of Group VIII metals and Group IB metals. The support has an ammonia adsorption capacity of 0.25 to 0.65 mmol / g as measured by the NH3-TPD test. When the catalyst is used in a reaction for producing organic amines by catalytic amination, the catalyst exhibits improved catalytic performance.

Description

Detailed Description of the Invention

[0001] [Technical Field] This application relates to the field of amination reactions, and in particular to catalysts, their preparation and use for producing organic amines by catalytic amination.

[0002] [Background technology] Amines are very important industrial organic compounds and are widely used in various fields (e.g., as solvents, medical intermediates, resin raw materials, textile additives, insecticides, rubber stabilizers, preservatives, and also in cleaning and plastics processing). The three main processes for producing amines are the hydroamination of carbonyl compounds, the hydroamination of alcohols, and the hydrogenation of nitriles. Hydroamination of carbonyl compounds, for example, involves the reaction of acetone, hydrogen, and ammonia to form isopropylamine. Examples of alcohol hydroamination include the hydroamination of ethanol with ammonia in the presence of hydrogen to form ethylamine, the hydroamination of isopropanol with ammonia in the presence of hydrogen to form isopropylamine, the hydroamination of butanol with ammonia in the presence of hydrogen to form butylamine, and the hydroamination of hexanediol with ammonia in the presence of hydrogen to form hexanediamine. Examples of nitrile hydrogenation include the hydrogenation of acetonitrile to ethylamine and the hydrogenation of adiponitrile to hexanediamine.

[0003] US Patent No. 4,409,399 discloses a process for producing fatty amines, in which the catalyst used consists of (1) copper oxide or hydroxide, (2) nickel oxide or hydroxide, and (3) a Group IIA metal oxide or hydroxide.

[0004] Chinese Patent Application No. CN102658162A discloses a catalyst for synthesizing ethyleneamines and a process for producing the same. The catalyst consists of three components: a main active component, a cofactor, and an aminating support. The main active component is one or more selected from Ni and Co, accounting for 1-40% of the total weight of the catalyst. The cofactor is one or more selected from the group consisting of Fe, Cu, Ru, Re, K, Zn, and B and their oxides, accounting for 0.1-20% of the total weight of the catalyst. The aminating support is obtained by aminating one or more supports selected from the group consisting of SiO2 and Al2O3.

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

[0006] Summary of the Invention It is an object of the present application to provide a catalyst useful for producing organic amines by catalytic amination, its preparation and use, which exhibits improved performance (e.g., at least one of improved catalytic activity, improved reaction conversion, improved product selectivity, and improved catalyst stability) when used for the amination reaction.

[0007] To achieve the above-mentioned object, in one aspect, the present application provides a catalyst useful for producing organic amines by catalytic amination, the catalyst 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 metals and Group IB metals; and the support has an ammonia adsorption capacity of 0.25 to 0.65 mmol / g as measured by an NH3-TPD test.

[0008] Preferably, the support comprises a matrix comprising a first support component and, optionally, a second support component, and a doping element, wherein the first support component is selected from alumina, silica, molecular sieve, aluminosilicate, or a combination thereof, and the second support component is selected from diatomaceous earth and titania, and the doping element is selected from a metal element, a non-metal element, or a combination thereof, excluding sodium and chlorine, wherein the metal element is at least one selected from the group consisting of Group IA metal elements, Group IIA metal elements, Group VA metal elements, and Lanthanide metal elements; and the non-metal element is at least one selected from the group consisting of Group IIIA non-metal elements, Group VA non-metal elements, Group VIA non-metal elements, and Group VIIA non-metal elements.

[0009] Preferably, the catalyst further comprises a metal promoter supported on the support, the metal promoter comprising at least one metal selected from the group consisting of Group VIB metals, Group VIIB metals, Group IB metals, Group IIB metals and Lanthanide metals.

[0010] In another aspect, there is provided a method for producing the catalyst of the present application, comprising the following steps 1) to 3): 1) providing an inorganic porous carrier containing aluminum and / or silicon, which has an ammonia adsorption capacity of 0.25 to 0.65 mmol / g as measured by an NH3-TPD test; 2) supporting the active metal component and, optionally, the metal cocatalyst on the support; and 3) subjecting the material obtained in step 2) to a heat treatment and optionally a reduction treatment to obtain said catalyst.

[0011] In yet another aspect, the present application provides a process for producing an organic amine, comprising: contacting an amination feedstock, an aminating agent, and a catalyst for an amination reaction according to the present application in the presence of hydrogen to obtain an organic amine, wherein the amination feedstock is selected from the group consisting of an alcohol, a ketone, an alcohol amine, an aldehyde, and combinations thereof; and the aminating agent is selected from the group consisting of ammonia, a primary amine, a secondary amine, and combinations thereof.

[0012] When the catalysts of the present application are used to produce organic amines by catalytic amination, they exhibit improved performance, particularly improved catalytic activity, reaction conversion, product selectivity and / or catalyst stability.

[0013] Other features and advantages of the present application are explained in detail in the detailed description that follows.

[0014] Detailed Description of the Invention The present application will be described in more detail below with reference to specific embodiments thereof. It should be noted that the specific embodiments of the present application are provided for illustrative purposes only and are not intended to be limiting in any way.

[0015] Any specific numerical value, including the endpoints of a numerical range, set forth in the context of this application should not be limited to that exact value, but should also be interpreted as encompassing all values ​​near that exact value (e.g., all values ​​within ±5% of that exact value). Furthermore, with respect to any numerical range described herein, any combination between the endpoints of the range, between each endpoint and any specific value within the range, or between any two specific values ​​within the range, can be made to provide one or more new numerical ranges, and such new numerical ranges should also be considered to be specifically set forth in this application.

[0016] Unless otherwise specified, terms used herein have the same meaning as commonly understood by one of ordinary skill in the art; if a term is defined herein and that definition differs from the common understanding in the art, the definition provided herein shall prevail.

[0017] In this application, the ammonia adsorption capacity of the support and catalyst is measured by the NH3-TPD test, and the ammonia adsorption capacity is expressed as the measured amount of ammonia desorption.

[0018] In this application, the specific surface area, pore volume and proportion of pores with different pore diameters of the support are measured by nitrogen adsorption-desorption method in accordance with GB / T6609.35-2009.

[0019] As used herein, the term "C2-C20" means having 2 to 20 carbon atoms (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms). Similarly, the term "C1-C12" means having 1 to 12 carbon atoms.

[0020] In this application, the particle size of the active metal component and the metal promoter is measured by XRD analysis.

[0021] In this application, pressures given are gauge pressures unless otherwise specified.

[0022] In the context of this application, in addition to the matters explicitly mentioned, any matter or matters not mentioned shall be deemed to be the same as those known in the art without any modifications. Furthermore, any of the embodiments described herein can be freely combined with one or more other embodiments described herein. Any technical solution or idea obtained in this way shall be considered to be part of the original disclosure or original description of this application, and shall not be considered to be new matter not disclosed or anticipated herein, unless it is obvious to a person skilled in the art that such a combination is obviously unreasonable.

[0023] All patent and non-patent literature cited herein, including but not limited to textbooks and journal articles, is hereby incorporated by reference in its entirety.

[0024] As described above, in a first aspect, the present application provides a catalyst useful for producing organic amines by catalytic amination, 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 metals and Group IB metals; and the support has an ammonia adsorption capacity of 0.25 to 0.65 mmol / g as measured by the NH3-TPD test.

[0025] According to the present 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 a combination thereof, more preferably selected from cobalt, nickel, or a combination thereof.

[0026] In the catalyst of the present application, a Group IB metal (e.g., copper, etc.) can be used alone as the active metal component, in which case it is typically used in a relatively large amount; a Group IB metal can also be used in combination with a Group VIII metal, in which case it is typically used in a relatively small amount. When used in combination with a Group VIII metal (e.g., cobalt, nickel, palladium, etc.), the Group IB metal is generally referred to herein as a metal cocatalyst.

[0027] In a preferred embodiment, the support has an ammonia adsorption capacity of 0.3 to 0.6 mmol / g as measured by the NH3-TPD test.

[0028] In a preferred embodiment, the support comprises a matrix comprising a first support component and, optionally, a second support component, and a doping element, wherein the first support component is selected from alumina, silica, molecular sieve, aluminosilicate, or a combination thereof, and the second support component is selected from diatomaceous earth and titania, and the doping element is selected from a metal element, a non-metal element, or a combination thereof, excluding sodium and chlorine, wherein the metal element is at least one selected from the group consisting of Group IA metal elements, Group IIA metal elements, Group VA metal elements, and lanthanide metal elements, preferably at least one selected from the group consisting of calcium, magnesium, potassium, bismuth, strontium, barium, and lanthanum; and the non-metal element is at least one selected from the group consisting of Group IIIA non-metal elements, Group VA non-metal elements, Group VIA non-metal elements, and Group VIIA non-metal elements, preferably at least one selected from the group consisting of boron, fluorine, phosphorus, sulfur, and selenium.

[0029] In a further preferred embodiment, the doping elements in the carrier are derived from metal cations and acid radical ions, but do not include sodium ions or chloride ions; the metal cation is at least one selected from the group consisting of Group IA metal ions, Group IIA metal ions, Group VA metal ions and lanthanide metal ions, preferably at least one selected from the group consisting of calcium ions, magnesium ions, potassium ions, bismuth ions, strontium ions, barium ions and lanthanum ions; and the acid radical ion is at least one selected from non-metal acid radical ions, preferably at least one selected from the group consisting of borate ions, fluoride ions, phosphate ions, sulfate ions and selenate ions.

[0030] In a preferred embodiment, the carrier has at least one of the following characteristics: The support has a carbon dioxide adsorption capacity of 0.05 to 0.4 mmol / g, preferably 0.05 to 0.3 mmol / g, more preferably 0.06 to 0.2 mmol / g, and when the support has a carbon dioxide adsorption capacity within the above range, it is preferable to improve the product selectivity of the catalyst and reduce the production of by-products; the doping element is present in the support in an amount of 0.03 to 6% by weight, preferably 0.05 to 6% by weight, more preferably 0.08 to 4% by weight, relative to the total weight of the matrix; The carrier is 120 to 240 m 2 / g, preferably 120 to 210 m 2 / g, more preferably 125 to 200m 2 / g specific surface area; The carrier has a pore volume of 0.45 to 1.2 ml / g, preferably 0.45 to 1.1 ml / g, more preferably 0.5 to 1 ml / g; The ratio of the pore volume of pores having a pore diameter in the range of 7 to 27 nm to the pore volume of the support is more than 65%, preferably 70% or more, more preferably 70 to 90%, and the ratio of the pore volume of pores having a pore diameter of less than 7 nm to the pore volume of the support is preferably 0 to 10%, for example 0 to 8%; when the support has the above-mentioned pore diameter distribution, it is preferable to increase the surface diffusivity of the catalyst and improve the activity and product selectivity of the catalyst; The matrix of the support comprises a combination of alumina and titania in a weight ratio of 1.5 to 5:1, preferably 2 to 4.5:1; and The alumina content in the support is 70% by weight or more, preferably 75% by weight or more, and more preferably 80 to 100% by weight, based on the total weight of the matrix.

[0031] In a preferred embodiment of the catalyst of the present application, the active metal component is present in an amount of 5 to 46 g, preferably 10 to 42 g, for example 13 to 40 g, per 100 g of the matrix.

[0032] In a preferred embodiment, the catalyst further comprises a metal promoter supported on the support, the metal promoter comprising at least one metal selected from the group consisting of Group VIB metals, Group VIIB metals, Group IB metals, Group IIB metals, and Lanthanide metals, preferably at least one metal selected from the group consisting of Cr, Mo, W, Mn, Re, Cu, Ag, Au, Zn, La, and Ce. More preferably, the metal promoter is present in an amount of 0 to 10 g, preferably 0.1 to 10 g, more preferably 0.5 to 8 g, per 100 g of the matrix.

[0033] In some further preferred embodiments, the metal promoter 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, calculated as elemental metals, is 0.05 to 15:1, preferably 0.1 to 12:1; or the metal promoter 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 0.2 to 20:1, preferably 0.3 to 6:1; or the metal promoter comprises a combination of at least one Group VIB metal, at least one Group IB metal, and at least one Group IB metal, wherein the weight ratio of the Group VIB metal to the Group IB metal to the Group IIB metal is 0.1 to 10:0.1 to 10:1, preferably 0.2 to 8:0.2 to 8:1. Particularly preferably, the Group VIIB metal is selected from manganese and / or rhenium, the Group IB metal is at least one selected from the group consisting 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.

[0034] According to the present application, the support for the catalyst can be obtained by any method known in the art that is useful for producing a support having the above-mentioned properties, although not particularly limited thereto. Preferably, the support can be prepared by a method comprising the following steps: successively molding, drying, and calcining a mixture containing a doping element and a matrix or a precursor thereof to obtain a support, wherein the matrix comprises a first support component and, optionally, a second support component, wherein the first support component is selected from alumina, silica, molecular sieves, aluminosilicates, or a combination thereof, and the second support component is selected from diatomaceous earth, titanium dioxide, or a combination thereof. The molecular sieve can be, for example, ZSM-5 molecular sieve or ZSM-11 molecular sieve. When a matrix precursor is used, the alumina precursor can be pseudoboehmite, and the silica precursor can be silicic acid, orthosilicic acid, or silica gel.

[0035] In the aforementioned method for producing a carrier, the matrix precursor is preferably pseudo-boehmite. Pseudo-boehmite can be prepared by at least one of the carbonization method, organoaluminum hydrolysis method, aluminum sulfate method, and nitric acid method. The specific surface area of ​​pseudo-boehmite is preferably 250 to 410 m. 2 / g, more preferably 260 to 400m 2 / g, more preferably 260 to 380 m 2 / g, e.g., 250-330m 2 / g or 265-410m 2 The pseudoboehmite preferably has a pore volume of 0.7 to 1.3 ml / g, more preferably 0.7 to 1.2 ml / g, and even more preferably 0.8 to 1.2 ml / g, for example, 0.8 to 1.3 ml / g or 0.78 to 1.2 ml / g. By using pseudoboehmite with a specific pore structure, a catalyst with better performance can be obtained.

[0036] In the above-mentioned method for producing a support, if the raw material providing the precursor of the matrix already contains the desired amount of doping element, molding can be simply carried out using such raw material, and if the raw material providing the precursor of the matrix does not contain the doping element or the content of the doping element is low (insufficient), additional doping element can be introduced.

[0037] In the aforementioned method for preparing the support, the doping element may be provided using a support modifier comprising at least one compound capable of providing a cation (excluding sodium ions) and / or anion (excluding chloride ions), wherein the cation is at least one selected from the group consisting of Group IA cations, Group IIA metal ions, Group VA metal ions, and lanthanide metal ions, preferably at least one selected from the group consisting of calcium ions, magnesium ions, potassium ions, bismuth ions, strontium ions, barium ions, and lanthanum ions; and the anion is at least one selected from the group consisting of non-metallic acid radical ions, preferably at least one selected from the group consisting of borate ions, fluoride ions, phosphate ions, sulfate ions, and selenate ions.

[0038] Preferably, the support modifier is at least one selected from the group consisting of boric acid, nickel borate, cobalt borate, potassium borate, hydrofluoric acid, potassium fluoride, cobalt fluoride, nickel fluoride, phosphoric acid, aluminum phosphate, tripotassium 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.

[0039] In the above-mentioned method for producing the carrier, the forming method may be selected from kneading, rolling, peeling, and the like.

[0040] In the aforementioned method for preparing the support, the support modifier is used in an amount such that the doping element is present in an amount of 0.03 to 6 wt %, preferably 0.05 to 6 wt %, more preferably 0.08 to 4 wt %, e.g., 0.08 to 1 wt %, based on the total weight of the matrix (e.g., 0.08 wt %, 0.1 wt %, 0.2 wt %, 0.3 wt %, 0.4 wt %, 0.45 wt %, 0.5 wt %, 0.55 wt %, 0.6 wt %, 0.7 wt %, 0.8 wt %, 0.85 wt %, 0.9 wt %, 0.95 wt %, 1 wt %, or a value between any two of them). Those skilled in the art can determine the amount of a component ingredient (e.g., support modifier) ​​based on the amount of said component in the final support; therefore, the amounts of some ingredients are not given herein.

[0041] In the aforementioned method for producing a carrier, the drying conditions are, for example, a temperature of 80 to 150°C (e.g., 80°C, 85°C, 90°C, 95°C, 100°C, 110°C, 115°C, 120°C, 125°C, 130°C, 140°C, 150°C, or a value between any two of them), for example, 100 to 150°C, 80 to 120°C, or 100 to 120°C, and 6 to 20 hours (e.g., 6 hours, 7 hours, 7.5 hours, 8 hours). , 8.5 hours, 9 hours, 9.5 hours, 10 hours, 10.5 hours, 10 hours, 11 hours, 11.5 hours, 12 hours, 12.5 hours, 13 hours, 14 hours, 14.5 hours, 15 hours, 15.5 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, or a value between any two thereof), for example, 10-20 hours, 5-15 hours, or 8-12 hours.

[0042] In the above-mentioned method for producing a carrier, the calcination conditions are 500 to 1100°C (for example, 600°C, 650°C, 680°C, 700°C, 750°C, 800°C, 850°C, 900°C, 950°C, 990°C, 1000°C, 1050°C, 1100°C, or a value between any two of them), for example, 600 to 1100°C, 550 to 1050°C, 530 to 1000°C, or 550 to 1000°C. The baking time may include a baking time of 2 to 20 hours (e.g., 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 9.5 hours, 10 hours, 10.5 hours, 11 hours, 12 hours, 15 hours, 18 hours, 20 hours, or a value between any two thereof), for example, 4 to 20 hours, 4 to 10 hours, or 5 to 8 hours.

[0043] The catalyst of the present application can be used after reduction. For example, it can be reduced using a hydrogen-containing gas at 350 to 500°C, preferably 350 to 450°C, e.g., 400 to 450°C. The hydrogen-containing gas can be pure hydrogen gas or hydrogen gas diluted with an inert gas (e.g., a mixture of nitrogen and hydrogen). The reduction temperature is gradually increased during the reduction, and the temperature increase is preferably not too rapid (e.g., 20°C or less per hour). The reduction time can be determined by observing the production of HO in the reduction system. That is, when no new HO is produced in the reduction system, the reduction is terminated. Those skilled in the art can select the reduction time accordingly, but a detailed description thereof will be omitted herein for brevity (e.g., the reduction time can be 2 to 5 hours at the highest temperature). The reduction can be carried out directly in the reactor, followed by a catalytic reaction. The reduction can also be carried out in a separate reactor, also known as extra-reactor reduction. Before the catalyst is discharged from the reactor, it may be reduced with a gas mixture containing oxygen and then passivated. The passivation temperature is, for example, 10 to 60°C, particularly 20 to 40°C. The catalyst that has undergone extra-reactor reduction and passivation can be activated, for example, at 150 to 250°C, preferably 170 to 200°C, before using hydrogen or a mixture of hydrogen and nitrogen. The activation time can be determined by observing the generation of HO in the activation system. That is, when no new HO is generated in the activation system, activation is terminated. Those skilled in the art can select the activation time accordingly, but a detailed description thereof will be omitted herein for brevity. For example, the activation time at the highest temperature may be, for example, 1 to 5 hours, preferably 2 to 3 hours. Alternatively, the catalyst can be used without activation, depending on the degree to which the active metal component and metal promoter of the catalyst have been oxidized.

[0044] In a second aspect, there is provided a method for producing the catalyst of the present application, comprising the following steps 1) to 3): 1) providing an inorganic porous carrier containing aluminum and / or silicon, which has an ammonia adsorption capacity of 0.25 to 0.65 mmol / g as measured by an NH3-TPD test; 2) supporting the active metal component and, optionally, the metal cocatalyst on the support; and 3) subjecting the material obtained in step 2) to a heat treatment and optionally a reduction treatment to obtain said catalyst; In a preferred embodiment, the support has an ammonia adsorption capacity of 0.3 to 0.6 mmol / g as measured by the NH3-TPD test.

[0045] In a preferred embodiment, the "step of providing an inorganic porous support containing aluminum and / or silicon" in step 1) comprises a step of successively shaping, drying and calcining a mixture containing a doping element and a matrix or a precursor thereof to obtain the support, wherein the matrix comprises a first support component and optionally a second support component, the first support component being selected from alumina, silica, molecular sieve, aluminosilicate or a combination thereof, and the second support component being selected from diatomaceous earth, titanium white powder or a combination thereof, preferably the first support component is alumina, and the precursor of the first support component is 250 to 410 m 2 / g, preferably 260 to 400m 2 / g, more preferably 260 to 380 m 2The pseudo-boehmite has a specific surface area of ​​0.7 to 1.3 ml / g, preferably 0.7 to 1.2 ml / g, and a pore volume of 0.8 to 1.2 ml / g; the doping element is selected from a metal element, a non-metal element, or a combination thereof, excluding sodium and chlorine, the metal element being at least one selected from the group consisting of Group IA metal elements, Group IIA metal elements, Group VA metal elements, and lanthanide metal elements, preferably at least one selected from the group consisting of calcium, magnesium, potassium, bismuth, strontium, barium, and lanthanum, and the non-metal element being at least one selected from the group consisting of Group IIIA non-metal elements, Group VA non-metal elements, Group VIA non-metal elements, and Group VIIA non-metal elements, preferably at least one selected from the group consisting of boron, fluorine, phosphorus, sulfur, and selenium.

[0046] In a further preferred embodiment, the doping element is provided using a support modifier, and the doping element and the support modifier may be selected as described above in the first aspect, a detailed description of which is omitted herein for brevity. Even more preferably, the support modifier is used in an amount such that the resulting support has a doping element content of 0.03 to 6 wt. %, preferably 0.05 to 6 wt. %, more preferably 0.08 to 4 wt. %, for example 0.08 to 1 wt. % (e.g., 0.08 wt. %, 0.1 wt. %, 0.2 wt. %, 0.3 wt. %, 0.4 wt. %, 0.45 wt. %, 0.5 wt. %, 0.55 wt. %, 0.6 wt. %, 0.7 wt. %, 0.8 wt. %, 0.85 wt. %, 0.9 wt. %, 0.95 wt. %, 1 wt. %, or a value between any two thereof), based on the total weight of the matrix.

[0047] In a further preferred embodiment, the shaping method may be selected from kneading, rolling, peeling, and the like.

[0048] In a more preferred embodiment, the drying conditions in step 1) include a temperature of 80 to 150°C and a drying time of 6 to 20 hours; and / or the firing conditions include a temperature of 500 to 1100°C and a firing time of 2 to 20 hours.

[0049] In a further preferred embodiment, said step 1) has the features as described above for the method for producing said carrier in the first aspect, a detailed description of which will be omitted here for the sake of brevity.

[0050] In a preferred embodiment, the supporting step in step 2) comprises impregnating the support with a solution containing a precursor of the active metal component and, optionally, a precursor of the metal promoter, and the impregnation solution preferably has a pH in the range of 3.5 to 5.5. By controlling the pH of the impregnation solution within the aforementioned range, the dispersibility of the active metal component can be further improved.

[0051] According to the present application, impregnation is carried out by immersing the support in an appropriate solution containing precursors of the active metal component and the metal promoter, resulting in the precursors being supported on the support by adsorption. Impregnation methods can be classified into dry impregnation, wet impregnation, multiple impregnation, mixed impregnation, spray impregnation, etc. Dry impregnation and wet impregnation refer to impregnation of a support in a dry state or pre-wetted with water with precursors of the active metal component, respectively. Multiple impregnation refers to multiple impregnations with a mixed solution of precursors of one or more components, or multiple impregnations with various precursors, with drying and calcination required after each impregnation to "anchor" the impregnated components. Mixed impregnation refers to the joint impregnation of precursors of the active metal component and the metal promoter when no precipitation reaction occurs between the precursors of the active metal component. Spray impregnation refers to spraying the impregnation solution onto a continuously rotating support with a spray gun so that the impregnation solution just fills and saturates the pore volume of the support. These impregnation methods can be appropriately selected depending on the actual conditions for preparing the catalyst of the present application.

[0052] In a preferred embodiment, the precursors of the active metal component and the metal promoter are soluble salts of the corresponding metals (e.g., nitrates, formates, oxalates, lactates, etc.). The solvent used to form the metal salt solution for impregnating the support is preferably water, although some organic solvents (e.g., ethanol, etc.) may also be used. The impregnation of the support with the metal salt solution can be carried out in any desired order or sequentially using multiple solutions containing one or more metal salts. All impregnation steps or a single impregnation step can be carried out in several stages, and the impregnation order can also be changed. The concentration of the solution is selected so that the desired amount of metal is supported on the support.

[0053] According to the present application, the support carrying the active metal component and, optionally, the metal promoter is subjected to heat treatment in step 3), which preferably includes calcination or a combination of drying and calcination. For example, the heat treatment may include a step of drying the impregnated support at 80 to 150°C, more preferably 80 to 120°C. The drying time can be appropriately selected depending on the drying temperature, the amount of material to be dried, the drying equipment, etc., and can be, for example, 6 to 20 hours, e.g., 8 hours, as long as the moisture content after drying does not affect the subsequent calcination. Furthermore, following drying, the support can be calcined at 150 to 500°C, preferably 300 to 500°C, for 1 to 6 hours to remove water of crystallization in the salt or decompose the salt into an oxide. When performing multiple impregnations, it is preferable to perform drying and calcination after each impregnation.

[0054] In the present application, the process of supporting the active metal component and the metal promoter does not substantially affect the microstructure of the catalyst, and therefore the resulting catalyst has a pore structure similar to that of the support.

[0055] In a third aspect, the present application provides a support that is an inorganic porous material containing aluminum and / or silicon, wherein the support has an ammonia adsorption capacity of 0.25 to 0.65 mmol / g as measured by an NH3-TPD test.

[0056] In a preferred embodiment, the support has an ammonia adsorption capacity of 0.3 to 0.6 mmol / g as measured by the NH3-TPD test.

[0057] In a preferred embodiment, the support comprises a matrix comprising a first support component, optionally a second support component, and a doping element, wherein the first support component is selected from alumina, silica, molecular sieve, aluminosilicate, or a combination thereof, and the second support component is selected from diatomaceous earth and titania, the doping element is selected from a metal element, a non-metal element, or a combination thereof, excluding sodium and chlorine, and the metal element is selected from a Group IA metal element, a Group IIA metal element, a Group VA metal element, or a combination thereof. and at least one selected from the group consisting of elements, and lanthanide series metal elements, preferably at least one selected from the group consisting of calcium, magnesium, potassium, bismuth, strontium, barium, and lanthanum; the non-metal element is at least one selected from the group consisting of Group IIIA non-metal elements, Group VA non-metal elements, Group VIA non-metal elements, and Group VIIA non-metal elements, preferably at least one selected from the group consisting of boron, fluorine, phosphorus, sulfur, and selenium.

[0058] In a further preferred embodiment, the doping elements in the carrier are derived from metal cations and acid radical ions, but do not include sodium ions or chloride ions; the metal cation is at least one selected from the group consisting of Group IA metal ions, Group IIA metal ions, Group VA metal ions and lanthanide metal ions, preferably at least one selected from the group consisting of calcium ions, magnesium ions, potassium ions, bismuth ions, strontium ions, barium ions and lanthanum ions; and the acid radical ion is at least one selected from non-metal acid radical ions, preferably at least one selected from the group consisting of borate ions, fluoride ions, phosphate ions, sulfate ions and selenate ions.

[0059] In a preferred embodiment, the carrier has at least one of the following characteristics: the carrier has a carbon dioxide adsorption capacity of 0.05 to 0.4 mmol / g, preferably 0.05 to 0.3 mmol / g, and more preferably 0.06 to 0.2 mmol / g; the doping element is present in the support in an amount of 0.03 to 6% by weight, preferably 0.05 to 6% by weight, more preferably 0.08 to 4% by weight, relative to the total weight of the matrix; The carrier is 120 to 240 m 2 / g, preferably 120 to 210 m 2 / g, more preferably 125 to 200m 2 / g specific surface area; The carrier has a pore volume of 0.45 to 1.2 ml / g, preferably 0.45 to 1.1 ml / g, more preferably 0.5 to 1 ml / g; the ratio of the pore volume of pores having a pore diameter in the range of 7 to 27 nm to the pore volume of the support is more than 65%, preferably 70% or more, more preferably 70 to 90%, and preferably the ratio of the pore volume of pores having a pore diameter of less than 7 nm to the pore volume of the support is 0 to 10%, for example 0 to 8%; The matrix of the support comprises a combination of alumina and titania in a weight ratio of 1.5 to 5:1, preferably 2 to 4.5:1; and The alumina content in the support is 70% by weight or more, preferably 75% by weight or more, and more preferably 80 to 100% by weight, based on the total weight of the matrix.

[0060] In a fourth aspect, the present application provides the use of the catalyst according to the present application or the support according to the present application for producing an organic amine by catalytic amination.

[0061] In a fifth aspect, the present application provides a process for producing an organic amine, comprising the step of contacting an amination feedstock and an aminating agent with the catalyst according to the present application in the presence of hydrogen for an amination reaction to obtain an organic amine.

[0062] In a preferred embodiment, the amination raw material is selected from the group consisting of alcohols, ketones, alcoholamines, aldehydes, and combinations thereof, more preferably selected from the group consisting of C2-C20 alcohols, C3-C20 ketones, C2-C20 alcoholamines, C2-C20 aldehydes, and mixtures thereof. Even more preferably, the amination raw material is ethanol, acetaldehyde, n-propanol, propionaldehyde, isopropanol, n-butanol, butyraldehyde, isobutanol, isobutyraldehyde, 2-ethylhexanol, 2-ethylhexaldehyde, octanol, octanal, dodecanol, dodecanal, hexadecanol, hexadecanal, cyclopentanol, cyclohexanol, cyclooctanol, cyclododecanol, benzyl alcohol, benzaldehyde, phenethyl alcohol, phenylacetaldehyde, 1,4- butanediol, 1,4-butanedial, 1,5-pentanediol, 1,5-glutaraldehyde, 1,6-hexanediol, 1,6-hexanedial, 1,8-octanediol, 1,8-octanedial, 1,12-dodecanediol, 1,12-dodecanedialdehyde, ethanolamine, propanolamine, isopropanolamine, 6-aminohexanol, diethanolamine, diisopropanolamine, dimethylethanolamine, acetone, ethylene glycol, 1,3-propanediol, and mixtures thereof.

[0063] In this application, the aminating agent refers to a reactant capable of providing an amino group and / or an amine group. Preferably, the aminating agent is selected from the group consisting of ammonia, primary amines, secondary amines, and combinations thereof, more preferably ammonia, C1-C12 primary amines, C2-C12 secondary amines, and mixtures thereof (e.g., at least one of alkylamines, cycloalkylamines, and aralkylamines, even more preferably C1-C4 alkylamines). Particularly preferably, the aminating agent is selected from the group consisting of ammonia, monomethylamine, dimethylamine, methylethylamine, monoethylamine, diethylamine, and mixtures thereof.

[0064] In a preferred embodiment, the amination conditions are such that the molar ratio of hydrogen to the aminating agent to the amination raw material is 1 to 5:2 to 35:1, preferably 1 to 5:2 to 33:1, and more preferably 1 to 5:2 to 30:1; the temperature is 105 to 220°C, preferably 110 to 220°C, and more preferably 130 to 200°C; the pressure is 0.7 to 25 MPa, preferably 0.8 to 25 MPa, and more preferably 1 to 15 MPa; and the liquid phase volumetric space velocity of the amination raw material is 0.06 to 1 m 3 / (m 3 h) including being; In some preferred embodiments, the amination raw material is a monohydric alcohol, and the amination conditions are such that the molar ratio of hydrogen to the aminating agent to the amination raw material is 1 to 4:2 to 10:1, preferably 1 to 4:2 to 9:1, and more preferably 1 to 4:2 to 8:1; the temperature is 130 to 210°C, and preferably 130 to 200°C; the pressure is 1 to 4 MPa, preferably 1 to 3.5 MPa, and more preferably 1 to 2.5 MPa; and the liquid phase volumetric space velocity of the amination raw material is 0.1 to 0.8 m 3 / (m 3 h) is included.

[0065] In some preferred embodiments, the amination raw material is a ketone or an aldehyde, and the amination conditions are such that the molar ratio of hydrogen to the aminating agent to the amination raw material is 1 to 4:2 to 6:1, and preferably 1 to 4:2 to 5:1; the temperature is 105 to 180°C, preferably 110 to 180°C, and more preferably 110 to 170°C; the pressure is 0.7 to 3.5 MPa, and preferably 0.7 to 2.5 MPa, and more preferably 0.8 to 2.5 MPa; and the liquid phase volumetric space velocity of the amination raw material is 0.1 to 1 m 3 / (m 3 ·h), preferably 0.1 to 0.8 m 3 / (m 3 h) is included.

[0066] In some preferred embodiments, the amination raw material is an alcohol amine, and the amination conditions include a molar ratio of hydrogen to the aminating agent to the amination raw material of 1 to 4:3 to 25:1, preferably 1 to 4:3 to 20:1; a temperature of 130 to 200°C, preferably 135 to 200°C; a pressure of 1 to 18 MPa, preferably 1 to 15 MPa, more preferably 1 to 11 MPa; and a liquid phase volumetric space velocity of the amination raw material of 0.06 to 0.8 m 3 / (m 3 h) is included.

[0067] In some preferred embodiments, the amination feedstock is a dihydric alcohol, and the amination conditions are such that the molar ratio of hydrogen to the aminating agent to the amination feedstock is 0.3 to 4:3 to 45:1, preferably 1 to 4:3 to 35:1, and more preferably 1 to 4:3 to 33:1; the temperature is 130 to 220°C, preferably 130 to 210°C; the pressure is 1 to 15 MPa, preferably 4 to 25 MPa; and the liquid phase volumetric space velocity of the amination feedstock is 0.06 to 0.8 m 3 / (m 3 ·h), preferably 0.1 to 0.8 m 3 / (m 3 h) is included.

[0068] In some preferred embodiments, the amination feedstock is a mixture of 1,6-hexanediol, cycloheximide, and 6-amino-1-hexanol, and the amination conditions are such that the molar ratio of hydrogen to the aminating agent to the amination feedstock is 0.3 to 4:3 to 45:1, preferably 1 to 4:3 to 35:1, more preferably 1 to 4:3 to 33:1, and even more preferably 1 to 4:3 to 30:1; the temperature is 130 to 220°C, preferably 130 to 210°C; the pressure is 1 to 25 MPa, preferably 2 to 25 MPa, and more preferably 4 to 25 MPa; and the liquid phase volumetric hourly space velocity of the amination feedstock is 0.06 to 0.8 m 3 / (m 3 ·h), preferably 0.1 to 0.8 m 3 / (m 3 h) is included.

[0069] First Type of Embodiment In a first type of embodiment of the present application, there is provided a catalyst having a function of catalyzing the hydroamination of an alcohol to produce an organic amine, the catalyst comprising a support, an active metal component supported on the support, and optionally a metal co-catalyst supported on the support, wherein the support is at least one selected from the group consisting of doped alumina, doped silica, doped molecular sieve, and doped aluminosilicate; the support has an ammonia adsorption capacity of 0.25 to 0.6 mmol / g, and the support has a carbon dioxide adsorption capacity of 0.05 to 0.3 mmol / g; and the active metal component is cobalt and / or nickel.

[0070] The catalyst of the first type of embodiment of the present application exhibits high catalytic activity and high selectivity when used in the hydroamination reaction. For example, when used in the hydroamination of ethanol, the catalyst exhibits high reaction activity and high selectivity for producing ethylamine while reducing the production of methylethylamine, methyldiethylamine, ethyl-n-propylamine, and ethyl-sec-butylamine. When used in the hydroamination of 1,6-hexanediol, the catalyst produces less heavy components and other impurities and has high selectivity for the produced hexanediamine. After long-term service life evaluation, it was found that the catalyst of the first type of embodiment of the present application exhibits stable catalytic performance and improved adsorption-desorption performance by controlling the acidity and alkalinity of the catalyst within an appropriate range, thereby promoting the diffusion of the reaction system, accelerating the reaction rate, reducing carbon deposition, and delaying the blockage of pore channels.

[0071] Preferably, the support has an ammonia adsorption capacity of 0.3 to 0.5 mmol / g, more preferably 0.3 to 0.42 mmol / g.

[0072] Preferably, the carrier has a carbon dioxide adsorption capacity of 0.06 to 0.2 mmol / g, more preferably 0.06 to 0.17 mmol / g.

[0073] Preferably, the carrier comprises a matrix which is at least one selected from the group consisting of alumina, silica, molecular sieve, and aluminosilicate, and a doping element containing a metal element and a nonmetal element. Preferably, the weight ratio of the metal element to the nonmetal element may be 1:0.05-50, more preferably 1:0.2-8.

[0074] More preferably, the metal element is at least one selected from the group consisting of Group IA metal elements, Group IIA metal elements, Group VA metal elements, and lanthanide metal elements, and even more preferably at least one selected from the group consisting of calcium, magnesium, potassium, bismuth, strontium, barium, and lanthanum.

[0075] More preferably, the non-metallic element is at least one selected from the group consisting of Group IIIA non-metallic elements, Group VA non-metallic elements, Group VIA non-metallic elements, and Group VIIA non-metallic elements, and even more preferably at least one selected from the group consisting of boron, fluorine, phosphorus, sulfur, and selenium.

[0076] More preferably, the doping elements in the carrier are derived from metal cations and acid radical ions, but do not include sodium ions or chloride ions. The doping elements are introduced during the preparation of the carrier, so that they are primarily present in the bulk phase of the carrier. More preferably, the metal cations are at least one selected from the group consisting of Group IA metal cations, Group IIA metal ions, Group VA metal ions, and lanthanide metal ions, more preferably at least one selected from the group consisting of calcium ions, magnesium ions, potassium ions, bismuth ions, strontium ions, barium ions, and lanthanum ions; and the acid radical ions are at least one selected from the group consisting of non-metal acid radical ions, more preferably at least one selected from the group consisting of borate ions, fluoride ions, phosphate ions, sulfate ions, and selenate ions.

[0077] Preferably, the doping element is present in the support in an amount of 0.03 to 2% by weight, more preferably 0.08 to 1% by weight, relative to the total weight of the matrix.

[0078] Preferably, the carrier has a thickness of 120 to 240 m 2 / g specific surface area.

[0079] Preferably, the support has a pore volume of 0.5 to 1 ml / g.

[0080] According to the first type of embodiment of the present application, the active metal component may be present in an amount of 5 to 42 g, preferably 10 to 35 g, more preferably 10 to 30 g per 100 g of the matrix.

[0081] According to a first embodiment of the present application, the catalyst may further contain a metal promoter to improve the catalytic performance, optimize the ratio of reaction products, and reduce undesired side reactions. The metal promoter may be at least one selected from the group consisting of Group VIB elements, Group VIIB elements, Group IB elements, Group IIB elements, and Lanthanide elements, and preferably at least one of Cr, Mo, W, Mn, Re, Cu, Ag, Au, Zn, La, and Ce. Preferably, the metal promoter is present in an amount of 0 to 10 g, preferably 0.5 to 6 g, per 100 g of the matrix.

[0082] In a first type of embodiment of the present application, there is also provided a process for producing an organic amine, comprising the step of contacting an amination feedstock and an aminating agent with the catalyst as described above in the presence of hydrogen for an amination reaction.

[0083] According to a first type of embodiment of the present application, the aminating raw material or aminating agent can be selected as described above, and a detailed description thereof will be omitted herein for the sake of brevity.

[0084] According to a first type embodiment of the present application, the amination conditions are such that the molar ratio of hydrogen to the aminating agent to the amination raw material is 1 to 5:2 to 35:1, the temperature is 130 to 200°C, the pressure is 1 to 15 MPa, and the liquid phase volumetric space velocity of the amination raw material is 0.06 to 1 m 3 / (m 3 h).

[0085] Preferably, the amination raw material is a monohydric alcohol, and the amination conditions are such that the molar ratio of hydrogen to the aminating agent to the amination raw material is 1 to 4:2 to 10:1, preferably 2 to 3:4 to 6:1, the temperature is 130 to 200°C, preferably 160 to 180°C, the pressure is 1 to 4 MPa, preferably 1 to 2 MPa, and the liquid phase volumetric space velocity of the amination raw material is 0.1 to 0.8 m 3 / (m 3 ·h), preferably 0.4 to 0.6 m 3 / (m 3 h) is included.

[0086] Preferably, the amination raw material is a ketone or an aldehyde, and the amination conditions are such that the molar ratio of hydrogen to the aminating agent to the amination raw material is 1 to 4:2 to 6:1, the temperature is 110 to 180°C, the pressure is 1 to 3.5 MPa, and the liquid phase volumetric space velocity of the amination raw material is 0.1 to 1 m 3 / (m 3 h) is included.

[0087] Preferably, the amination raw material is an alcohol amine, and the amination conditions are such that the molar ratio of hydrogen to the aminating agent to the amination raw material is 1 to 4:3 to 20:1, preferably 2 to 3:10 to 15:1, the temperature is 135 to 200°C, preferably 170 to 190°C, the pressure is 1 to 11 MPa, preferably 8 to 10 MPa, and the liquid phase volumetric space velocity of the amination raw material is 0.06 to 0.8 m 3 / (m 3 ·h), preferably 0.4 to 0.6 m 3 / (m 3 h) is included.

[0088] Preferably, the amination raw material is a dihydric alcohol, and the amination conditions are such that the molar ratio of hydrogen to the aminating agent to the amination raw material is 0.3 to 4:3 to 45:1, preferably 1 to 4:3 to 35:1, more preferably 2 to 3:10 to 15:1, the temperature is 130 to 210°C, preferably 180 to 190°C, the pressure is 1 to 15 MPa, preferably 8 to 10 MPa, and the liquid phase volumetric space velocity of the amination raw material is 0.1 to 0.8 m 3 / (m 3 ·h), preferably 0.4 to 0.6 m 3 / (m 3 h) is included.

[0089] Preferably, the amination raw material is a mixture of 1,6-hexanediol, hexamethyleneimine, and 6-amino-1-hexanol (abbreviated as aminohexanol), and the amination conditions are such that the molar ratio of hydrogen to the aminating agent to the amination raw material is 0.3 to 4:3 to 45:1, preferably 1 to 4:3 to 35:1, and more preferably 3 to 4:10 to 20:1, the temperature is 130 to 210°C, and preferably 180 to 200°C, the pressure is 1 to 15 MPa, and preferably 5 to 10 MPa, and the liquid phase volumetric space velocity of the amination raw material is 0.1 to 0.8 m 3 / (m 3 ·h), preferably 0.4 to 0.6 m 3 / (m 3 h) is included.

[0090] Second Type of Embodiment In a second type of embodiment of the present application, there is provided a catalyst having a function of producing an amine by catalytic amination, the catalyst comprising a support, an active metal component supported on the support, and a metal promoter supported on the support, the active metal component being cobalt and / or nickel, the metal promoter being a combination of at least one Group VIIB metal and at least one Group IB metal, and the support having an ammonia adsorption capacity of 0.3 to 0.6 mmol / g.

[0091] Preferably, the support has an ammonia adsorption capacity of 0.3 to 0.56 mmol / g, more preferably 0.35 to 0.45 mmol / g.

[0092] The catalyst of the second type of embodiment of the present application contains a specific metal promoter and has high catalytic activity and, at the same time, high selectivity.

[0093] Preferably, the support comprises a matrix comprising alumina and, optionally, an additional support selected from silica and / or molecular sieves, and a doping element. More preferably, the doping element is present in the support in an amount of 0.05 to 6% by weight, more preferably 0.08 to 4% by weight, relative to the weight of the matrix.

[0094] More preferably, the support is mainly composed of (doped) alumina, and further contains (doped) silica, etc., which can further improve the pore structure and structural stability of the catalyst. Particularly preferably, the alumina content of the support is 75 wt % or more, preferably 80 to 100 wt %, based on the total weight of the matrix.

[0095] Preferably, the doping element in the support is a non-metallic element, preferably at least one selected from the group consisting of boron, fluorine, phosphorus, sulfur and selenium, and more preferably, the doping element is incorporated during the preparation of the support in the form of at least one selected from the group consisting of borate ions, fluoride ions, phosphate ions, sulfate ions and selenate ions.

[0096] Preferably, the ratio of the pore volume of pores having a pore diameter in the range of 7 to 27 nm to the pore volume of the support is 70 to 90%.

[0097] Preferably, the ratio of the pore volume of pores having a pore diameter of less than 7 nm to the pore volume of the support is 0 to 8%.

[0098] Preferably, the ratio of the pore volume of pores having a pore diameter of more than 27 nm to the pore volume of the support is 15 to 30%.

[0099] Preferably, the carrier has a thickness of 125 to 200 m 2 / g specific surface area.

[0100] Preferably, the support has a pore volume of 0.45 to 1.1 ml / g.

[0101] Preferably, the active metal component may be present in an amount of 8 to 45 g (e.g., 8 g, 9 g, 15 g, 18 g, 20 g, 23 g, 25 g, 26 g, 30 g, 35 g, 36 g, 38 g, 40 g, 42 g, 45 g, or a value between any two thereof) per 100 g of matrix.

[0102] Preferably, the metal promoter is present in an amount of 0.1 to 10 g (e.g., 0.1 g, 0.5 g, 1 g, 2 g, 3 g, 4 g, 5 g, 6 g, 7 g, 8 g, 8.5 g, 8.7 g, 9 g, 10 g, or a value between any two thereof) per 100 g of matrix.

[0103] According to a second type of embodiment of the present application, the catalyst further comprises a metal promoter to improve the catalytic performance, optimize the ratio of reaction products, and reduce undesirable side reactions. The metal promoter is a mixture of at least one Group VIIB metal and at least one Group IB metal, and the weight ratio of the Group VIIB metal to the Group IB metal in the metal promoter is preferably 0.05 to 15:1, more preferably 0.1 to 12:1, and even more preferably 0.5 to 2:1. Preferably, the Group VIIB metal is selected from manganese and / or rhenium. Preferably, the Group IB metal is at least one selected from the group consisting of copper, silver, and gold. The present inventors have found that by using a preferred combination of metal promoters, a catalyst with better catalytic effect can be obtained.

[0104] According to a second type of embodiment of the present application, the use of a support with a specific pore structure and ammonia adsorption capacity can provide a catalyst that exhibits high catalytic activity and high selectivity when used for the hydroamination of alcohols; when used for the hydroamination of ethanol, it can provide a catalyst that produces almost no by-products, including methylethylamine, methyldiethylamine, ethyl-n-propylamine, ethyl-sec-butylamine, etc. When used for the hydroamination of 1,6-hexanediol, the production of heavy components and other impurities is reduced. After long-term testing, it was found that the catalyst has stable catalytic performance, and by controlling the acidity of the catalyst (especially the ammonia adsorption capacity) within an appropriate range, the adsorption-desorption performance of the catalyst is improved. Combined with the pore channels having a specific structure, this promotes the diffusion of the reaction system, accelerates the reaction rate, reduces carbon deposition, and delays pore channel blockage.

[0105] In a second type of embodiment of the present application, there is also provided a process for producing an organic amine, comprising the step of contacting an amination feedstock and an aminating agent with the catalyst as described above in the presence of hydrogen for an amination reaction.

[0106] According to a second type of embodiment of the present application, the aminating raw material or aminating agent can be selected as described above, and a detailed description thereof will be omitted herein for the sake of brevity.

[0107] According to a second type of embodiment of the present application, the amination conditions are such that the molar ratio of hydrogen to the aminating agent to the amination raw material is 1 to 5:2 to 33:1, the temperature is 110 to 220°C, the pressure is 0.8 to 25 MPa, and the liquid phase volumetric space velocity of the amination raw material is 0.06 to 1 m 3 / (m 3 h).

[0108] Preferably, when the amination raw material is a monohydric alcohol, the amination conditions are a molar ratio of hydrogen to the aminating agent to the amination raw material of 1 to 4:2 to 10:1, a temperature of 130 to 210°C, a pressure of 1 to 3.5 MPa, and a liquid phase volumetric space velocity of the amination raw material of 0.1 to 0.8 m 3 / (m 3 h) is included.

[0109] Preferably, when the amination raw material is a ketone or an aldehyde, the amination conditions are a molar ratio of hydrogen to the aminating agent to the amination raw material of 1 to 4:2 to 5:1, a temperature of 110 to 170°C, a pressure of 0.8 to 2.5 MPa, and a liquid phase volumetric space velocity of the amination raw material of 0.1 to 1 m 3 / (m 3 h) is included.

[0110] Preferably, when the amination raw material is an alcohol amine, the amination conditions are a molar ratio of hydrogen to the aminating agent to the amination raw material of 1 to 4:3 to 25:1, a temperature of 130 to 200°C, a pressure of 1 to 18 MPa, and a liquid phase volumetric space velocity of the amination raw material of 0.06 to 0.8 m 3 / (m 3 h) is included.

[0111] Preferably, when the amination raw material is a mixture of 1,6-hexanediol, hexamethyleneimine, and 6-amino-1-hexanol or a dihydric alcohol, the amination conditions are a molar ratio of hydrogen to the aminating agent to the amination raw material of 1 to 4:3 to 33:1, a temperature of 130 to 220°C, a pressure of 4 to 25 MPa, and a liquid phase volumetric space velocity of the amination raw material of 0.06 to 0.8 m 3 / (m 3 h) is included.

[0112] Third Type of Embodiment In a third type of embodiment of the present application, there is provided a catalyst capable of catalyzing the hydroamination of alcohols, the catalyst comprising a support, a metal active component supported on the support, and a metal promoter supported on the support, the metal active component being cobalt and / or nickel, the metal promoter being a combination of at least one Group VIIB metal and at least one Group IIB metal, and the support having an ammonia adsorption capacity of 0.3 to 0.7 mmol / g.

[0113] The catalyst of the third type of embodiment of the present application contains a specific metal promoter and has high catalytic activity, and at the same time has high selectivity and produces almost no by-products.

[0114] Preferably, the support has an ammonia adsorption capacity of 0.3 to 0.6 mmol / g and a carbon dioxide adsorption capacity of 0.05 to 0.3 mmol / g.

[0115] Preferably, the support comprises a matrix and a doping element, the matrix comprising an alumina support and optionally at least one additional support selected from the group consisting of silica, molecular sieves and diatomaceous earth. More preferably, the doping element is present in the support in an amount of 0.05 to 6 wt. %, more preferably 0.08 to 4 wt. %, based on the total weight of the matrix.

[0116] More preferably, the support is mainly composed of a (doped) alumina support and may further contain (doped) silica, etc., which can further improve the channel diffusivity and pore structure stability of the catalyst. Particularly preferably, the content of the alumina support in the support is 70 wt % or more, preferably 80 to 100 wt %, based on the total weight of the matrix.

[0117] Preferably, the doping element in the support is selected from metal elements and nonmetal elements, and does not include sodium or chlorine. The weight ratio of metal elements to nonmetal elements is preferably 1:0.1 to 40. The doping element is present in the support precursor or is added during the preparation of the support, so that the doping element is primarily present in the bulk phase of the support.

[0118] More preferably, the metal element may be at least one selected from the group consisting of Group IA metal elements, Group IIA metal elements, Group VA metal elements, and lanthanide metal elements, and more preferably at least one selected from the group consisting of calcium, magnesium, potassium, bismuth, strontium, barium, and lanthanum.

[0119] More preferably, the non-metallic element can be derived from at least one non-metallic acid radical ion, more preferably at least one selected from the group consisting of borate ion, fluoride ion, phosphate ion, sulfate ion, and selenate ion. The non-metallic element is at least one selected from the group consisting of boron, fluorine, phosphorus, sulfur, and selenium.

[0120] Preferably, the ratio of the pore volume of pores having a pore diameter in the range of 7 to 27 nm to the total pore volume of the support is greater than 65%, preferably 70 to 90%, more preferably 70 to 75%. More preferably, the ratio of the pore volume of pores having a pore diameter of less than 7 nm to the total pore volume of the support is 0 to 10%, preferably 5 to 8%. More preferably, the ratio of the pore volume of pores having a pore diameter of more than 27 nm to the total pore volume of the support is 10 to 30%, preferably 20 to 30%.

[0121] Preferably, the carrier has a thickness of 120 to 205 m 2 / g specific surface area.

[0122] Preferably, the support has a pore volume of 0.45 to 1.2 ml / g.

[0123] Preferably, the carrier has a carbon dioxide adsorption capacity of 0.05 to 0.4 mmol / g.

[0124] Preferably, the metal active ingredient is present in an amount of 14 to 46 g (e.g., 14 g, 15 g, 20 g, 25 g, 30 g, 32 g, 35 g, 38 g, 40 g, 42 g, 45 g, 46 g, or a value between any two thereof) per 100 g of matrix.

[0125] Preferably, the metal promoter is present in an amount of 0.1 to 10 g (e.g., 0.1 g, 0.5 g, 1 g, 1.2 g, 1.5 g, 1.8 g, 2 g, 3 g, 4 g, 5 g, 6 g, 7 g, 7.2 g, 7.5 g, 7.8 g, 8 g, 9 g, 10 g, or a value between any two thereof) per 100 g of matrix.

[0126] According to a second type of embodiment of the present application, the catalyst further comprises a metal promoter as described above to improve the performance of the catalyst, optimize the ratio of reaction products, and reduce undesired side reactions. The weight ratio of the Group VIIB metal to the Group IIB metal in the metal promoter is preferably 0.2 to 20:1, more preferably 0.3 to 6:1, and more preferably 1 to 5:1. Preferably, the Group VIIB metal is selected from manganese and / or rhenium. Preferably, the Group IIB metal is selected from zinc.

[0127] According to a third embodiment of the present application, the use of a carrier with a specific pore structure, ammonia adsorption capacity, and carbon dioxide adsorption capacity allows the catalyst to exhibit high catalytic activity and, at the same time, high selectivity when used for the hydroamination of alcohols; when used for the hydroamination of n-propanol, there is almost no production of other impurities; when used for the hydroamination of 1,6-hexanediol, there is even less production of heavy components and other impurities. After long-term service evaluation, it was found that the catalyst has stable catalytic performance, and by controlling the acidity and alkalinity of the catalyst within an appropriate range, the adsorption and desorption performance of reaction intermediates on the catalyst surface is improved, thereby promoting the diffusion of the reaction system, accelerating the reaction rate, reducing carbon deposition and pore channel blockage, and effectively extending the useful service life of the catalyst.

[0128] In a third type of embodiment of the present application, there is also provided a process for producing an organic amine, comprising the step of contacting an amination feedstock and an aminating agent with the catalyst as described above in the presence of hydrogen for an amination reaction.

[0129] According to a third type of embodiment of the present application, the aminating raw material or aminating agent can be selected as described above, and a detailed description thereof will be omitted herein for the sake of brevity.

[0130] According to a third type embodiment of the present application, the amination conditions are such that the molar ratio of hydrogen to the aminating agent to the amination raw material is 1 to 5:2 to 30:1, the temperature is 110 to 220°C, the pressure is 0.8 to 25 MPa, and the liquid phase volumetric space velocity of the amination raw material is 0.06 to 1 m 3 / (m 3 h).

[0131] Preferably, the amination raw material is a monohydric alcohol, and the amination conditions are a molar ratio of hydrogen to the aminating agent to the amination raw material of 1 to 4:2 to 9:1, a temperature of 130 to 200°C, a pressure of 1 to 2.5 MPa, and a liquid phase volumetric space velocity of the amination raw material of 0.1 to 0.8 m 3 / (m 3 h) is included.

[0132] Preferably, the amination raw material is a ketone or an aldehyde, and the amination conditions are a molar ratio of hydrogen to the aminating agent to the amination raw material of 1 to 4:2 to 6:1, a temperature of 110 to 180°C, a pressure of 0.8 to 2.5 MPa, and a liquid phase volumetric space velocity of the amination raw material of 0.1 to 0.8 m 3 / (m 3 h) is included.

[0133] Preferably, the amination raw material is an alcohol amine, and the amination conditions are a molar ratio of hydrogen to the aminating agent to the amination raw material of 1 to 4:3 to 20:1, a temperature of 130 to 200°C, a pressure of 1 to 15 MPa, and a liquid phase volumetric space velocity of the amination raw material of 0.06 to 0.8 m 3 / (m 3 h) is included.

[0134] Preferably, the amination raw material is a mixture of 1,6-hexanediol, cycloheximide, and 6-amino-1-hexanol or a dihydric alcohol, and the amination conditions are a molar ratio of hydrogen to the aminating agent to the amination raw material of 1 to 4:3 to 30:1, a temperature of 130 to 220°C, a pressure of 1 to 25 MPa, and a liquid phase volumetric space velocity of the amination raw material of 0.1 to 0.8 m 3 / (m 3 h) is included.

[0135] Fourth Type of Embodiment In a fourth type of embodiment of the present application, there is provided a catalyst capable of catalyzing the amination of alcohols, the catalyst comprising a support, an active metal component supported on the support, and a metal promoter supported on the support, the active metal component being cobalt and / or nickel, the metal promoter being a combination of at least one Group VIB metal, at least one Group IB metal, and at least one Group IIB metal, and the support having an ammonia adsorption capacity of 0.25 to 0.6 mmol / g.

[0136] The catalyst of the fourth type of embodiment of the present application contains a specific metal promoter and has high catalytic activity, and at the same time has high selectivity and produces almost no by-products.

[0137] Preferably, the support has an ammonia adsorption capacity of 0.3 to 0.6 mmol / g.

[0138] Preferably, the support comprises a matrix and a doping element, the matrix comprises an alumina support and an additional support, the additional support being selected from silica and / or a molecular sieve.

[0139] Preferably, silica precursor and / or molecular sieve precursor are added during the preparation of the alumina precursor used in the carrier, which can further significantly improve the catalyst diffusion and pore structure stability after the carrier is prepared. Preferably, the alumina content in the carrier is 70% by weight or more, preferably 80-97% by weight, based on the total weight of the matrix.

[0140] Preferably, the doping element is present in the support in an amount of 0.05 to 5% by weight, preferably 0.08 to 3% by weight, relative to the total weight of the matrix.

[0141] Preferably, the doping element is incorporated in the form of at least one selected from the group consisting of borate ions, fluoride ions, phosphate ions, sulfate ions, and selenate ions. Preferably, the doping element is at least one selected from the group consisting of boron, fluorine, phosphorus, sulfur, and selenium. According to a fourth type of embodiment of the present application, the nonmetallic element is incorporated during the preparation process of the precursor of the support, so that the doping element is mainly present in the bulk phase of the support, rather than being attached to its surface.

[0142] Preferably, the ratio of the pore volume of pores having a pore diameter in the range of 7 to 27 nm to the total pore volume of the support is more than 65%, preferably 70 to 90%, and more preferably, the ratio of the pore volume of pores having a pore diameter of less than 7 nm to the total pore volume of the support is 0 to 8%, preferably 0 to 5%.

[0143] Preferably, the carrier has a thickness of 120 to 210 m 2 / g specific surface area.

[0144] Preferably, the support has a pore volume of 0.45 to 1.1 ml / g.

[0145] Preferably, the active metal component may be present in an amount of 10 to 46 g, preferably 18 to 38 g, per 100 g of matrix.

[0146] Preferably, the metal promoter may be present in an amount of 0.1 to 10 g, preferably 0.5 to 6 g, per 100 g of matrix.

[0147] According to a fourth embodiment of the present application, the catalyst further comprises a metal promoter as described above to improve the catalytic performance, optimize the ratio of reaction products, and reduce undesirable side reactions. The weight ratio of the Group VIB metal, Group IB metal, and Group IIB metal in the metal promoter is preferably 0.1-10:0.1-10:1, more preferably 0.2-8:0.2-8:1, and 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 at least one selected from the group consisting of copper, silver, and gold. Preferably, the Group IIB metal is selected from zinc.

[0148] According to a fourth embodiment of the present application, the use of a support with a specific pore structure and ammonia adsorption capacity allows the catalyst to have high catalytic activity and, at the same time, high selectivity when used for the hydroamination of alcohols; when used for the hydroamination of n-propanol, there is almost no production of other impurities; when used for the hydroamination of 1,6-hexanediol, there is less production of heavy components and other impurities. After long-term testing, the catalyst exhibited stable catalytic performance, and it was found that modifying the support improved the adsorption-desorption performance of the catalyst, promoted the diffusion of the reaction system, accelerated the reaction rate, reduced carbon deposition, and delayed the blockage of pore channels.

[0149] In a fourth type of embodiment of the present application, there is also provided a process for producing an organic amine, comprising the step of contacting an amination feedstock and an aminating agent with the catalyst as described above in the presence of hydrogen for an amination reaction.

[0150] According to a fourth type of embodiment of the present application, the aminating raw material or aminating agent can be selected as described above, and a detailed description thereof will be omitted herein for the sake of brevity.

[0151] According to a fourth type embodiment of the present application, the amination conditions are such that the molar ratio of hydrogen to the aminating agent to the amination raw material is 1 to 5:2 to 35:1, the temperature is 105 to 220°C, the pressure is 0.7 to 25 MPa, and the liquid phase volumetric space velocity of the amination raw material is 0.06 to 1 m 3 / (m 3 h).

[0152] Preferably, the amination raw material is a monohydric alcohol, and the amination conditions are a molar ratio of hydrogen to the aminating agent to the amination raw material of 1 to 4:2 to 8:1, a temperature of 130 to 200°C, a pressure of 1 to 2.5 MPa, and a liquid phase volumetric space velocity of the amination raw material of 0.1 to 0.8 m 3 / (m 3 h) is included.

[0153] Preferably, the amination raw material is a ketone or an aldehyde, and the amination conditions are a molar ratio of hydrogen to the aminating agent to the amination raw material of 1 to 4:2 to 5:1, a temperature of 105 to 180°C, a pressure of 0.7 to 2.5 MPa, and a liquid phase volumetric space velocity of the amination raw material of 0.1 to 0.8 m 3 / (m 3 h) is included.

[0154] Preferably, the amination raw material is an alcohol amine, and the amination conditions are a molar ratio of hydrogen to the aminating agent to the amination raw material of 1 to 4:3 to 25:1, a temperature of 130 to 200°C, a pressure of 5 to 18 MPa, and a liquid phase volumetric space velocity of the amination raw material of 0.06 to 0.8 m 3 / (m 3 h) is included.

[0155] Preferably, the amination raw material is a mixture of 1,6-hexanediol, cycloheximide, and 6-amino-1-hexanol or a dihydric alcohol, and the amination conditions are a molar ratio of hydrogen to the aminating agent to the amination raw material of 0.3 to 4:3 to 45:1, preferably 1 to 4:3 to 35:1, a temperature of 130 to 220°C, a pressure of 2 to 25 MPa, and a liquid phase volumetric space velocity of the amination raw material of 0.1 to 0.8 m 3 / (m 3 h) is included.

[0156] Fifth Type of Embodiment In a fifth type of embodiment of the present application, there is provided a titanium-containing catalyst having an amination function, the catalyst comprising a support, an active metal component supported on the support, and optionally a metal promoter supported on the support, the support comprising a matrix and optionally a doping element, the matrix comprising alumina and titania in a weight ratio of 1.5 to 5:1, the active metal component being cobalt and / or nickel, and the catalyst having an ammonia adsorption capacity of 0.2 to 0.7 mmol / g, preferably 0.3 to 0.4 mmol / g.

[0157] The catalyst of the fifth embodiment of the present application has high catalytic activity and, at the same time, high selectivity when used for the hydroamination of alcohols. In particular, when the catalyst is used for the hydroamination of 1,6-hexanediol, the production of heavy components and other impurities is reduced and the selectivity for hexanediamine is high. After long-term testing, the catalyst was found to have stable catalytic performance, accelerated reaction rate, reduced carbon deposition, and delayed blockage of pore channels.

[0158] Titania has strong acidity, containing both B- and L-acids, and, unlike alumina, has strong interactions with components dispersed on titania. Composite supports composed of alumina and titania have various catalytic effects for various reactions. Through careful research and careful selection, the inventors of the present application have found that incorporating an appropriate amount of titania into pseudoboehmite during the formation of the support can effectively improve the catalytic performance of the resulting catalyst. Preferably, the weight ratio of alumina to titania is 2 to 4.5:1. Using such a ratio can further improve the catalytic performance of the resulting catalyst.

[0159] Preferably, the active metal component may be present in an amount of 13 to 40 g, preferably 20 to 36 g, per 100 g of matrix.

[0160] Preferably, the metal promoter may be present in an amount of 0 to 10 g, preferably 2.5 to 8 g, per 100 g of matrix.

[0161] According to a fifth embodiment of the present application, the titanium-containing catalyst may further comprise a metal promoter to improve the catalytic performance, optimize the reaction product ratio, and reduce undesired side reactions. The metal promoter may be at least one selected from the group consisting of Group VIB elements, Group VIIB elements, Group IB elements, Group IIB elements, and Lanthanide elements, and may be 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.

[0162] Preferably, the titanium-containing catalyst has a carbon dioxide adsorption capacity of 0.07 to 0.2 mmol / g.

[0163] Preferably, the titanium-containing catalyst has a catalyst content of 130 to 180 m 2 / g specific surface area.

[0164] Preferably, the titanium-containing catalyst has a pore volume of 0.55 to 0.75 ml / g.

[0165] Preferably, in the titanium-containing catalyst, the ratio of the pore volume of pores having a pore radius of less than 4 nm to 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 a value between any two thereof), and the ratio of the pore volume of pores having a pore radius of more than 10 nm to the total pore volume is preferably less than 15% (e.g., The ratio of the pore volume of pores having a pore radius of 4 to 10 nm to the total pore volume is 65% or more (e.g., 66%, 70%, 72%, 73%, 75%, 76.5%, 77%, 77.5%, 78.5%, 79%, 80%, or a value between any two of them).

[0166] Preferably, the support of the titanium-containing catalyst is doped with sulfur in an amount of 0.1 to 0.5 g, more preferably 0.15 to 0.4 g, per 100 g of matrix.

[0167] In a fifth type of embodiment of the present application, supporting the active metal component and the metal promoter does not substantially affect the ammonia adsorption capacity, carbon dioxide adsorption capacity, specific surface area, pore structure characteristics, etc. of the catalyst, and therefore the properties of the catalyst related to the support are similar to those described above (for example, the difference is within ±5%), and detailed description thereof will be omitted in this specification for the sake of brevity.

[0168] Preferably, the titanium-containing catalyst may be in the form of strips, sheets, clover or toothed spheres.

[0169] The catalyst according to the fifth type of embodiment of the present application may be prepared by a supporting method by first providing a support comprising a matrix containing alumina and titania in a weight ratio of 2-5:1 and optionally a doping element, and then supporting an active metal component and optionally a metal promoter on the support.

[0170] In a fifth type of embodiment of the present application, there is provided a method for producing a titanium-containing catalyst having an amination function, which includes the following 1) and 2): 1) kneading, shaping, and calcining pseudo-boehmite and titania to obtain a carrier, wherein the pseudo-boehmite and titania are used in amounts such that the weight ratio of alumina to titania in the resulting carrier is 1.5 to 5:1; 2) supporting an active metal component and optionally a metal promoter on the resulting support, wherein the active metal component comprises cobalt and / or nickel.

[0171] Preferably, the pseudo-boehmite and titania are used in amounts such that the weight ratio of the alumina to the titania in the resulting carrier is 2 to 4.5:1.

[0172] Preferably, the pseudo-boehmite 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, preferably aluminum isopropoxide.

[0173] Preferably, the titania is provided by titanium white powder, which is prepared by precipitation and / or sol-gel methods. The raw material capable of providing the titanium used in the method can be an organic titanium source (e.g., an organic titanate) 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, titanium phosphate, etc., and the organic titanium source can be one or more of titanium alkoxides of fatty alcohols and organic titanates. The organotitanate is preferably an organotitanate having the formula M4TiO4, where M is an alkyl group preferably having 1 to 4 carbon atoms, and the four Ms can be the same or different, and preferably the organotitanate is one or more selected from isopropyl titanate, n-propyl titanate, tetrabutyl titanate, and tetraethyl titanate. Specific examples of sources that can provide titanium can be, but are not limited to, TiOCl, titanium tetrachloride, titanium sulfate, titanyl sulfate, tetrapropyl titanate (including various isomers of tetrapropyl titanate, such as tetraisopropyl titanate, tetra-n-propyl titanate), tetrabutyl titanate (including various isomers of tetrabutyl titanate, such as tetra-n-butyl titanate), and tetraethyl titanate.

[0174] Preferably, the content of sulfate radicals in the titanium white powder is 0.2 to 3 wt %. The titanium white powder is more preferably prepared by the titanium sulfate ammonia hydrolysis method or the titanium oxysulfate ammonia hydrolysis method. By using such titanium white powder, a catalyst can be obtained that includes a support having a more desirable pore channel structure and has better catalytic performance.

[0175] Preferably, the active metal component is used in an amount such that the active metal component is present in an amount of 13 to 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 a value between any two thereof) per 100 g of support.

[0176] Preferably, a metal promoter may be supported on a support to improve catalyst performance, optimize the reaction product ratio, and reduce undesired side reactions. The metal promoter is used in an amount such that the metal promoter is present in an amount of 0 to 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 a value between any two thereof) per 100 g of support.

[0177] Preferably, the metal promoter may be at least one selected from the group consisting of Group VIB metals, Group VIIB metals, Group IB metals, Group IIB metals and Lanthanide metals, and may be 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.

[0178] Preferably, there are no special requirements for the conditions of kneading, molding, and calcination in step 1). To obtain a carrier with appropriate strength, kneading is carried out in the presence of 2 to 10 g of acid per 100 g of powder (particularly, 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). The calcination temperature in step 1) can be 550 to 1100°C, preferably 800 to 1050°C. The calcination time in step 1) can be 2 to 6 hours.

[0179] Preferably, in step 2), the supporting step may be carried out by impregnation, i.e., the support may be impregnated with a solution containing the active metal component precursor and optionally the metal promoter precursor, followed by drying and calcination.

[0180] Preferably, the method may further include a step of reducing the product obtained in step 2) to obtain a catalyst having an active metal component and a reducible metal promoter present in a reduced state. The reduction can be carried out using a hydrogen-containing gas at 350 to 500°C, preferably 350 to 450°C. The hydrogen-containing gas may be pure hydrogen gas or hydrogen gas diluted with an inert gas (e.g., a mixture of nitrogen and hydrogen). The reduction temperature is gradually increased during the reduction, and the temperature increase is preferably not too rapid (e.g., 20°C or less per hour). The reduction time can be determined by observing the production of HO in the reduction system. That is, when no new HO is produced in the reduction system, the reduction is terminated. Those skilled in the art can select the reduction time accordingly, but detailed description thereof will be omitted herein for brevity (e.g., the reduction time can be 2 to 5 hours at the highest temperature).

[0181] The reduction may be carried out directly in the reactor, followed by the catalytic reaction. It is also possible to carry out the reduction in a separate reactor, also known as extra-reactor reduction. Before the catalyst is discharged from the reactor, it may be reduced with an oxygen-containing gas mixture and then passivated. The passivation temperature is, for example, from 10 to 60°C, particularly from 20 to 40°C. The catalyst that has undergone extra-reactor reduction and passivation can be activated, for example, at 150 to 250°C, preferably 170 to 200°C, before using hydrogen or a mixture of hydrogen and nitrogen. The activation time can be determined by observing the generation of HO in the activation system. That is, when no new HO is generated in the activation system, activation is terminated. Those skilled in the art can select the activation time accordingly, but a detailed description thereof will be omitted herein for brevity. For example, the activation time at the highest temperature may be, for example, from 1 to 5 hours, preferably from 2 to 3 hours, or the catalyst can be used without activation depending on the degree to which the active metal component and metal promoter of the catalyst have been oxidized.

[0182] In a fifth type of embodiment of the present application, there is also provided a process for producing an organic amine, comprising contacting ammonia and / or an organic amine with an alcohol in the presence of the aforementioned titanium-containing catalyst for an amination reaction.

[0183] Preferably, the alcohol may be at least one selected from the group consisting of substituted or unsubstituted monohydric alcohols having 2 to 20 carbon atoms and substituted or unsubstituted dihydric alcohols having 2 to 20 carbon atoms (the substituent may be an amino group), such as at least one of ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-ethylhexanol, octanol, dodecanol, hexadecanol, cyclopentanol, cyclohexanol, benzyl alcohol, phenethyl alcohol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-butanedial, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanedial, 1,8-octanedial, 1,12-dodecanediol, ethanolamine (2-aminoethanol), 6-amino-1-hexanol (abbreviated as aminohexanol), etc.

[0184] Preferably, the organic amine may be a primary amine and / or a secondary amine. For example, an alkylamine having 1 to 4 carbon atoms (e.g., at least one of monomethylamine, dimethylamine, methylethylamine, monoethylamine, diethylamine, etc.) can be used. The amination reaction is preferably carried out using excess ammonia or amine. For example, ammonia or an organic amine can be used in an amount of 1 to 50 mol, preferably 3 to 20 mol, and more preferably 3 to 15 mol per mol of hydroxyl groups in the alcohol. The amination reaction of the alcohol is carried out in the presence of hydrogen, i.e., in a hydrogenated state. Hydrogen can be used in an amount of 1 to 10 mol per mol of hydroxyl groups in the alcohol. The hydrogen partial pressure is, for example, 0.05 MPa to 2 MPa. The temperature of the amination reaction can be 100 to 300°C. The pressure of the amination reaction can be 0.1 MPa to 25 MPa, preferably 1 MPa to 15 MPa. The liquid volumetric space velocity of the alcohol is 0.1 m 3 / (m 3 h) to 0.8m 3 / (m 3 ·h)

[0185] For example, the amination reaction may be, for example, the hydroamination of ethanol to produce ethylamine, the hydroamination of n-propanol to produce n-propylamine, the hydroamination of isopropanol to produce isopropylamine, the hydroamination of n-butanol to produce n-butylamine, the hydroamination of ethylene glycol to produce ethylenediamine, the hydroamination of ethanolamine to produce ethylene glycol, the hydroamination of 1,3-propanediol to produce 1,3-propanediamine, the hydroamination of 1,4-butanediol to produce 1,4-butanediamine, the hydroamination of 1,6-hexanediol to produce 1,6-hexanediamine, or the hydroamination of 1,12-dodecanediol to produce 1,12-dodecanediamine.

[0186] According to a fifth type of embodiment of the present application, the amination reaction can be carried out batchwise or continuously. The amination reaction can be a gas phase reaction or a liquid phase trickle bed reaction.

[0187] Also provided herein are some specific embodiments for carrying out an amination reaction using the catalyst according to the fifth type of embodiment of the present application.

[0188] For example, the present application provides a process for producing 1,6-hexanediol from 1,6-hexanediol using the catalyst according to a fifth type embodiment of the present application, the process being carried out using 1,6-hexanediol, ammonia and hydrogen at a temperature of 130 to 200°C, a pressure of 1 to 11 MPa, and a liquid volumetric hourly space velocity of 1,6-hexanediol feed of 0.1 to 0.8 m 3 / (m 3 h), and a step of carrying out a hydroamination reaction using hydrogen, ammonia, and hexanediol in a molar ratio of 1 to 4:3 to 20:1 to produce hexanediamine, 6-amino-1-hexanol, and hexamethyleneimine.

[0189] The present application provides a process for producing 1,6-hexanediamine from 1,6-hexanediol, hexamethyleneimine, and 6-amino-1-hexanol using the catalyst according to a fifth type embodiment, the process being carried out using a mixture of 1,6-hexanediol, hexamethyleneimine, and 6-amino-1-hexanol, ammonia, and hydrogen at a reaction temperature of 130 to 200°C, a reaction pressure of 1 to 11 MPa, and a liquid volumetric hourly space velocity of 0.1 to 0.8 m 3 / (m 3 h), and a step of carrying out a hydroamination reaction using hydrogen, ammonia, and the mixture in a molar ratio of 1 to 4:3 to 20:1 to produce a reaction solution containing 1,6-hexanediamine, 6-amino-1-hexanol, and cycloheximide.

[0190] In a particularly preferred embodiment, the present application discloses the following technical solutions: A1. A catalyst having the function of catalyzing alcohol hydroamination to produce an organic amine, the catalyst comprising a carrier, an active metal component, and an optional metal co-catalyst, the active metal component and the optional metal co-catalyst being supported on the carrier, the carrier being at least one selected from the group consisting of doped alumina, doped silica, doped molecular sieve, and doped aluminosilicate; the carrier having an ammonia adsorption capacity of 0.25 to 0.6 mmol / g and a carbon dioxide adsorption capacity of 0.05 to 0.3 mmol / g; the active metal component being cobalt and / or nickel.

[0191] A2, the support has an ammonia adsorption capacity of 0.3 to 0.5 mmol / g; and / or the support has a carbon dioxide adsorption capacity of 0.06 to 0.2 mmol / g; and / or the content of the doping element in the support accounts for 0.03-2 wt %, preferably 0.08-1 wt %, of the total weight of elements other than the doping element in the support; and / or the doping element in the support comprises a metal element and a non-metal element, wherein the metal element is at least one selected from the group consisting of Group IA metal elements, Group IIA metal elements, Group VA metal elements and Lanthanide metal elements, preferably at least one selected from the group consisting of calcium, magnesium, potassium, bismuth, strontium, barium and lanthanum; the non-metal element is at least one selected from the group consisting of Group IIIA non-metal elements, Group VA non-metal elements, Group VIA non-metal elements and Group VIIA non-metal elements, preferably at least one selected from the group consisting of boron, fluorine, phosphorus, sulfur and selenium; preferably the doping element in the support is derived from a metal cation and an acid radical ion, but does not include a sodium ion or a chloride ion; the metal cation is at least one selected from the group consisting of a Group IA metal ion, a Group IIA metal ion, a Group VA metal ion, and a lanthanide metal ion, and is preferably at least one selected from the group consisting of a calcium ion, a magnesium ion, a potassium ion, a bismuth ion, a strontium ion, a barium ion, and a lanthanum ion; the acid radical ion is at least one selected from the group consisting of a non-metal acid radical ion, and is preferably at least one selected from the group consisting of a borate ion, a fluoride ion, a phosphate ion, a sulfate ion, and a selenate ion; And / or the carrier is 120 to 240 m 2 / g specific surface area; and / or the support has a pore volume of 0.5 to 1 ml / g; And / or the catalyst according to item A1, wherein the content of the active metal component is 5 to 42 g, preferably 10 to 35 g, per 100 g of the matrix.

[0192] A3. The catalyst according to item A1 or A2, wherein the support is prepared by a method including successively shaping, drying, and calcining a mixture containing the doping element and a support source, and the support source is at least one selected from the group consisting of pseudoboehmite, silica, molecular sieves, and aluminosilicates.

[0193] A4, the doping element is provided by a support modifier, preferably the support modifier is at least one of a compound capable of providing a cation and an anion, the cation being at least one selected from the group consisting of a Group IA cation, a Group IIA metal ion, a Group VA metal ion, and a lanthanide metal ion, preferably at least one selected from the group consisting of a calcium ion, a magnesium ion, a potassium ion, a bismuth ion, a strontium ion, a barium ion, and a lanthanum ion; and / or the anion is at least one selected from the group consisting of non-metallic acid radical ions, preferably at least one selected from the group consisting of borate ions, fluoride ions, phosphate ions, sulfate ions, and selenate ions.

[0194] A5, the carrier modifier is at least one selected from the group consisting of boric acid, nickel borate, cobalt borate, potassium borate, hydrofluoric acid, potassium fluoride, cobalt fluoride, nickel fluoride, phosphoric acid, aluminum phosphate, tripotassium 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; Preferably, the pseudo-boehmite has a particle size of 250 to 330 m 2 / g and a pore volume of 0.8 to 1.3 ml / g.

[0195] A6, the drying conditions include a temperature of 80 to 150°C and a time of 6 to 20 hours; and / or the catalyst according to any one of items A3 to A5, wherein the calcination conditions include a temperature of 600 to 1100°C and a time of 2 to 20 hours.

[0196] A7. A method for producing the catalyst according to any one of items A1 to A6, comprising a step of supporting the active metal component and, optionally, the metal promoter on the support.

[0197] A8, a carrier as defined in any one of items A1 to A6.

[0198] A9. Use of the catalyst according to any one of items A1 to A6, or the method according to item A7, or the support according to item A8, in amination for the production of organic amines.

[0199] A10, a process for producing an organic amine, comprising a step of contacting an amination raw material and an aminating agent with the catalyst according to any one of items A1 to A6 in the presence of hydrogen for an amination reaction; Or alternatively, the method includes the steps of screening a catalyst comprising the support defined in any one of items A1 to A6, and contacting an amination raw material and an aminating agent with the screened catalyst in the presence of hydrogen for an amination reaction.

[0200] A11, the amination conditions are that the molar ratio of hydrogen to the aminating agent to the amination raw material is 1 to 5:2 to 35:1, the temperature is 130 to 200°C, the pressure is 1 to 15 MPa, and the liquid phase volumetric space velocity of the amination raw material is 0.06 to 1 m 3 / (m 3 h) including being; And / or, the amination raw material is at least one selected from the group consisting of C2 to C20 alcohols, C3 to C20 ketones, C2 to C20 alcoholamines, and C2 to C20 aldehydes, and is preferably ethanol, acetaldehyde, n-propanol, propionaldehyde, isopropanol, n-butanol, butyraldehyde, isobutanol, isobutyraldehyde, 2-ethylhexanol, 2-ethylhexaldehyde, octanol, octanal, dodecanol, dodecanal, hexadecanol, hexadecanal, cyclopentanol, cyclohexanol, cyclooctanol ... at least one of dodecanol, benzyl alcohol, benzaldehyde, phenethyl alcohol, phenylacetaldehyde, 1,4-butanediol, 1,4-butanedial, 1,5-pentanediol, 1,5-glutaraldehyde, 1,6-hexanediol, 1,6-hexanedial, 1,8-octanediol, 1,8-octanedial, 1,12-dodecanediol, 1,12-dodecanedialdehyde, ethanolamine, propanolamine, isopropanolamine, 6-aminohexanol, diethanolamine, acetone, ethylene glycol, and 1,3-propanediol; And / or the process according to item A10, wherein the aminating agent is at least one selected from the group consisting of ammonia, C1-C12 primary amines and C2-C12 secondary amines, preferably at least one of ammonia, monomethylamine, dimethylamine, methylethylamine, monoethylamine and diethylamine.

[0201] A12: When the amination raw material is a monohydric alcohol, the amination conditions are such that the molar ratio of hydrogen to the aminating agent to the amination raw material is 1 to 4:2 to 10:1, the temperature is 130 to 200°C, the pressure is 1 to 4 MPa, and the liquid phase volumetric space velocity of the amination raw material is 0.1 to 0.8 m 3 / (m 3 h) including being; Alternatively, when the amination raw material is a ketone or an aldehyde, the amination conditions are a molar ratio of hydrogen to the aminating agent to the amination raw material of 1 to 4:2 to 6:1, a temperature of 110 to 180°C, a pressure of 1 to 3.5 MPa, and a liquid phase volumetric space velocity of the amination raw material of 0.1 to 1 m 3 / (m 3 h) including being; Alternatively, when the amination raw material is an alcohol amine, the amination conditions are a molar ratio of hydrogen to the aminating agent to the amination raw material of 1 to 4:3 to 20:1, a temperature of 135 to 200°C, a pressure of 1 to 11 MPa, and a liquid phase volumetric space velocity of the amination raw material of 0.06 to 0.8 m 3 / (m 3 h) including being; Alternatively, when the amination raw material is a dihydric alcohol, the amination conditions are a molar ratio of hydrogen to the aminating agent to the amination raw material of 1 to 4:3 to 35:1, a temperature of 130 to 210°C, a pressure of 1 to 15 MPa, and a liquid phase volumetric space velocity of the amination raw material of 0.1 to 0.8 m 3 / (m 3 h) including being; Alternatively, when the amination raw material is a mixture of 1,6-hexanediol, hexamethyleneimine, and 6-amino-1-hexanol, the amination conditions are a molar ratio of hydrogen to the aminating agent to the amination raw material of 1 to 4:3 to 35:1, a temperature of 130 to 210°C, a pressure of 1 to 15 MPa, and a liquid phase volumetric space velocity of the amination raw material of 0.1 to 0.8 m 3 / (m 3 The process according to item A11, comprising: h).

[0202] B1. A catalyst having the function of catalyzing amination to produce an amine, comprising a support and an active metal component and a metal cocatalyst supported on the support, wherein the active metal component is cobalt and / or nickel; and the metal cocatalyst is a combination of at least one Group VIIB metal and at least one Group IB metal.

[0203] B2. The catalyst according to item B1, wherein the support comprises an alumina support, a doping element, and optionally an additional support selected from silica and / or a molecular sieve; the support has an ammonia adsorption capacity of 0.3 to 0.6 mmol / g; and the ratio of the pore volume of pores having a pore diameter in the range of 7 to 27 nm to the pore volume of the support is 70% or more.

[0204] B3, the content of the alumina support in the support is 75% by weight or more, preferably 80 to 100% by weight, based on the total amount of the alumina support and the additional support; and / or the content of said doping element is 0.05 to 6% by weight, preferably 0.08 to 4% by weight, relative to the weight of said matrix; and / or the doping element in the support is a non-metallic element, preferably incorporated during the preparation of the support in the form of at least one selected from the group consisting of borate ions, fluoride ions, phosphate ions, sulfate ions and selenate ions; and / or the support has an ammonia adsorption capacity of 0.3 to 0.56 mmol / g; and / or the ratio of the pore volume of pores having a pore diameter in the range of 7 to 27 nm to the pore volume of the support is 70 to 90%, and the ratio of the pore volume of pores having a pore diameter of less than 7 nm to the pore volume of the support is 0 to 8%; And / or the carrier is 125 to 200 m 2 / g specific surface area; and / or the support has a pore volume of 0.45 to 1.1 ml / g; and / or the active metal component is present in an amount of 8 to 45 g per 100 g of the matrix; and / or the content of the metal promoter is 0.1 to 10 g per 100 g of the matrix; and / or the weight ratio of the Group VIIB metal to the Group IB metal in the metal cocatalyst is 0.05 to 15:1, preferably 0.1 to 12:1; and / or said Group VIIB metal is selected from manganese and / or rhenium; And / or the catalyst according to item B1 or B2, wherein the Group IB metal is at least one selected from the group consisting of copper, silver and gold.

[0205] B4 The catalyst according to any one of items B1 to B3, wherein the support is prepared by a method comprising successively shaping, drying and calcining a mixture comprising an alumina precursor, a doping element, and optionally an additional support precursor, wherein the additional support precursor is selected from a silica precursor and / or a molecular sieve precursor, and the doping element is provided by a support modifier, and the support modifier is at least one inorganic acid. B5. The catalyst according to item B4, wherein the inorganic acid is at least one selected from inorganic acids containing non-metal acid radical ions, preferably at least one selected from boric acid, hydrofluoric acid, phosphoric acid, sulfuric acid, and selenic acid.

[0206] B6, the alumina precursor is pseudoboehmite, and the pseudoboehmite has a content of 260 to 380 m 2 / g and a pore volume of 0.78 to 1.2 ml / g.

[0207] B7, the drying conditions include a temperature of 80 to 150°C and a time of 6 to 20 hours; And / or the catalyst according to any one of items B4 to B6, wherein the calcination conditions include a temperature of 550 to 1050°C and a time of 2 to 20 hours.

[0208] B8. A method for producing the catalyst according to any one of items B1 to B7, comprising supporting the active metal component and the metal promoter on the support.

[0209] B9, a carrier as defined in any one of items B2 to B7.

[0210] B10: Use of the catalyst according to any one of items B1 to B7, or the method according to item B8, or the support according to item B9, in amination to produce an organic amine.

[0211] B11, a process for producing an organic amine, comprising the steps of: contacting an amination raw material and an aminating agent with the catalyst according to any one of items B1 to B7 in the presence of hydrogen for an amination reaction; Alternatively, the method includes the steps of screening a catalyst comprising the support defined in any one of items B1 to B7, and contacting an amination raw material and an aminating agent with the screened catalyst in the presence of hydrogen for an amination reaction.

[0212] B12, the amination conditions are that the molar ratio of hydrogen to the aminating agent to the amination raw material is 1 to 5:2 to 33:1, the temperature is 110 to 220°C, the pressure is 0.8 to 25 MPa, and the liquid phase volumetric space velocity of the amination raw material is 0.06 to 1 m 3 / (m 3 h) including being; and / or the amination raw material is at least one selected from the group consisting of C2 to C20 alcohols, C3 to C20 ketones, C2 to C20 alcoholamines, and C2 to C20 aldehydes, and is preferably ethanol, acetaldehyde, n-propanol, propionaldehyde, isopropanol, n-butanol, butylaldehyde, isobutanol, isobutylaldehyde, 2-ethylhexanol, 2-ethylhexaldehyde, octanol, octanal, dodecanol, dodecanal, hexadecanol, hexadecanal, cyclopentanol, cyclohexanol, cyclooctanol, or cyclododecanol. at least one of ethanol, benzyl alcohol, benzaldehyde, phenethyl alcohol, phenylacetaldehyde, 1,4-butanediol, 1,4-butanedial, 1,5-pentanediol, 1,5-glutaraldehyde, 1,6-hexanediol, 1,6-hexanedial, 1,8-octanedial, 1,8-octanedial, ethanolamine, propanolamine, isopropanolamine, 6-aminohexanol, diethanolamine, diisopropanolamine, dimethylethanolamine, acetone, ethylene glycol, 1,3-propanediol, and 1,12-dodecanediol; And / or the method according to Item B11, wherein the aminating agent is at least one selected from the group consisting of ammonia, C1-C12 primary amines, and C1-C12 secondary amines, and preferably at least one of ammonia, monomethylamine, dimethylamine, methylethylamine, monoethylamine, and diethylamine.

[0213] B13: When the amination raw material is a monohydric alcohol, the amination conditions are such that the molar ratio of hydrogen to the aminating agent to the amination raw material is 1 to 4:2 to 10:1, the temperature is 130 to 210°C, the pressure is 1 to 3.5 MPa, and the liquid phase volumetric space velocity of the amination raw material is 0.1 to 0.8 m 3 / (m 3 h) including being; Alternatively, when the amination raw material is a ketone or an aldehyde, the amination conditions are a molar ratio of hydrogen to the aminating agent to the amination raw material of 1 to 4:2 to 5:1, a temperature of 110 to 170°C, a pressure of 0.8 to 2.5 MPa, and a liquid phase volumetric space velocity of the amination raw material of 0.1 to 1 m 3 / (m 3 h) including being; Alternatively, when the amination raw material is an alcohol amine, the amination conditions are a molar ratio of hydrogen to the aminating agent to the amination raw material of 1 to 4:3 to 25:1, a temperature of 130 to 200°C, a pressure of 1 to 18 MPa, and a liquid phase volumetric space velocity of the amination raw material of 0.06 to 0.8 m 3 / (m 3 h) including being; Alternatively, when the amination raw material is a mixture of 1,6-hexanediol, hexamethyleneimine, and 6-amino-1-hexanol or a dihydric alcohol, the amination conditions are a molar ratio of hydrogen to the aminating agent to the amination raw material of 1 to 4:3 to 33:1, a temperature of 130 to 220°C, a pressure of 4 to 25 MPa, and a liquid phase volumetric space velocity of the amination raw material of 0.06 to 0.8 m 3 / (m 3 The method according to item B12, comprising: h).

[0214] C1. A catalyst having the function of catalyzing alcohol hydroamination, comprising a support, and a metal active component and a metal cocatalyst supported on the support, wherein the metal active component is cobalt and / or nickel; and the metal cocatalyst is a combination of at least one Group VIIB metal and at least one Group IIB metal.

[0215] C2. The catalyst according to item C1, wherein the support comprises an alumina support, a doping element, and optionally an additional support which is at least one selected from the group consisting of silica, molecular sieves, and diatomaceous earth; the support has an ammonia adsorption capacity of 0.3 to 0.7 mmol / g and a carbon dioxide adsorption capacity of 0.05 to 0.4 mmol / g; and the ratio of the pore volume of pores having a pore diameter in the range of 7 to 27 nm to the pore volume of the support is more than 65%.

[0216] C3, the content of the alumina support in the support is 70% by weight or more, preferably 80 to 100% by weight, based on the total amount of the alumina support and the additional support; and / or said doping element is present in the support in an amount of 0.05 to 6% by weight, preferably 0.08 to 4% by weight, relative to the total weight of said matrix; and / or the doping element in the carrier is selected from metal elements and non-metal elements, and does not contain sodium or chlorine; the metal element is at least one selected from the group consisting of Group IA metal elements, Group IIA metal elements, Group VA metal elements and Lanthanide metal elements, preferably at least one of calcium, magnesium, potassium, bismuth, strontium, barium ions and lanthanum; the non-metal element is derived from at least one non-metal acid radical ion, preferably at least one selected from the group consisting of borate ions, fluoride ions, phosphate ions, sulfate ions and selenate ions; and / or the support has an ammonia adsorption capacity of 0.3 to 0.6 mmol / g and a carbon dioxide adsorption capacity of 0.05 to 0.3 mmol / g; and / or the ratio of the pore volume of pores having a pore diameter in the range of 7 to 27 nm to the pore volume of the support is 70 to 90%, and the ratio of the pore volume of pores having a pore diameter of less than 7 nm to the pore volume of the support is 0 to 10%; and / or the carrier is 120 to 205 m 2 / g specific surface area; and / or the support has a pore volume of 0.45 to 1.2 ml / g; and / or the content of the metal active component is 14 to 46 g per 100 g of the matrix; and / or the content of the metal promoter is 0.1 to 10 g per 100 g of the matrix; and / or the weight ratio of the Group VIIB metal to the Group IIB metal in the metal cocatalyst is 0.2 to 20:1, preferably 0.3 to 6:1; and / or said Group VIIB metal is selected from manganese and / or rhenium; and / or the catalyst according to item C1 or C2, wherein the Group IIB metal is selected from zinc.

[0217] C4. The catalyst according to any one of items C1 to C3, wherein the support is prepared by a method comprising successively shaping, drying and calcining a mixture comprising the doping element, an alumina precursor and optionally an additional support precursor, wherein the additional support precursor is at least one selected from the group consisting of a silica precursor, a molecular sieve precursor and a diatomaceous earth precursor.

[0218] C5. The catalyst according to item C4, wherein the doping element is provided by a support modifier which is at least one selected from the group consisting of boric acid, nickel borate, cobalt borate, potassium borate, hydrofluoric acid, potassium fluoride, cobalt fluoride, nickel fluoride, phosphoric acid, aluminum phosphate, tripotassium 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.

[0219] C6. The alumina precursor is boehmite, and the boehmite has a specific surface area of 265 to 410 m 2 / g and a pore volume of 0.7 to 1.2 ml / g, the catalyst according to item C4 or C5.

[0220] C7. The drying conditions include that the temperature is 80 to 150 °C and the time is 6 to 20 hours; and / or the calcination conditions include that the temperature is 500 to 1100 °C and the time is 2 to 20 hours, the catalyst according to any one of items C4 to C6. C8. A method for producing the catalyst according to any one of items C1 to C7, including a step of supporting the metal active component and the metal promoter on the carrier.

[0221] C9. A carrier defined by any one of items C2 to C7.

[0222] C10. Use of the catalyst according to any one of items C1 to C7, or the method according to item C8, or the carrier according to item C9, in amination for producing an organic amine.

[0223] C11. A method for producing an organic amine, including the following steps: a step of contacting an amination raw material and an aminating agent with the catalyst according to any one of items C1 to C7 in the presence of hydrogen for an amination reaction; alternatively, the method includes a step of screening a catalyst containing the carrier defined by any one of items C1 to C7, and a step of contacting the amination raw material and the aminating agent with the screened catalyst in the presence of hydrogen for an amination reaction.

[0224] C11. The amination conditions include that the molar ratio of hydrogen, the aminating agent, and the amination raw material is 1 to 5:2 to 30:1, the temperature is 110 to 220 °C, the pressure is 0.8 to 25 MPa, and the liquid-phase volume space velocity of the amination raw material is 0.06 to 1 m 3 / (m 3 ·h). And / or, the amination raw material is at least one selected from the group consisting of C2 to C20 alcohols, C3 to C20 ketones, C2 to C20 alcoholamines, and C2 to C20 aldehydes, and is preferably ethanol, acetaldehyde, n-propanol, propionaldehyde, isopropanol, n-butanol, butyraldehyde, isobutanol, isobutyraldehyde, 2-ethylhexanol, 2-ethylhexaldehyde, octanol, octanal, dodecanol, dodecanal, hexadecanol, hexadecanal, cyclopentanol, cyclohexanol, cyclooctanol ... at least one of clododecanol, benzyl alcohol, benzaldehyde, phenethyl alcohol, phenylacetaldehyde, 1,4-butanediol, 1,4-butanedial, 1,5-pentanediol, 1,5-glutaraldehyde, 1,6-hexanediol, 1,6-hexanedial, 1,8-octanedial, 1,8-octanedial, ethanolamine, propanolamine, isopropanolamine, 6-aminohexanol, diethanolamine, dimethylethanolamine, acetone, ethylene glycol, 1,3-propanediol, and 1,12-dodecanediol; And / or the method according to item C11, wherein the aminating agent is at least one selected from the group consisting of ammonia, C1-C12 primary amines and C1-C12 secondary amines, preferably at least one of ammonia, monomethylamine, dimethylamine, methylethylamine, monoethylamine and diethylamine. C13: When the amination raw material is a monohydric alcohol, the amination conditions are such that the molar ratio of hydrogen to the aminating agent to the amination raw material is 1 to 4:2 to 9:1, the temperature is 130 to 200°C, the pressure is 1 to 2.5 MPa, and the liquid phase volumetric space velocity of the amination raw material is 0.1 to 0.8 m 3 / (m 3 h) including being; Alternatively, when the amination raw material is a ketone or an aldehyde, the amination conditions are a molar ratio of hydrogen to the aminating agent to the amination raw material of 1 to 4:2 to 6:1, a temperature of 110 to 180°C, a pressure of 0.8 to 2.5 MPa, and a liquid phase volumetric space velocity of the amination raw material of 0.1 to 0.8 m 3 / (m 3 h) including being; Alternatively, when the amination raw material is an alcohol amine, the amination conditions are a molar ratio of hydrogen to the aminating agent to the amination raw material of 1 to 4:3 to 20:1, a temperature of 130 to 200°C, a pressure of 1 to 15 MPa, and a liquid phase volumetric space velocity of the amination raw material of 0.06 to 0.8 m 3 / (m 3 h) including being; Alternatively, when the amination raw material is a mixture of 1,6-hexanediol, hexamethyleneimine, and 6-amino-1-hexanol or a dihydric alcohol, the amination conditions are a molar ratio of hydrogen to the aminating agent to the amination raw material of 1 to 4:3 to 30:1, a temperature of 130 to 220°C, a pressure of 1 to 25 MPa, and a liquid phase volumetric space velocity of the amination raw material of 0.1 to 0.8 m 3 / (m 3 The method according to item C12, comprising: h).

[0225] D1. A catalyst having the function of catalyzing the amination of alcohols, comprising a support, an active metal component supported on the support, and a metal cocatalyst supported on the support, wherein the active metal component is cobalt and / or nickel; and the metal cocatalyst is a combination of at least one Group VIB metal, at least one Group IB metal, and at least one Group IIB metal.

[0226] D2. The catalyst according to item D1, wherein the support comprises an alumina support, a doping element, and an additional support selected from silica and / or a molecular sieve; the support has an ammonia adsorption capacity of 0.25 to 0.6 mmol / g; and the ratio of the pore volume of pores having a pore diameter in the range of 7 to 27 nm to the pore volume of the support is more than 65%.

[0227] D3, the content of the alumina support in the support is 70% by weight or more, preferably 80 to 97% by weight, based on the total amount of the alumina support and the additional support; and / or the content of the doping element is 0.05-5 wt. %, preferably 0.08-3 wt. %, based on the weight of the support; and / or said doping element in said support is a non-metallic element, preferably incorporated in the form of at least one selected from the group consisting of borate ions, fluoride ions, phosphate ions, sulfate ions and selenate ions; and / or the support has an ammonia adsorption capacity of 0.3 to 0.6 mmol / g; and / or the ratio of the pore volume of pores having a pore diameter in the range of 7 to 27 nm to the pore volume of the support is 70 to 90%, and the ratio of the pore volume of pores having a pore diameter of less than 7 nm to the pore volume of the support is 0 to 8%; And / or the carrier is 120 to 210 m 2 / g specific surface area; and / or the support has a pore volume of 0.45 to 1.1 ml / g; and / or the active metal component is present in an amount of 10 to 46 g, preferably 18 to 38 g, per 100 g of the support; and / or the content of the metal promoter is 0.1 to 10 g, preferably 0.5 to 6 g, per 100 g of the support; and / or the metal co-catalyst comprises a Group VIA metal, a Group IB metal, and the Group IIB metal in a weight ratio of 0.1-10:0.1-10:1, preferably 0.2-8:0.2-8:1; And / or, the Group VIB metal is selected from molybdenum and / or tungsten; And / or, the Group IB metal is at least one selected from the group consisting of copper, silver and gold; And / or, the Group IIB metal is selected from zinc, the catalyst according to item D1 or D2.

[0228] D4. The carrier is prepared by a method including the steps of continuously forming, drying and firing a mixture including the alumina precursor, the doping element and an additional carrier precursor, and the additional carrier precursor is selected from a silica precursor and / or a molecular sieve precursor, the catalyst according to any one of items D1 to D3.

[0229] D5. The doping element is provided by at least one of boric acid, hydrofluoric acid, phosphoric acid, sulfuric acid, and selenic acid, the catalyst according to item D4.

[0230] D6. The alumina precursor is pseudo-boehmite, and the pseudo-boehmite has a specific surface area of 260 to 400 m 2 / g and a pore volume of 0.8 to 1.2 ml / g, the catalyst according to item D4 or D5.

[0231] D7. The drying conditions include a temperature of 80 to 150 °C and a time of 6 to 20 hours; And / or, the firing conditions include a temperature of 500 to 1100 °C and a time of 2 to 20 hours, the catalyst according to any one of items D4 to D6.

[0232] D8. A method for manufacturing the catalyst according to any one of items D1 to D7, including the step of supporting the active metal component and the metal promoter on the carrier.

[0233] D9. A carrier defined by any one of items D2 to D7.

[0234] D10. Use of the catalyst according to any one of items D1 to D7, or the method according to item D8, or the support according to item D9, in amination to produce an organic amine.

[0235] D11, A method for producing an organic amine, comprising the step of contacting an amination feedstock and an aminating agent with a catalyst defined in any one of items D1 to D7 in the presence of hydrogen for an amination reaction.

[0236] D12, the amination conditions are that the molar ratio of hydrogen to the aminating agent to the amination raw material is 1 to 5:2 to 35:1, the temperature is 105 to 220°C, the pressure is 0.7 to 25 MPa, and the liquid phase volumetric space velocity of the amination raw material is 0.06 to 1 m 3 / (m 3 h) including being; And / or, the amination raw material is at least one selected from the group consisting of C2 to C20 alcohols, C3 to C20 ketones, C2 to C20 alcoholamines, and C2 to C20 aldehydes, and is preferably ethanol, acetaldehyde, n-propanol, propionaldehyde, isopropanol, n-butanol, butyraldehyde, isobutanol, isobutyraldehyde, 2-ethylhexanol, 2-ethylhexaldehyde, octanol, octanal, dodecanol, dodecanal, hexadecanol, hexadecanal, cyclopentanol, cyclohexanol, cyclooctanol ... at least one of clododecanol, benzyl alcohol, benzaldehyde, phenethyl alcohol, phenylacetaldehyde, 1,4-butanediol, 1,4-butanedial, 1,5-pentanediol, 1,5-glutaraldehyde, 1,6-hexanediol, 1,6-hexanedial, 1,8-octanedial, 1,8-octanedial, ethanolamine, propanolamine, isopropanolamine, 6-aminohexanol, diethanolamine, dimethylethanolamine, acetone, ethylene glycol, 1,3-propanediol, and 1,12-dodecanediol; And / or the method according to Item D11, wherein the aminating agent is at least one selected from the group consisting of ammonia, C1-C12 primary amines, and C1-C12 secondary amines, preferably at least one selected from the group consisting of ammonia, monomethylamine, dimethylamine, methylethylamine, monoethylamine, and diethylamine.

[0237] D13: When the amination raw material is a monohydric alcohol, the amination conditions are a molar ratio of hydrogen to the aminating agent to the amination raw material of 1 to 4:2 to 8:1, a temperature of 130 to 200°C, a pressure of 1 to 2.5 MPa, and a liquid phase volumetric space velocity of the amination raw material of 0.1 to 0.8 m 3 / (m 3 h) including being; Alternatively, when the amination raw material is a ketone or an aldehyde, the amination conditions are a molar ratio of hydrogen to the aminating agent to the amination raw material of 1 to 4:2 to 5:1, a temperature of 105 to 180°C, a pressure of 0.7 to 2.5 MPa, and a liquid phase volumetric space velocity of the amination raw material of 0.1 to 0.8 m 3 / (m 3 h) including being; Alternatively, when the amination raw material is an alcohol amine, the amination conditions are a molar ratio of hydrogen to the aminating agent to the amination raw material of 1 to 4:3 to 25:1, a temperature of 130 to 200°C, a pressure of 5 to 18 MPa, and a liquid phase volumetric space velocity of the amination raw material of 0.06 to 0.8 m 3 / (m 3 h) including being; Alternatively, when the amination raw material is a mixture of 1,6-hexanediol, hexamethyleneimine, and 6-amino-1-hexanol or a dihydric alcohol, the amination conditions are a molar ratio of hydrogen to the aminating agent to the amination raw material of 1 to 4:3 to 35:1, a temperature of 130 to 220°C, a pressure of 2 to 25 MPa, and a liquid phase volumetric space velocity of the amination raw material of 0.1 to 0.8 m 3 / (m3 The method according to item D12, comprising: h).

[0238] E1. A titanium-containing catalyst with amination function, comprising a support, an active metal component, and optionally a metal promoter supported on the support, wherein the catalyst comprises alumina and titania in a weight ratio of 1.5 to 5:1, and the active metal component is cobalt and / or nickel.

[0239] E2, the weight ratio of alumina to titania is 2 to 4.5:1; and / or the active metal component is present in an amount of 13 to 40 g, preferably 20 to 36 g, per 100 g of the support; and / or the content of the metal promoter is 0 to 10 g, preferably 2.5 to 8 g, per 100 g of the support; and / or the titanium-containing catalyst according to item E1, wherein the metal promoter is at least one selected from the group consisting of Group VIB elements, Group VIIB elements, Group IB elements, Group IIB elements and Lanthanide elements, preferably at least one of Cr, Mo, W, Mn, Re, Cu, Ag, Au, Zn, La and Ce.

[0240] E4, the titanium-containing catalyst has an ammonia adsorption capacity of 0.3 to 0.4 mmol / g, a carbon dioxide adsorption capacity of 0.07 to 0.2 mmol / g, and a specific surface area of ​​130 to 180 m 2 / g, the pore volume is 0.55 to 0.75 ml / g, the ratio of the pore volume of pores having a pore radius of less than 4 nm to the total pore volume is less than 20%, and the ratio of the pore volume of pores having a pore radius of more than 10 nm to the total pore volume is less than 15%; and / or the titanium-containing catalyst according to any one of items E1 to E3, wherein the support is doped with sulfur in an amount of 0.1 to 0.5 g, preferably 0.15 to 0.4 g, per 100 g of alumina and titania.

[0241] E5, a method for producing a titanium-containing catalyst having an amination function, comprising the following (1) and (2): (1) kneading, molding, and calcining pseudo-boehmite and titanium white powder to obtain a carrier, wherein the pseudo-boehmite and titanium white powder are used in amounts such that the weight ratio of alumina to titania in the obtained carrier is 2 to 5:1; (2) supporting an active metal component and optionally a metal promoter on the resulting support, wherein the active metal component comprises cobalt and / or nickel.

[0242] E6, the pseudoboehmite and the titanium white powder are used in amounts such that the weight ratio of the alumina to the titania in the resulting support is 2 to 4.5:1; and / or the pseudo-boehmite is prepared by at least one of a carbonization method, an organoaluminum hydrolysis method, an aluminum sulfate method, and a nitric acid method, and is preferably prepared by the carbonization method or the aluminum sulfate method; And / or the method according to item E4, wherein the titanium white powder is prepared by a precipitation method and / or a sol-gel method, preferably the titanium white powder is prepared by using titanyl sulfate as a raw material.

[0243] E7. The method according to item E5, wherein the content of sulfate in the titanium white powder is 0.2 to 3% by weight.

[0244] E8, the active metal component is used in an amount such that it is present in an amount of 13 to 40 g, preferably 20 to 36 g, per 100 g of the support; and / or the content of the metal promoter is such that the metal promoter is present in an amount of 0 to 10 g, preferably 2.5 to 8 g, per 100 g of the support; and / or the method according to any one of items E4 to E6, wherein the metal promoter is at least one selected from the group consisting of Group VIB elements, Group VIIB elements, Group IB elements, Group IIB elements and Lanthanide elements, preferably at least one of Cr, Mo, W, Mn, Re, Cu, Ag, Au, Zn, La and Ce.

[0245] E8, a titanium-containing catalyst obtained by the method described in any one of items E4 to E7.

[0246] E9, Use of a titanium-containing catalyst according to any one of paragraphs E1 to E3 or E8, or a process according to any one of paragraphs E4 to E7, in the amination of an alcohol.

[0247] E10, comprising contacting ammonia and / or an organic amine with an alcohol in the presence of a titanium-containing catalyst according to any one of items E1-E3 or E8 for an amination reaction; Or alternatively, the titanium-containing catalyst is prepared by the method described in any one of items E4 to E7, and then ammonia and / or an organic amine are contacted with an alcohol in the presence of the obtained titanium-containing catalyst for an amination reaction.

[0248] [Example] The present application is further illustrated by, but not limited to, the following examples.

[0249] In the following examples and comparative examples, unless otherwise specified, the agents and starting materials used are commercially available products that are chemically pure.

[0250] The test equipment and methods used in the following examples are as follows: 1) NH3-TPD test Test equipment: Autochem 2920 fully automatic chemisorption instrument (automated catalyst characterization system), manufactured by MICROMERITICS, USA; Test conditions: Approximately 0.1 g of sample was accurately weighed and placed in a sample tube. While purging with helium gas, the tube was heated to 600°C at a rate of 10°C / min, held for 1 hour, and then cooled to 120°C. The gas was then switched to a 10% NH3-He mixed gas and allowed to adsorb for 60 minutes. After that, the gas was switched back to helium gas and purged for 1 hour. After the baseline stabilized, counting began. The resulting material was heated to 600°C at a rate of 10°C / min, held for 30 minutes, and recording was stopped to terminate the test. The peak area was integrated to determine the amount of NH3 desorption, which was used to characterize the ammonia adsorption capacity of the sample.

[0251] 2) CO2-TPD test Test equipment: Autochem 2920 fully automatic chemisorption instrument (automated catalyst characterization system), manufactured by MICROMERITICS, USA; Test conditions: Approximately 0.1 g of sample was accurately weighed and placed in a sample tube. While purging with helium gas, the tube was heated to 600°C at a rate of 10°C / min. The tube was then left to dwell for 1 hour. The tube was then cooled to 120°C. The gas was then replaced with a 10% CO2-He mixed gas. The tube was then allowed to adsorb for 60 minutes, after which the gas was replaced with helium gas and purged for 1 hour. After the baseline stabilized, counting began. The tube was then heated to 600°C at a rate of 10°C / min. The tube was then held for 30 minutes. Recording was then stopped, and the test was terminated. The peak area was integrated to determine the amount of CO2 desorption, which was used to characterize the CO2 adsorption capacity of the sample.

[0252] 3) BET test Testing equipment: Fully automatic physicochemical adsorption analyzer (automated micropore & chemical adsorption analyzer), manufactured by MICROMERITICS, USA; Test conditions: Test gas: N2 (purity 99.999%); Degassing conditions: Heat to 350 °C at a rate of 10 °C / min and evacuate for 4 hours; Analysis conditions: Obtain the specific surface area and pore volume by fully analyzing the mesopore isotherm.

[0253] 4)XRD analysis Test equipment: Empyrean X-ray diffractometer manufactured by PANalytical BV with a Cu target anode target and a Pixcel 3D detector; Test conditions: tube voltage 40 kV, tube current 40 mA, divergence slit 1 / 4°, anti-divergence slit 1 / 2°, receiving slit height 7.5 mm, scanning speed 0.013° / step, scanning range 5°~90°.

[0254] The particle sizes of the active metal components and metal promoters, if present, were obtained by calculation using the Scherrer equation.

[0255] Example Series I The first type of embodiment of the present application will be explained in more detail below with reference to the examples in Example Series I. In the following examples in Example Series I, the pseudo-boehmite powder used had an (Al2O3) content of 72% by weight on a dry basis.

[0256] Example I-1 Calcium nitrate tetrahydrate (analytical pure), nitric acid and dilute phosphoric acid aqueous solutions were dissolved in pseudoboehmite powder (specific surface area 298 m 2 The resulting mixture was extruded into strips with a diameter of 5 mm, cut into pieces with a length of 4 mm, dried at 100°C for 12 hours, and calcined at 720°C for 8 hours to obtain the desired support. Calculated as Al2O3, the amount of calcium nitrate tetrahydrate (analytical pure) used per 100 g of pseudoboehmite powder was 2.95 g, the amount of nitric acid was 6.5 g, and the amount of phosphoric acid was 0.63 g.

[0257] 176.4 g of cobalt nitrate hexahydrate (technical grade, 98% purity) was dissolved in water to obtain 182 mL of solution, which was then spray-impregnated twice onto 100 g of the obtained support, dried at 120°C for 8 hours after each spray-impregnation, then calcined at 400°C for 4 hours, and then reduced with hydrogen at a temperature gradually increasing at a rate of 20°C / hour, and finally reduced at 430°C for 3 hours to obtain catalyst AI-1.

[0258] Example I-2 Aqueous solutions of analytically pure potassium nitrate, nitric acid, and dilute aqueous solutions of boric acid were dissolved in pseudoboehmite powder (specific surface area 286 m 2 The resulting mixture was continuously added to a solution of 100 g of pseudoboehmite powder (having a pore volume of 0.88 ml / g and a mass of 100 g of boehmite powder), extruded into cloverleaf-shaped granules with a thickness of 3 mm, dried at 120°C for 8 hours, and then calcined at 690°C for 10 hours to obtain the desired support. The amount of potassium nitrate (analytical pure) used was 0.26 g, the amount of nitric acid was 5.2 g, and the amount of boric acid was 4.57 g, calculated as Al2O3, per 100 g of pseudoboehmite powder.

[0259] 151.7 g of nickel nitrate hexahydrate (technical grade, 98% purity) was dissolved in water to obtain 168 mL of solution, which was then spray-impregnated twice onto 100 g of the obtained support, dried at 120°C for 4 hours after each spray impregnation, then calcined at 390°C for 4 hours, and then reduced with hydrogen at a temperature gradually increasing at a rate of 20°C / hour, and finally reduced at 440°C for 3 hours to obtain catalyst AI-2.

[0260] Example I-3 Aqueous magnesium nitrate hexahydrate (analytical pure), dilute aqueous solutions of nitric acid and sulfuric acid were dissolved in pseudoboehmite powder (specific surface area 310 m 2The resulting mixture was continuously added to a powder of pseudoboehmite (having a pore volume of 0.92 ml / g and a particle size of 0.92 ml / g) while kneading, extruded into toothed spheres with a diameter of 4 mm, dried at 100°C for 15 hours, and then calcined at 780°C for 10 hours to obtain the desired support. Calculated as Al2O3, the amount of magnesium nitrate hexahydrate (analytically pure) used per 100 g of pseudoboehmite powder was 0.84 g, the amount of nitric acid was 6.1 g, and the amount of sulfuric acid was 1.22 g.

[0261] 50.4 g of cobalt nitrate hexahydrate (technical grade, 98% purity) and 32.6 g of 50 wt % manganese nitrate aqueous solution were dissolved in water to obtain 156 mL of solution. The solution was supported on 100 g of the obtained support by spray impregnation twice, and after each spray impregnation, it was dried at 120 ° C for 4 hours and calcined at 400 ° C for 4 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20 ° C / hour, and finally reduced at 430 ° C for 3 hours to obtain catalyst AI-3.

[0262] Example I-4 Bismuth nitrate pentahydrate (analytical pure) aqueous solution, dilute aqueous solutions of nitric acid and phosphoric acid were dissolved in pseudoboehmite powder (specific surface area 321 m 2 The resulting mixture was continuously added to a powder of pseudoboehmite (having a pore volume of 0.93 ml / g and a diameter of 5 mm), extruded into strips of 5 mm diameter, cut into pieces of 4 mm length, dried at 80°C for 20 hours, and then calcined at 660°C for 15 hours to obtain the desired support. The amount of bismuth nitrate pentahydrate (analytically pure), nitric acid, and phosphoric acid used per 100 g of pseudoboehmite powder was 1.86 g, 6.5 g, and 1.9 g, calculated as Al2O3.

[0263] 75.6 g of cobalt nitrate hexahydrate (technical grade, 98% purity) and 50.6 g of nickel nitrate hexahydrate (technical grade, 98% purity) were dissolved in water to obtain 166 mL of solution. The solution was twice supported on 100 g of the obtained support by spray impregnation, and after each spray impregnation, it was dried at 120 ° C for 4 hours, then calcined at 400 ° C for 4 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20 ° C / hour, and finally reduced at 430 ° C for 3 hours to obtain catalyst AI-4.

[0264] Example I-5 Aqueous solutions of barium nitrate (analytical pure), nitric acid, and dilute aqueous solutions of boric acid were dissolved in pseudoboehmite powder (specific surface area 275 m 2 The resulting mixture was continuously added to a solution of 100 g of pseudoboehmite powder (0.85 ml / g, pore volume 0.85 ml / g) while kneading, extruded into cloverleaf-shaped granules with a thickness of 3 mm, dried at 150°C for 6 hours, and calcined at 810°C for 5 hours to obtain the desired support. The amount of barium nitrate (analytical pure) used was 0.19 g, the amount of nitric acid was 6.5 g, and the amount of boric acid was 2.29 g, calculated as Al2O3, per 100 g of pseudoboehmite powder.

[0265] 126.4 g of nickel nitrate hexahydrate (technical grade, 98% purity) and 2.9 g of ammonium perrhenate (99% purity) were dissolved in water to obtain 160 mL of solution. The solution was twice supported on 100 g of the obtained support by spray impregnation, and after each spray impregnation, it was dried at 120 ° C for 4 hours, then calcined at 390 ° C for 4 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20 ° C / hour, and finally reduced at 440 ° C for 3 hours to obtain catalyst AI-5.

[0266] Example I-6 Aqueous solutions of cesium nitrate (analytical pure), nitric acid, and dilute aqueous solutions of sulfuric acid were added to pseudoboehmite powder (specific surface area 269 m 2 The resulting mixture was continuously added to a powder of 100 g of pseudoboehmite (having a pore volume of 0.86 ml / g and a pore volume of 0.86 ml / g), extruded into 4 mm diameter toothed spheres, dried at 120°C for 8 hours, and calcined at 830°C for 4 hours to obtain the desired support. Calculated as Al2O3, the amount of cesium nitrate, nitric acid, and sulfuric acid used per 100 g of pseudoboehmite powder was 0.03 g, 6.2 g, and 0.09 g, respectively.

[0267] 201.6 g of cobalt nitrate hexahydrate (technical grade, with a purity of 98%) was dissolved in water to obtain 156 mL of solution; 7.4 g of ammonium molybdate tetrahydrate (analytical pure) was dissolved in water to obtain 78 mL of solution; the cobalt nitrate solution was supported twice on 100 g of the obtained support by spray impregnation; then, the ammonium molybdate solution was supported once on the support by spray impregnation, and after spray impregnation, it was dried at 120 ° C for 4 hours and calcined at 400 ° C for 4 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20 ° C / hour, and finally reduced at 430 ° C for 3 hours to obtain catalyst AI-6.

[0268] Example I-7 Aqueous solutions of lanthanum nitrate hexahydrate (analytical pure), nitric acid, and sulfuric acid were dissolved in a dilute solution of pseudoboehmite powder (specific surface area 259 m 2 The resulting mixture was extruded into 4 mm diameter serrated spheres, dried at 100°C for 10 hours, and calcined at 980°C for 5 hours to obtain the desired support. Calculated as Al2O3, the amount of lanthanum nitrate hexahydrate (analytical pure) used per 100 g of pseudoboehmite powder was 0.47 g, the amount of nitric acid was 5 g, and the amount of sulfuric acid was 0.61 g.

[0269] 100.8 g of cobalt nitrate hexahydrate (technical grade, 98% purity) and 14.1 g of copper nitrate trihydrate (analytical purity) were dissolved in water to obtain 176 mL of solution, which was then spray-impregnated twice onto 100 g of the obtained support, dried at 120°C for 4 hours after each spray-impregnation, then calcined at 400°C for 4 hours, and then reduced with hydrogen at a temperature gradually increasing at a rate of 20°C / hour, and finally reduced at 430°C for 3 hours to obtain catalyst AI-7.

[0270] Example I-8 Aqueous solutions of lanthanum nitrate hexahydrate (analytical pure), nitric acid, and dilute aqueous solutions of hydrofluoric acid were dissolved in pseudoboehmite powder (specific surface area 291 m). 2The resulting mixture was continuously added to a mixture of 100 g of pseudoboehmite powder (0.93 ml / g, pore volume 0.93 ml / g) while kneading, extruded into 4 mm diameter toothed spheres, dried at 90°C for 12 hours, and then calcined at 900°C for 3 hours to obtain the desired support. Calculated as Al2O3, the amount of lanthanum nitrate hexahydrate (analytical pure) used was 0.62 g, the amount of nitric acid was 5.5 g, and the amount of hydrofluoric acid was 0.05 g per 100 g of pseudoboehmite powder.

[0271] 126 g of cobalt nitrate hexahydrate (technical grade, 98% purity) and 25.3 g of nickel nitrate hexahydrate (technical grade, 98% purity) were dissolved in water to obtain 177 mL of solution. The solution was supported on 100 g of the obtained support by spray impregnation three times, and after each spray impregnation, it was dried at 120 ° C for 4 hours, then calcined at 400 ° C for 4 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20 ° C / hour, and finally reduced at 430 ° C for 3 hours to obtain catalyst AI-8.

[0272] Example I-9 Aqueous solutions of calcium nitrate tetrahydrate (analytical pure), nitric acid, and dilute aqueous solutions of hydrofluoric acid were dissolved in pseudoboehmite powder (specific surface area 312 m 2 The resulting mixture was continuously added to a solution of 1.02 ml / g of calcium nitrate tetrahydrate (having a pore volume of 1.02 ml / g) while kneading, extruded into cloverleaf-shaped granules with a thickness of 4 mm, dried at 100°C for 8 hours, and then calcined at 930°C for 3 hours to obtain the desired support. The amount of calcium nitrate tetrahydrate (analytically pure), nitric acid, and hydrofluoric acid used per 100 g of pseudoboehmite powder, calculated as Al2O3, was 3.54 g, 6.5 g, and 0.13 g, respectively.

[0273] 176.4 g of cobalt nitrate hexahydrate (technical grade, 98% purity) and 1.3 g of silver nitrate (analytical purity) were dissolved in water to obtain 188 mL of solution, which was then spray-impregnated onto 100 g of the obtained support three times, dried at 120°C for 4 hours after each spray-impregnation, then calcined at 390°C for 4 hours, and then reduced with hydrogen at a temperature gradually increasing at a rate of 20°C / hour, and finally reduced at 440°C for 3 hours to obtain catalyst AI-9.

[0274] Example I-10 Silica gel powder (specific surface area 385m 2 The silica gel (having a pore volume of 0.95 ml / g and a pore volume of 0.95 ml / g) was used as the raw material and formed into toothed spheres with a diameter of 4 mm by ball rolling in a dilute acid solution containing magnesium nitrate, nitric acid, and sulfuric acid. The spheres were dried at 80°C for 15 hours and then calcined at 750°C for 8 hours to obtain the desired support. Calculated as SiO2, the amount of magnesium nitrate hexahydrate (analytical pure) per 100 g of silica gel powder was 8.44 g, the amount of nitric acid was 6.1 g, and the amount of sulfuric acid was 4.28 g.

[0275] The remaining procedures were the same as those described in Example 3 to obtain catalyst AI-10.

[0276] Example I-11 Aqueous solutions of potassium nitrate (analytical pure), nitric acid, and dilute aqueous solutions of phosphoric acid were dissolved in pseudoboehmite powder (specific surface area 261 m 2 The resulting mixture was continuously added to a powder of pseudoboehmite (having a pore volume of 0.83 ml / g and a pore volume of 0.83 ml / g) while kneading, extruded into toothed spheres with a diameter of 4 mm, dried at 100°C for 10 hours, and then calcined at 1030°C for 5 hours to obtain the desired support. Calculated as Al2O3, the amount of potassium nitrate (analytical pure) used 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.

[0277] The remaining procedures were the same as those described in Example 3 to obtain catalyst AI-11.

[0278] Example I-12 ZSM-5 powder (specific surface area 354m 2ZSM-5 powder (having a SiO2 / Al2O3 ratio of 61 / g, a pore volume of 0.57 ml / g, a crystallinity of 97.5%) was kneaded, and an aqueous solution of calcium nitrate tetrahydrate (analytically pure), nitric acid, and a dilute aqueous solution of phosphoric acid were successively added while kneading. The resulting material was extruded into toothed spheres with a diameter of 3.0 mm, dried at 120°C for 10 hours, and then calcined at 920°C for 5 hours to obtain the desired support. Per 100 g of ZSM-5 powder, the amount of calcium nitrate tetrahydrate (analytically pure) was 1.56 g, the amount of nitric acid was 8.2 g, and the amount of phosphoric acid was 2.9 g.

[0279] The remaining procedures were the same as those described in Example 7 to obtain catalyst AI-12.

[0280] Example I-13 The preparation of the carrier was the same as that described in Example I-7. 2.56 g of palladium chloride (with 99.5% purity) and 38.2 g of copper nitrate trihydrate (analytical purity) were dissolved in water to obtain 171 mL of solution. The solution was twice supported on 100 g of the obtained support by spray impregnation, and after each spray impregnation, it was dried at 120 ° C for 4 hours, then calcined at 400 ° C for 4 hours, and then gradually increased in temperature at a rate of 20 ° C / hour to reduce hydrogen, and finally reduced at 230 ° C for 3 hours to obtain catalyst AI-13.

[0281] Comparative example I-1 A catalyst was prepared in the same manner as in Example 5, except that the amounts of boric acid used were 3.43 g, barium nitrate (analytical pure) used was 4.76 g, and nitric acid used was 6.5 g, calculated as Al2O3, per 100 g of pseudo-boehmite powder used. The resulting catalyst was designated DI-1.

[0282] Comparative example I-2 A catalyst was prepared in the same manner as in Example 3, except that only a dilute aqueous solution of nitric acid was added during the kneading process, and the amount of nitric acid used was 6.1 g, calculated as Al2O3, per 100 g of pseudo-boehmite powder used. The resulting catalyst was designated DI-2.

[0283] Comparative example I-3 A catalyst was prepared in the same manner as in Example 3, except that during the kneading process, nitric acid and a dilute aqueous solution of phosphoric acid were added, and the amount of phosphoric acid used was 15.82 g and the amount of nitric acid used was 6.2 g, calculated as Al2O3, per 100 g of pseudo-boehmite powder used. The resulting catalyst was designated DI-3.

[0284] Test Example I-1 The elemental composition of the support and catalyst was analyzed by plasma emission spectroscopy. The content of elements (ions) other than the support was expressed as the weight of the element per 100 g of matrix, i.e., the support calculated based on the undoped elements (e.g., when pseudoboehmite was used as the support source, it was calculated based on Al2O3). The obtained support was characterized by NH3-TPD, CO2-TPD, and BET nitrogen adsorption / desorption methods. The results are shown in Table I-1.

[0285] [Table 1]

[0286] Test Example I-2 This example illustrates a process for producing 1,6-hexanediamine by hydroamination of 1,6-hexanediol using a catalyst according to a first type of embodiment of the present application.

[0287] 100 mL of the catalyst obtained in the previous example was measured and placed in a fixed-bed reactor and activated with hydrogen at 220°C for 2 hours. The mixture was then cooled to 165°C, and the system pressure was increased to 8.8 MPa using hydrogen. Ammonia was metered into the reaction system via a metering pump, preheated to 100°C, and delivered to the top of the reactor. Melted 1,6-hexanediol was supplied to the top of the reactor via a metering pump, and hydrogen was steadily introduced via a gas mass flow meter. The molar ratio of hydrogen to ammonia to 1,6-hexanediol was 3:14:1, and the liquid-phase volumetric space velocity of 1,6-hexanediol was 0.42 h / min. -1The catalytic amination reaction was carried out in a reactor at a reaction temperature of 185°C and a reaction pressure of 8.8 MPa. After the reaction stabilized (i.e., after 360 hours of reaction), the reaction solution was sampled and analyzed. The analytical results are shown in Table I-2.

[0288] The analysis of the samples was carried out by gas chromatography and calibrated using the correction factors of the formulated standards; Conversion and selectivity were calculated based on the molar content of each component in the reaction solution.

[0289]

number

[0290] The selectivity for hexamethyleneimine is calculated by changing the numerator in the above formula for calculating the selectivity for hexanediamine to the molar content of hexamethyleneimine, the selectivity for aminohexanol is calculated by changing the numerator in the above formula for calculating the selectivity for hexanediamine to the molar content of aminohexanol, etc., and the selectivity for "other" is calculated by changing the numerator in the above formula for calculating the selectivity for hexanediamine to twice the molar content of the amine dimer, which refers to the dimer of 1,6-hexanediamine (i.e., bis(hexamethylene)triamine, also known as N-(6-aminohexyl)-1,6-hexanediamine), and the dimer of 1,6-hexanediamine and hexamethyleneimine (i.e., N-(6-aminohexyl)hexamethyleneimine)).

[0291] [Table 2]

[0292] As can be seen from the data in Table I-2, the catalysts of the present invention have higher conversions and higher activities than the comparative catalysts, indicating that the catalysts of the present invention provide faster reaction rates.

[0293] All catalysts were tested for 360 hours and then discharged for characterization. The catalysts DI-1, DI-2, and DI-3 obtained in the comparative examples showed obvious decreases in specific surface area and pore volume, with their carbon deposition amounts of 11 wt%, 9.1 wt%, and 8.9 wt%, respectively, while the catalysts obtained in the examples of the present application showed no obvious changes in specific surface area and pore volume, with their carbon deposition amounts of less than 2 wt%.

[0294] Furthermore, when catalysts AI-1 to AI-11 were subjected to catalytic reaction for 1000 hours, samples of the reaction solution were taken and analyzed. The conversion and selectivity did not change significantly compared to those after 360 hours; that is, the conversion decreased by less than 2%, and the selectivity decreased by less than 1%. On the other hand, when catalysts DI-1 to DI-3 were subjected to catalytic reaction for 1000 hours, the conversion and selectivity of catalysts DI-1 to DI-3 decreased significantly compared to those after 360 hours. The conversion decreased to 31%, 28%, and 35%, respectively. The selectivity to hexanediamine decreased to 25%, 23%, and 26%, respectively.

[0295] Test Example I-3 This test example illustrates a process for producing ethylamine by hydroamination of ethanol using a catalyst according to a first type of embodiment of the present application.

[0296] 100 mL of catalyst AI-3 obtained in Example I-3 was measured and placed in a fixed-bed reactor and activated with hydrogen at 220°C for 2 hours. The system was then cooled to 160°C, and the system pressure was increased to 1.75 MPa using hydrogen. Ammonia was metered into the reaction system via a metering pump, preheated to 110°C, and delivered to the top of the reactor. Ethanol was supplied to the top of the reactor via a metering pump, and hydrogen was steadily introduced via a gas mass flow meter. The molar ratio of hydrogen, ammonia, and ethanol was 2:5:1, and the liquid phase volumetric space velocity of ethanol was 0.5 h / min. -1The catalytic amination reaction was carried out in a 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 analytical conditions and the calculation methods for conversion and selectivity were the same as in Test Example I-2). The analytical results are shown in Table I-3.

[0297] [Table 3]

[0298] Test Example I-4 This example illustrates a process for producing ethylenediamine by hydroamination of ethanolamine using a catalyst according to the first type of embodiment of the present application. 100 mL of catalyst AI-3 obtained in Example I-3 was measured and placed in a fixed-bed reactor and activated with hydrogen at 220°C for 2 hours. The system was then cooled to 180°C, and the system pressure was increased to 9.6 MPa using hydrogen. Ammonia was metered into the reaction system via a metering pump, preheated to 100°C, and delivered to the top of the reactor. Ethanolamine was supplied to the top of the reactor via a metering pump, and hydrogen was steadily introduced via a gas mass flow meter. The molar ratio of hydrogen, ammonia, and ethanolamine was 3:12:1, and the liquid phase volumetric space velocity of ethanolamine was 0.5 h / min. -1 The catalytic amination reaction was carried out in a reactor at a reaction temperature of 180°C and a reaction pressure of 9.6 MPa. After the reaction stabilized, the reaction solution was sampled and analyzed (the analytical conditions and the calculation methods for conversion and selectivity were the same as in Test Example I-2). The analytical results are shown in Table I-4.

[0299] [Table 4]

[0300] Test Example I-5 This test example illustrates a process for producing hexanediamine from a mixture of 1,6-hexanediol, hexamethyleneimine, and aminohexanol using a catalyst according to a first type of embodiment of the present application.

[0301] 100 mL of catalyst AI-3 obtained in Example I-3 was measured and placed in a fixed-bed reactor and activated with hydrogen at 220°C for 2 hours. The system was then cooled to 170°C, and the system pressure was increased to 8.2 MPa using hydrogen. Ammonia was metered into the reaction system via a metering pump, preheated to 110°C, and delivered to the top of the reactor. A mixed solution of 53 wt% 1,6-hexanediol, 30 wt% hexamethyleneimine, and 17 wt% 6-amino-1-hexanol was fed to the top of the reactor via a metering pump, and hydrogen was steadily introduced via a gas mass flow meter. The molar ratio of hydrogen to ammonia to the total amount of the three substances in the mixed solution was 4:15:1, and the liquid phase volumetric space velocity of the mixed solution was 0.5 h / min. -1 The catalytic amination reaction was carried out in a reactor at a reaction temperature of 190°C and a reaction pressure of 8.2 MPa. After the reaction stabilized, the reaction solution was sampled and analyzed (the analytical conditions and the calculation methods for conversion and selectivity were the same as in Test Example I-2). The analytical results are shown in Table I-5.

[0302] [Table 5]

[0303] Example Series II The second type of embodiment of the present application will be further described in detail below with reference to examples in Example Series II. In the following examples in Example Series II, pseudoboehmite powder was prepared by the aluminum sulfate method and had an (Al2O3) content of 72 wt% on a dry basis; silica sol was purchased from Qingdao Ocean Chemical Co., Ltd. under the trade name JN-40.

[0304] Example II-1 Pseudo-boehmite powder (specific surface area 346m 2The powder (having a pore volume of 1.13 ml / g, a phosphorus content of 0.22 g per 100 g of powder calculated as Al2O3) was kneaded with a dilute aqueous solution of nitric acid containing 15% by volume, extruded into strips with a diameter of 5 mm, dried at 120°C for 12 hours, and calcined at 800°C for 5 hours to obtain a support. The parameters of the support are shown in Table II-1.

[0305] 186.5 g of cobalt nitrate hexahydrate (industrial grade, 98% purity), 19.5 g of a 50 wt % manganese nitrate aqueous solution, and 14.13 g of copper nitrate trihydrate were dissolved in water to obtain 132 mL of solution. The solution was twice supported on 100 g of the obtained support by spray impregnation, and after each spray impregnation, it was dried at 120 ° C for 4 hours, then calcined at 400 ° C for 2 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20 ° C / hour, and finally reduced at 480 ° C for 2 hours to obtain Catalyst A-II-1.

[0306] Example II-2 Pseudo-boehmite powder (specific surface area 333m 2 The powder (having a boron content of 0.53 g per 100 g of powder calculated as Al2O3, a pore volume of 1.04 ml / g, and an average particle size of 1.04 ml / g) was mixed with a dilute aqueous solution of nitric acid containing 10% by volume, extruded into clover-shaped granules with a thickness of 3 mm, dried at 150°C for 6 hours, and then calcined at 820°C for 4 hours to obtain a support. The parameters of the support are shown in Table II-1.

[0307] 151.7 g of nickel nitrate hexahydrate (industrial grade, 98% purity), 13.0 g of a 50 wt % manganese nitrate aqueous solution, and 8.48 g of copper nitrate trihydrate were dissolved in water to obtain 148 mL of solution. The solution was supported twice on 100 g of the obtained support by spray impregnation. After each spray impregnation, it 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 obtain 78 mL of solution. The solution was supported on the obtained intermediate product by spray impregnation, dried at 120 °C for 4 hours, and then calcined at 370 °C for 4 hours. The solution was then reduced with hydrogen while gradually increasing the temperature at a rate of 20 °C / hour, and finally reduced at 450 °C for 3 hours to obtain Catalyst A-II-2.

[0308] Example II-3 Pseudo-boehmite powder (specific surface area 369m 2 The silica sol and sulphur dioxide (with a pore volume of 0.99 ml / g, a sulfur content of 2.88 g per 100 g of powder calculated as Al2O3) were mixed uniformly, kneaded with a dilute aqueous acid solution containing 15% by volume of nitric acid, extruded into toothed spheres with a diameter of 4 mm, dried at 100°C for 20 hours, and then calcined at 840°C for 5 hours to obtain a support. The parameters of the support are shown in Table II-1.

[0309] 45.4g of cobalt nitrate hexahydrate (industrial grade, 98% purity) and 1.57g of silver nitrate were dissolved in water to obtain 102mL of solution. This solution was supported twice on 100g of the obtained support by spray impregnation, and after each spray impregnation, it was dried at 120°C for 4 hours and then calcined at 400°C for 4 hours. 1.50g of ammonium perrhenate was dissolved in water to obtain 70mL of solution. This solution was supported on the obtained intermediate product by spray impregnation, dried at 120°C for 4 hours, then calcined at 390°C for 4 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20°C / hour, and finally reduced at 420°C for 4 hours to obtain catalyst A-II-3.

[0310] Example II-4 Pseudo-boehmite powder (specific surface area 375m 2 SiO2 / g, pore volume 1.15 ml / g, fluorine content 0.08 g per 100 g of powder calculated as Al2O3) and ZSM-5 (commercial product, manufactured by Nankai University, SiO2 / Al2O3 = 45 (molar ratio)) were uniformly mixed, kneaded with a dilute acid solution containing 12 vol% nitric acid, extruded into a cylindrical rod with a diameter of 4 mm, dried at 120°C for 8 hours, and calcined at 810°C for 4 hours to obtain a support. The support parameters are shown in Table II-1.

[0311] 126.0 g of cobalt nitrate hexahydrate (industrial grade, 98% purity) and 0.79 g of silver nitrate were dissolved in water to obtain 192 mL of solution. This solution was supported twice on 100 g of the obtained support by spray impregnation, and after each spray impregnation, it 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 obtain 81 mL of solution. This solution was supported on the obtained intermediate product by spray impregnation, dried at 120 ° C for 4 hours, and then calcined at 400 ° C for 3 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20 ° C / hour, and finally reduced at 420 ° C for 4 hours to obtain catalyst A-II-4.

[0312] Example II-5 Pseudo-boehmite powder (specific surface area 298m 2 The powder (having a pore volume of 0.85 ml / g, a phosphorus content of 0.18 g per 100 g of powder calculated as Al2O3) was kneaded with a dilute aqueous solution containing 15% by volume of nitric acid, extruded into a cylindrical rod with a diameter of 2.5 mm, dried at 110°C for 14 hours, and then calcined at 890°C for 4 hours to obtain a support. The parameters of the support are shown in Table II-1.

[0313] 75.6g of cobalt nitrate hexahydrate (industrial grade, 98% purity), 13.0g of 50wt% manganese nitrate aqueous solution, and 3.15g of silver nitrate were dissolved in water to obtain 112mL of solution. This solution was supported twice on 100g of the obtained support by spray impregnation, and after each spray impregnation, it was dried at 120°C for 4 hours and then calcined at 380°C for 4 hours. 2.90g of ammonium perrhenate was dissolved in water to obtain 70mL of solution. This solution was supported on the obtained intermediate product by spray impregnation, dried at 120°C for 4 hours, and then calcined at 400°C for 2 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20°C / hour, and finally reduced at 450°C for 3 hours to obtain catalyst A-II-5.

[0314] Example II-6 Pseudo-boehmite powder (specific surface area 348m 2The silica sol and sucrose (having a boron content of 3.66 g per 100 g of powder calculated as Al2O3, a pore volume of 1.09 ml / g, and an Al2O3-based boron content of 3.66 g per 100 g of powder) were mixed uniformly, kneaded with a dilute aqueous solution of nitric acid containing 15% by volume, extruded into a cylindrical rod with a diameter of 4 mm, dried at 120°C for 7 hours, and then calcined at 810°C for 6 hours to obtain a support. The parameters of the support are shown in Table II-1.

[0315] 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 obtain 146 mL of solution. The solution was supported twice on 100 g of the obtained support by spray impregnation, and after each spray impregnation, it 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 obtain 74 mL of solution. The solution was supported on the obtained intermediate product by spray impregnation, dried at 120 ° C for 4 hours, and then calcined at 350 ° C for 6 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20 ° C / hour, and finally reduced at 440 ° C for 3 hours to obtain catalyst A-II-6.

[0316] Example II-7 Pseudo-boehmite powder (specific surface area 374m 2 The silica sol and sulphur dioxide (with a pore volume of 1.18 ml / g, a sulfur content of 0.81 g per 100 g of powder calculated as Al2O3) were mixed uniformly, kneaded with a dilute aqueous acid solution containing 10% by volume of nitric acid, extruded into a cylindrical rod with a diameter of 4 mm, dried at 120°C for 7 hours, and then calcined at 750°C for 6 hours to obtain a support. The parameters of the support are shown in Table II-1.

[0317] 201.6g of cobalt nitrate hexahydrate (industrial grade, 98% purity), 11.30g of copper nitrate trihydrate, and 9.80g of 50wt% manganese nitrate aqueous solution were dissolved in water to obtain 132mL of solution. This solution was supported twice on 100g of the obtained support by spray impregnation, and after each spray impregnation, it was dried at 120°C for 4 hours and then calcined at 380°C for 4 hours. 4.70g of ammonium perrhenate was dissolved in water to obtain 74mL of solution. This solution was supported on the obtained intermediate product by spray impregnation, dried at 120°C for 4 hours, then calcined at 400°C for 2 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20°C / hour, and finally reduced at 460°C for 2 hours to obtain catalyst A-II-7.

[0318] Example II-8 Pseudo-boehmite powder (specific surface area 355m 2 The silica sol and sulphur dioxide (having a pore volume of 1.05 ml / g, a sulfur content of 0.88 g per 100 g of powder calculated as Al2O3) were mixed uniformly, kneaded with a dilute aqueous acid solution containing 10% by volume of nitric acid, extruded into a cylindrical rod with a diameter of 4 mm, dried at 120°C for 7 hours, and calcined at 810°C for 6 hours to obtain a support. The parameters of the support are shown in Table II-1.

[0319] 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 obtain 116 mL of solution. The solution was twice supported on 100 g of the obtained support by spray impregnation, and after each spray impregnation, it was dried at 120 ° C for 4 hours, then calcined at 360 ° C for 4 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20 ° C / hour, and finally reduced at 420 ° C for 5 hours to obtain catalyst A-II-8.

[0320] Example II-9 Pseudo-boehmite powder (specific surface area 380m 2The silica sol and SiO2 (having a fluorine content of 0.82 g per 100 g of powder calculated as Al2O3, a pore volume of 1.01 ml / g, and an Al2O3-based fluorine content of 0.82 g per 100 g of powder) were mixed uniformly, kneaded with a dilute aqueous acid solution containing 15% by volume of nitric acid, extruded into a cylindrical rod with a diameter of 4 mm, dried at 120°C for 7 hours, and then calcined at 810°C for 6 hours to obtain a support. The parameters of the support are shown in Table II-1.

[0321] 176.4 g of cobalt nitrate hexahydrate (industrial grade, 98% purity), 13.0 g of 50 wt% manganese nitrate aqueous solution, and 1.57 g of silver nitrate were dissolved in water to obtain 154 mL of solution. This solution was supported twice on 100 g of the obtained support by spray impregnation, and after each spray impregnation, it 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 obtain 74 mL of solution. This solution was supported on the obtained intermediate product by spray impregnation, dried at 120 ° C for 4 hours, and then calcined at 380 ° C for 3 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20 ° C / hour, and finally reduced at 450 ° C for 3 hours to obtain catalyst A-II-9.

[0322] Example II-10 Pseudo-boehmite powder (specific surface area 328m 2 The powder (having a pore volume of 0.97 ml / g, a sulfur content of 0.95 g per 100 g of powder calculated as Al2O3) was kneaded with a dilute aqueous solution containing 5% by volume of nitric acid, extruded into a cylindrical rod with a diameter of 4 mm, dried at 120°C for 7 hours, and then calcined at 810°C for 6 hours to obtain a support. The parameters of the support are shown in Table II-1.

[0323] 226.8 g of cobalt nitrate hexahydrate (industrial grade, 98% purity), 26.1 g of 50 wt% manganese nitrate aqueous solution, and 0.79 g of silver nitrate were dissolved in water to obtain 162 mL of solution. This solution was supported twice on 100 g of the obtained support by spray impregnation, and after each spray impregnation, it 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 obtain 74 mL of solution. This solution was supported on the obtained intermediate product by spray impregnation, dried at 120 ° C for 4 hours, and then calcined at 420 ° C for 2 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20 ° C / hour, and finally reduced at 430 ° C for 4 hours to obtain catalyst A-II-10.

[0324] Example II-11 Pseudo-boehmite powder (specific surface area 304m 2 The silica sol and the silica sol were homogeneously mixed, kneaded with a dilute aqueous solution of nitric acid containing 5% by volume, extruded into a cylindrical rod with a diameter of 4 mm, dried at 120°C for 7 hours, and calcined at 810°C for 6 hours to obtain a support. The parameters of the support are shown in Table II-1.

[0325] 141.1g of cobalt nitrate hexahydrate (industrial grade, 98% purity), 13.0g of 50wt% manganese nitrate aqueous solution, and 0.79g of silver nitrate were dissolved in water to obtain 152mL of solution. This solution was supported twice on 100g of the obtained support by spray impregnation, and after each spray impregnation, it was dried at 120°C for 4 hours and then calcined at 380°C for 4 hours. 2.90g of ammonium perrhenate was dissolved in water to obtain 74mL of solution. This solution was supported on the obtained intermediate product by spray impregnation, dried at 120°C for 4 hours, then calcined at 400°C for 4 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20°C / hour, and finally reduced at 460°C for 2 hours to obtain catalyst A-II-11.

[0326] Example II-12 The pseudo-boehmite powder used did not contain any doping elements and had a viscosity of 298 m2 A catalyst was prepared as described in Example II-3, except that the resulting catalyst had a specific surface area of ​​1.08 ml / g and a pore volume of 1.08 ml / g, and was designated A-II-12.

[0327] Comparative Example II-1 Pseudo-boehmite powder (specific surface area 376m 2 The silica sol and sulphur-free silica were mixed uniformly, kneaded with a dilute aqueous acid solution containing 10% by volume of nitric acid, extruded into toothed spheres with a diameter of 4 mm, dried at 120°C for 5 hours, and calcined at 860°C for 6 hours to obtain a support. The parameters of the support are shown in Table II-1.

[0328] The remaining procedures were the same as those described in Example 8 to obtain catalyst D-II-1.

[0329] Comparative Example II-2 Pseudo-boehmite powder (specific surface area 358m 2 The silica sol was homogeneously mixed with the silica sol, kneaded with a dilute acid solution containing 10% by volume of nitric acid, extruded into toothed spheres with a diameter of 4 mm, dried at 100°C for 12 hours, and calcined at 890°C for 6 hours to obtain a support. The parameters of the support are shown in Table II-1.

[0330] 226.8g of cobalt nitrate hexahydrate (technical grade, 98% purity) and 0.79g of silver nitrate were dissolved in water to obtain 162mL of solution. This solution was supported twice on 100g of the obtained support by spray impregnation, and after each spray impregnation, it was dried at 120°C for 4 hours, then calcined at 380°C for 4 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20°C / hour, and finally reduced at 450°C for 4 hours to obtain catalyst D-II-2.

[0331] Test Example II-1 The elemental composition of the support and catalyst was analyzed by plasma emission spectroscopy, and the contents of the doping elements, active metal components, and metal promoters of the support and catalyst were expressed by weight per 100 g of matrix. The support obtained was characterized by NH3-TPD and BET nitrogen adsorption-desorption methods. The results are shown in Table II-1.

[0332] [Table 6]

[0333] Test Example II-2 This test example illustrates a process for producing 1,6-hexanediamine by hydroamination of 1,6-hexanediol using a catalyst according to a second type of embodiment of the present application.

[0334] 100 mL of the catalyst obtained in each of the examples and comparative examples was measured and placed in a fixed-bed reactor and activated using hydrogen at 220°C for 2 hours. The catalyst was then cooled to 168°C, and the system pressure was increased to 9.5 MPa using hydrogen. Ammonia was metered into the reaction system via a metering pump, preheated to 155°C, and delivered to the top of the reactor. Melted 1,6-hexanediol was supplied to the top of the reactor via a metering pump, and hydrogen was steadily introduced via a gas mass flow meter. The molar ratio of hydrogen to ammonia to 1,6-hexanediol was 3:8:1, and the liquid phase volumetric space velocity of 1,6-hexanediol was 0.5 h / min. -1 The catalytic amination reaction was carried out in a reactor at a reaction temperature of 200°C and a reaction pressure of 11 MPa. After the reaction stabilized (i.e., after 500 hours of reaction), the reaction solution was sampled and analyzed. The analytical results are shown in Table II-2.

[0335] Samples were analyzed by gas chromatography and calibrated using the correction factors of formulated standards.

[0336] The conversion and selectivity were calculated based on the molar content of each component in the reaction solution, using the same calculation method as described in Test Example I-2.

[0337] [Table 7]

[0338] As can be seen from the data in Table II-2, the catalysts of the present application exhibit higher conversion and higher selectivity of hexanediamine, improved catalytic activity compared to catalysts not included in the present application, and lower selectivity to "other," i.e., amines having 12 or more carbon atoms, indicating that the catalysts of the present application have lower carbon deposition and higher stability.

[0339] Catalysts A-II-3 and D-II-2 were each subjected to a 500-hour long-term stability test, followed by BET and XRD tests on the catalysts before and after use. The results are shown in Table II-3. The results show that the specific surface area, pore volume, and particle size of the active metal of Catalyst A-II-3 remained essentially unchanged, while the specific surface area and pore volume of Catalyst D-II-2 decreased to some extent, and the particle size of the active metal increased significantly compared to the catalyst before reaction, indicating that the present catalysts have better stability and less carbon deposition.

[0340] [Table 8]

[0341] Test Example II-3 100 mL of catalyst A-II-3 obtained in Example II-3 was measured and placed in a fixed-bed reactor and activated with hydrogen at 240°C for 2 hours. The system was then cooled to 168°C, and the system pressure was increased to 1.8 MPa using hydrogen. Ammonia was metered into the reaction system via a metering pump, preheated to 160°C, and delivered to the top of the reactor. Ethanol was supplied to the top of the reactor via a metering pump, and hydrogen was steadily introduced via a gas mass flow meter. The molar ratio of hydrogen, ammonia, and ethanol was 3:5:1, and the liquid phase volumetric space velocity of ethanol was 0.6 h / s . -1The catalytic amination reaction was carried out in a reactor at a reaction temperature of 185°C and a reaction pressure of 2.8 MPa. After the reaction stabilized, the reaction solution was sampled and analyzed. The analytical results are shown in Table II-4.

[0342] [Table 9]

[0343] Test Example II-4 100 mL of catalyst A-II-5 obtained in Example II-5 was measured and placed in a fixed-bed reactor and activated with hydrogen at 240°C for 2 hours. The system was then cooled to 168°C, and the system pressure was increased to 8 MPa using hydrogen. Ammonia was metered into the reaction system via a metering pump, preheated to 150°C, and delivered to the top of the reactor. Ethanolamine was fed to the top of the reactor via a metering pump, and hydrogen was steadily introduced via a gas mass flow meter. The molar ratio of hydrogen, ammonia, and ethanolamine was 3:8:1, and the liquid phase volumetric space velocity of ethanolamine was 0.6 h / min. -1 The catalytic amination reaction was carried out in a reactor at a reaction temperature of 195°C and a reaction pressure of 9.5 MPa. After the reaction stabilized, the reaction solution was sampled and analyzed (the analytical conditions and the calculation methods for conversion and selectivity were the same as in Test Example II-2). The analytical results are shown in Table II-5.

[0344] [Table 10]

[0345] Example Series III The third type of embodiment of the present application will be described in more detail with reference to the examples in Example Series III. In the following examples in Example Series III, pseudoboehmite powder was prepared by the aluminum sulfate method and had an (Al2O3) content of 72 wt% on a dry basis; silica sol was purchased from Qingdao Ocean Chemical Co., Ltd. under the trade name JN-40.

[0346] Example III-1 Pseudo-boehmite powder (specific surface area 375m 2 The support was obtained by kneading a sintered body (having a boron content of 3.89 g per 100 g of Al2O3, a pore volume of 0.99 ml / g, and a dilute aqueous solution of acid (containing a weighed amount of calcium nitrate, with a calcium content of 0.11 g per 100 g of Al2O3), extruding it into strips with a diameter of 5 mm, drying it at 120°C for 12 hours, and calcining it at 800°C for 10 hours. The support parameters are shown in Table III-1.

[0347] 176.4 g of cobalt nitrate hexahydrate (technical grade, 98% purity), 26.1 g of 50 wt % manganese nitrate aqueous solution, and 6.83 g of zinc nitrate were dissolved in water to obtain 138 mL of solution. The solution was twice supported on 100 g of the obtained support by spray impregnation, and after each spray impregnation, it was dried at 120 ° C for 4 hours, then calcined at 400 ° C for 4 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20 ° C / hour, and finally reduced at 430 ° C for 3 hours to obtain Catalyst A-III-1.

[0348] Example III-2 Pseudo-boehmite powder (specific surface area 405m 2 / g, pore volume 1.06 ml / g, sulfur content 0.79 g per 100 g of Al2O3) was kneaded with a dilute aqueous acid solution containing 5 volume % of nitric acid (magnesium nitrate was contained in a weighed amount using a magnesium content of 0.78 g per 100 g of Al2O3), extruded into clover-shaped granules with a thickness of 3 mm, dried at 120°C for 15 hours, and then calcined at 840°C for 4 hours to obtain a support. The parameters of the support are shown in Table III-1.

[0349] 161.8g of nickel nitrate hexahydrate (technical grade, 98% purity), 39.1g of 50wt% manganese nitrate aqueous solution, and 6.83g of zinc nitrate were dissolved in water to obtain 146mL of solution. The solution was supported on 100g of the obtained support twice by spray impregnation, and after each spray impregnation, it was dried at 120°C for 5 hours, then calcined at 390°C for 4 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20°C / hour, and finally reduced at 440°C for 3 hours to obtain catalyst A-III-2.

[0350] Example III-3 Pseudo-boehmite powder (specific surface area 386m 2 The silica sol and the sulphur dioxide (Al2O3) were homogeneously mixed and kneaded with a dilute aqueous acid solution containing 5% by volume of nitric acid (containing a weighed amount of potassium nitrate, with a potassium content of 2.1 g per 100 g of Al2O3), extruded into toothed spheres with a diameter of 4 mm, dried at 100°C for 20 hours, and then calcined at 850°C for 6 hours to obtain a support. The parameters of the support are shown in Table III-1.

[0351] 50.4g of cobalt nitrate hexahydrate (technical grade, 98% purity), 13.0g of 50wt% manganese nitrate aqueous solution, and 6.83g of zinc nitrate solution were dissolved in water to obtain 104mL of solution.This solution was supported twice on 100g of the obtained support by spray impregnation, and after each spray impregnation, it was dried at 120°C for 4 hours, then calcined at 400°C for 4 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20°C / hour, and finally reduced at 430°C for 3 hours to obtain catalyst A-III-3.

[0352] Example III-4 Pseudo-boehmite powder (specific surface area 398m 2The support was obtained by homogeneously mixing ZSM-5 (commercially available from Nankai University, SiO / AlO = 45 (molar ratio)) and kneading it with a dilute aqueous solution of 5% by volume of nitric acid (bismuth nitrate was weighed using 1.8 g of bismuth per 100 g of pseudoboehmite powder, calculated as AlO). The mixture was extruded into 4 mm diameter toothed spheres, dried at 140 °C for 10 hours, and calcined at 750 °C for 10 hours. The support parameters are listed in Table III-1.

[0353] 100.8g of cobalt nitrate hexahydrate (technical grade, 98% purity), 3.3g of 50wt% manganese nitrate aqueous solution, and 4.55g of zinc nitrate solution were dissolved in water to obtain 188mL of solution. This solution was supported twice on 100g of the obtained support by spray impregnation, and after each spray impregnation, it was dried at 120°C for 4 hours, then calcined at 400°C for 4 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20°C / hour, and finally reduced at 430°C for 3 hours to obtain catalyst A-III-4.

[0354] Example III-5 Pseudo-boehmite powder (specific surface area 375m 2 / g, pore volume 1.15 ml / g, phosphorus content 0.33 g per 100 g of Al2O3) was kneaded with a dilute aqueous acid solution containing 5 volume % of nitric acid (containing a weighed amount of barium nitrate with a barium content of 1.7 g per 100 g of Al2O3), extruded into toothed spheres with a diameter of 4 mm, dried at 150 °C for 6 hours, and then calcined at 950 °C for 3 hours to obtain a support. The parameters of the support are shown in Table III-1.

[0355] 75.6g of cobalt nitrate hexahydrate (industrial grade, 98% purity) and 4.55g of zinc nitrate solution were dissolved in water to obtain 104mL of solution. This solution was supported twice on 100g of the obtained support by spray impregnation, and after each spray impregnation, it was dried at 120°C for 4 hours and then calcined at 380°C for 4 hours. 2.9g of ammonium perrhenate was dissolved in water to obtain 45mL of solution. This solution was supported on the obtained intermediate product by spray impregnation, dried at 120°C for 4 hours, and then calcined at 380°C for 4 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 30°C / hour, and finally reduced at 450°C for 4 hours to obtain catalyst A-III-5.

[0356] Example III-6 Pseudo-boehmite powder (specific surface area 320m 2 The silica sol and the sintered silica gel (having a pore volume of 1.03 ml / g, a boron content of 0.24 g per 100 g of Al2O3) were homogeneously mixed, kneaded with a dilute aqueous acid solution containing 5% by volume of nitric acid (containing a weighed amount of calcium nitrate with a calcium content of 1.20 g per 100 g of Al2O3), extruded into strips with a diameter of 5 mm, cut into 4 mm lengths, dried at 110°C for 16 hours, and then calcined at 880°C for 5 hours to obtain the support. The parameters of the support are shown in Table III-1.

[0357] 126.4 g of nickel nitrate hexahydrate (industrial grade, 98% purity) and 22.75 g of zinc nitrate were dissolved in water to obtain 150 mL of solution. The solution was supported twice on 100 g of the obtained support by spray impregnation, and after each spray impregnation, it 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 obtain 67 mL of solution. The solution was supported on the obtained intermediate product by spray impregnation, dried at 120 ° C for 4 hours, and then calcined at 400 ° C for 4 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20 ° C / hour, and finally reduced at 430 ° C for 3 hours to obtain catalyst A-III-6.

[0358] Example III-7 Pseudo-boehmite powder (specific surface area 355m 2 The silica sol and the sulphur dioxide (Al2O3) were homogeneously mixed and kneaded with a dilute aqueous acid solution containing 5% by volume of nitric acid (magnesium nitrate was measured using a magnesium content of 1.4 g per 100 g of Al2O3), extruded into strips with a diameter of 5 mm, dried at 120°C for 15 hours, and calcined at 550°C for 20 hours to obtain a support. The parameters of the support are shown in Table III-1.

[0359] 201.6 g of cobalt nitrate hexahydrate (industrial grade, 98% purity) and 2.28 g of zinc nitrate were dissolved in water to obtain 136 mL of solution. The solution was supported twice on 100 g of the obtained support by spray impregnation, and after each spray impregnation, it 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 obtain 62 mL of solution. The solution was supported on the obtained intermediate product by spray impregnation, dried at 120 ° C for 4 hours, and then calcined at 400 ° C for 4 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20 ° C / hour, and finally reduced at 480 ° C for 2 hours to obtain catalyst A-III-7.

[0360] Example III-8 Pseudo-boehmite powder (specific surface area 275m 2 / g, pore volume 0.99 ml / g, fluorine content 0.08 g per 100 g of Al2O3) was mixed with a dilute acid solution containing 5 volume % of nitric acid (calcium nitrate was contained in a weighed amount using a calcium content of 0.80 g per 100 g of Al2O3), extruded into strips with a diameter of 5 mm, dried at 150°C for 8 hours, and calcined at 800°C for 8 hours to obtain a support. The parameters of the support are shown in Table III-1.

[0361] 100.8g of cobalt nitrate hexahydrate (industrial grade, 98% purity) and 13.65g of zinc nitrate were dissolved in water to obtain 122mL of solution. This solution was supported twice on 100g of the obtained support by spray impregnation, and after each spray impregnation, it was dried at 120°C for 4 hours and then calcined at 400°C for 4 hours. 1.40g of ammonium perrhenate was dissolved in water to obtain 55mL of solution. This solution was supported on the obtained intermediate product by spray impregnation, dried at 120°C for 4 hours, and then calcined at 400°C for 4 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20°C / hour, and finally reduced at 450°C for 3 hours to obtain catalyst A-III-8.

[0362] Example III-9 Pseudo-boehmite powder (specific surface area 379m 2 / g, pore volume 0.99 ml / g, phosphorus content 0.2 g per 100 g of Al2O3) was kneaded with a dilute acid solution containing 5 volume % of nitric acid (calcium nitrate was contained in a weighed amount using a calcium content of 1.30 g per 100 g of Al2O3), extruded into a cylindrical rod with a diameter of 5 mm, dried at 100 °C for 18 hours, and then calcined at 880 °C for 4 hours to obtain a support. The parameters of the support are shown in Table III-1.

[0363] 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 obtain 152 mL of solution. The solution was supported twice on 100 g of the obtained support by spray impregnation, and after each spray impregnation, it 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 obtain 70 mL of solution. The solution was supported on the obtained intermediate product by spray impregnation, dried at 120 ° C for 4 hours, and then calcined at 420 ° C for 3 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20 ° C / hour, and finally reduced at 420 ° C for 6 hours to obtain catalyst A-III-9.

[0364] Example III-10 Pseudo-boehmite powder (specific surface area 392m2 / g, pore volume 0.99 ml / g, sulfur content 0.97 g per 100 g of Al2O3) was mixed with a dilute aqueous acid solution containing 5 volume % nitric acid (calcium nitrate was contained in a weighed amount using a calcium content of 0.05 g per 100 g of Al2O3), extruded into strips with a diameter of 5 mm, dried at 80°C for 20 hours, and calcined at 700°C for 10 hours to obtain a support. The parameters of the support are shown in Table III-1.

[0365] 226.8g of cobalt nitrate hexahydrate (industrial grade, 98% purity), 26.1g of 50wt% manganese nitrate, and 2.28g of zinc nitrate were dissolved in water to obtain 162mL of solution. This solution was supported twice on 100g of the obtained support by spray impregnation, and after each spray impregnation, it was dried at 120°C for 6 hours and then calcined at 400°C for 4 hours. 2.88g of ammonium perrhenate was dissolved in water to obtain 75mL of solution. This solution was supported on the obtained intermediate product by spray impregnation, dried at 120°C for 4 hours, and then calcined at 400°C for 4 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20°C / hour, and finally reduced at 440°C for 4 hours to obtain catalyst A-III-10.

[0366] Example III-11 Pseudo-boehmite powder (specific surface area 315m 2 / g, pore volume 0.99 ml / g, phosphorus content 4.64 g per 100 g of Al2O3) was kneaded with a dilute aqueous acid solution containing 5 volume % of nitric acid (calcium nitrate was contained in a weighed amount with a calcium content of 1.25 g per 100 g of Al2O3), extruded into a clover with a diameter of 3 mm, dried at 120 °C for 8 hours, and then calcined at 750 °C for 8 hours to obtain a support. The parameters of the support are shown in Table III-1.

[0367] 141.1g of cobalt nitrate hexahydrate (industrial grade, 98% purity), 32.6g of 50wt% manganese nitrate aqueous solution, and 2.28g of zinc nitrate were dissolved in water to obtain 154mL of solution. This solution was supported twice on 100g of the obtained support by spray impregnation, and after each spray impregnation, it was dried at 120°C for 4 hours and then calcined at 400°C for 4 hours. 5.76g of ammonium perrhenate was dissolved in water to obtain 71mL of solution. This solution was supported on the obtained intermediate product by spray impregnation, dried at 120°C for 4 hours, and then calcined at 390°C for 6 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20°C / hour, and finally reduced at 450°C for 3 hours to obtain catalyst A-III-11.

[0368] Example III-12 The pseudo-boehmite powder used does not contain any doping elements and has a viscosity of 366 m 2 Catalyst A-III-12 was prepared as described in Example III-6, except that it had a specific surface area of ​​1.05 ml / g and a pore volume of 1.05 ml / g.

[0369] Comparative example III-1 The pseudo-boehmite powder used does not contain any doping elements and has a viscosity of 325 m 2 / g specific surface area and pore volume of 0.95 ml / g, and a catalyst was prepared as described in Example III-6, except that zinc nitrate was replaced with 15.2 g of nickel nitrate hexahydrate (technical grade, with a purity of 98%) to obtain catalyst D-III-1.

[0370] Comparative example III-2 The pseudo-boehmite powder used did not contain any doping elements and had a viscosity of 349 m 2 / g specific surface area and pore volume of 1.13 ml / g, and a catalyst was prepared as described in Example III-9, except that manganese nitrate and ammonium perrhenate were replaced with 20.1 g of cobalt nitrate hexahydrate (technical grade, with a purity of 98%) to obtain catalyst D-III-3.

[0371] Comparative example III-3 Pseudo-boehmite powder (specific surface area 396m 2 A catalyst was prepared as described in Example III-2 using a zeolite (AlO) having a pore volume of 1.21 ml / g, a pore volume of 1.21 ml / g, and a sulfur content of 4.25 g per 100 g of AlO) and replacing zinc nitrate with 5.79 g of non-hydrated iron nitrate to obtain catalyst D-III-3.

[0372] Test Example III-1 The elemental compositions of the support and catalyst were analyzed by plasma emission spectroscopy. The contents of doping elements, active metal components, and metal promoters were expressed by weight per 100 g of matrix. The support obtained was characterized by NH3-TPD, CO2-TPD, and BET nitrogen adsorption-desorption methods. The results are shown in Table III-1.

[0373] [Table 11]

[0374] Test Example III-2 This example illustrates a process for producing 1,6-hexanediamine by hydroamination of 1,6-hexanediol using a catalyst according to a third type of embodiment of the present application.

[0375] 100 mL of the catalyst obtained in each of the examples and comparative examples was measured and placed in a fixed-bed reactor and activated using hydrogen at 220°C for 2 hours. The catalyst was then cooled to 168°C, and the system pressure was increased to 12 MPa using hydrogen. Ammonia was metered into the reaction system via a metering pump, preheated to 160°C, and delivered to the top of the reactor. Melted 1,6-hexanediol was supplied to the top of the reactor via a metering pump, and hydrogen was steadily introduced via a gas mass flow meter. The molar ratio of hydrogen, ammonia, and 1,6-hexanediol was 3:8:1, and the liquid phase volumetric space velocity of 1,6-hexanediol was 0.6 h / min. -1The catalytic amination reaction was carried out in a reactor at a reaction temperature of 205°C and a reaction pressure of 13 MPa. After the reaction stabilized (i.e., after 10 hours of reaction), the reaction solution was sampled and analyzed. The analytical results are shown in Table III-2.

[0376] Samples were analyzed by gas chromatography and calibrated using the correction factors of formulated standards.

[0377] The conversion and selectivity were calculated based on the molar content of each component in the reaction solution, using the same calculation method as described in Test Example I-2.

[0378] [Table 12]

[0379] The catalysts were subjected to a 500-hour long-term stability test under the same conditions, and then BET and XRD tests were performed on the catalysts before and after use. The results showed that the specific surface area and pore volume of catalysts A-III-1 to A-III-11 did not change substantially after use (i.e., the decrease was 2% or less), while the specific surface area and pore volume of catalysts D-III-1 to D-III-3 decreased significantly after use (both by more than 8%), indicating that the present catalysts have better stability and less carbon deposition.

[0380] Further testing revealed that catalyst A-III-2 still showed a decrease in conversion of less than 5% after 1000 hours of use, and the decrease in specific surface area and pore volume was less than 5%, indicating that the catalyst of the present invention has a longer service life.

[0381] Test Example III-3 This test example illustrates a process for producing n-propylamine by hydroamination of n-propanol using a catalyst according to a third type of embodiment of the present application.

[0382] 100 ml of catalyst A-III-2 obtained in Example III-3 was measured and placed in a fixed-bed reactor and activated with hydrogen at 220°C for 2 hours. The reactor was then cooled to 172°C, and the system pressure was increased to 1.5 MPa using hydrogen. Ammonia was metered into the reaction system via a metering pump, preheated to 150°C, and delivered to the top of the reactor. n-Propanol was supplied to the top of the reactor via a metering pump, and hydrogen was steadily introduced via a gas mass flow meter. The molar ratio of hydrogen, ammonia, and n-propanol was 3:5:1, and the liquid phase volumetric space velocity of propanol was 0.75 h / min. -1 The catalytic amination reaction was carried out in a reactor at a reaction temperature of 180°C and a reaction pressure of 2 MPa. After the reaction stabilized, the reaction solution was sampled and analyzed (the analytical conditions and the calculation methods for conversion and selectivity were the same as those in Test Example III-2). The analytical results are shown in Table III-3.

[0383] [Table 13]

[0384] Example Series IV The fourth type of embodiment of the present application will be further described in detail below with reference to the examples in Example Series IV. In the following examples in Example Series IV, the pseudoboehmite powder used has an (Al2O3) content of 72 wt% on a dry basis; the silica sol was purchased from Qingdao Ocean Chemical Co., Ltd. under the trade name JN-40.

[0385] Example IV-1 Pseudoboehmite powder (specific surface area 380 m) prepared by the aluminum sulfate method 2The pseudo-boehmite powder containing sulfur as a doping element had a pore volume of 1.02 ml / g, a pore volume of 1.02 ml / g, and an S content of 2.15 g per 100 g of pseudo-boehmite powder calculated as Al2O3; in preparing the pseudo-boehmite powder, water glass (i.e., aqueous sodium silicate solution) was first added as an SiO2 precursor. As a result, the mass of SiO2 derived from the SiO2 precursor in the calcined support accounted for 4% of the total mass of the support.) The pseudo-boehmite powder was kneaded with a dilute acid solution containing 5% by volume of nitric acid, extruded into strips with a diameter of 5 mm, cut into 4 mm lengths, dried at 120°C for 8 hours, and calcined at 650°C for 5 hours to obtain the desired support.

[0386] 186.5g of cobalt nitrate hexahydrate (technical grade, 98% purity), 6.83g of zinc nitrate hexahydrate (analytical purity), and 5.65g of copper nitrate trihydrate (analytical purity) were dissolved in water to obtain 148mL of solution. This solution was supported twice on 100g of the obtained support by spray impregnation, and after each spray impregnation, it was dried at 120°C for 4 hours and then calcined at 400°C for 4 hours. 1.8g of ammonium molybdate tetrahydrate (analytical purity) was dissolved in water to obtain 74mL of solution. This solution was supported on the above-obtained intermediate product by spray impregnation, dried at 120°C for 4 hours, then calcined at 400°C for 4 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20°C / hour, and finally reduced at 430°C for 3 hours to obtain catalyst A-IV-1.

[0387] Example IV-2 Pseudoboehmite powder (specific surface area 375 m) prepared by the aluminum sulfate method 2Pseudo-boehmite powder containing a boron doping element, having a pore volume of 0.98 ml / g, a B content of 0.53 g per 100 g of pseudo-boehmite powder calculated as Al2O3; in preparing the pseudo-boehmite powder, water glass (i.e., aqueous sodium silicate solution) was first added as an SiO2 precursor. As a result, the mass of SiO2 derived from the SiO2 precursor in the calcined support accounted for 11% of the total mass of the support.) was kneaded with a dilute acid solution containing 5% by volume of nitric acid, extruded into clover-shaped granules with a thickness of 3 mm, dried at 100°C for 12 hours, and calcined at 590°C for 8 hours to obtain the desired support.

[0388] 151.7 g of nickel nitrate hexahydrate (industrial grade, 98% purity), 6.83 g of zinc nitrate hexahydrate (analytical purity), and 5.65 g of copper nitrate trihydrate (analytical purity) were dissolved in water to obtain 156 mL of solution. The solution was supported twice on 100 g of the obtained support by spray impregnation, and after each spray impregnation, it 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 obtain 78 mL of solution. The solution was supported on the obtained intermediate product by spray impregnation, dried at 120 ° C for 4 hours, and then calcined at 400 ° C for 4 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20 ° C / hour, and finally reduced at 430 ° C for 3 hours to obtain catalyst A-IV-2.

[0389] Example IV-3 Pseudoboehmite powder (specific surface area 380 m) prepared by the aluminum sulfate method 2The pseudo-boehmite powder containing sulfur as a doping element was prepared, having a pore volume of 1.02 ml / g, an S content of 2.15 g per 100 g of pseudo-boehmite powder calculated as Al2O3, and a water glass (i.e., aqueous sodium silicate solution) as the SiO2 precursor. The mass of SiO2 derived from the SiO2 precursor in the calcined support accounted for 4% of the total mass of the support. The resulting pseudo-boehmite powder was kneaded with a dilute acid solution containing 5% by volume of nitric acid, extruded into strips with a diameter of 5 mm, cut into 4 mm lengths, dried at 120°C for 8 hours, and calcined at 650°C for 5 hours to obtain the desired support.

[0390] 55.4 g of cobalt nitrate hexahydrate (technical grade, 98% purity), 6.83 g of zinc nitrate hexahydrate (analytical purity), and 5.65 g of copper nitrate trihydrate (analytical purity) were dissolved in water to obtain 144 mL of solution. The solution was supported twice on 100 g of the obtained support by spray impregnation, and after each spray impregnation, it was dried at 120 ° C for 4 hours and then calcined at 400 ° C for 4 hours. 1.8 g of ammonium molybdate tetrahydrate was dissolved in water to obtain 72 mL of solution. The solution was supported on the above-obtained intermediate product by spray impregnation, dried at 120 ° C for 4 hours, and then calcined at 400 ° C for 4 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20 ° C / hour, and finally reduced at 430 ° C for 3 hours to obtain catalyst A-IV-3.

[0391] Example IV-4 Pseudoboehmite powder (specific surface area 340 m) prepared by the aluminum sulfate method 2Pseudo-boehmite powder containing phosphorus doping element, having a SiO2 / Al2O3 molar ratio of 45 / g, a pore volume of 1.13 ml / g, and a P content of 0.18 g per 100 g of pseudo-boehmite powder calculated as Al2O3. In preparing the pseudo-boehmite powder, ZSM-5 molecular sieve precursor (ZSM-5 powder available from the Catalyst Factory of Nankai University, SiO2 / Al2O3 = 45 (molar ratio), hereinafter the same) was first added. As a result, the mass of Al2O3 derived from the pseudo-boehmite powder in the calcined support accounted for 85% of the total mass of the support) was kneaded with a dilute acid solution containing 5% by volume of nitric acid, extruded into toothed spheres with a diameter of 4 mm, dried at 80°C for 20 hours, and then calcined at 530°C for 6 hours to obtain the desired support.

[0392] 126 g of cobalt nitrate hexahydrate (technical grade, 98% purity), 4.55 g of zinc nitrate, and 0.79 g of silver nitrate (analytical pure) were dissolved in water to obtain 210 mL of solution. The solution was supported twice on 100 g of the obtained support by spray impregnation, and after each spray impregnation, it was dried at 120 ° C for 4 hours and then calcined at 400 ° C for 4 hours. 3.7 g of ammonium molybdate tetrahydrate (analytical pure) was dissolved in water to obtain 105 mL of solution. The solution was supported on the obtained intermediate product by spray impregnation, dried at 120 ° C for 4 hours, and then calcined at 400 ° C for 4 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20 ° C / hour, and finally reduced at 430 ° C for 3 hours to obtain catalyst A-IV-4.

[0393] Example IV-5 The support was prepared as described in Example IV-4, except that the ZSM-5 molecular sieve precursor was added at the beginning of the preparation of the pseudo-boehmite powder, so that the Al2O3 from the pseudo-boehmite powder in the calcined support accounted for 85% of the total mass of the support.

[0394] 126 g of cobalt nitrate hexahydrate (technical grade, 98% purity), 9.1 g of zinc nitrate hexahydrate (analytical purity), and 1.57 g of silver nitrate (analytical purity) were dissolved in water to obtain 208 mL of solution. The solution was supported twice on 100 g of the obtained support by spray impregnation, and after each spray impregnation, it was dried at 120 ° C for 4 hours and then calcined at 400 ° C for 4 hours. 7.4 g of ammonium molybdate tetrahydrate (analytical purity) was dissolved in water to obtain 104 mL of solution. The solution was supported on the obtained intermediate product by spray impregnation, dried at 120 ° C for 4 hours, and then calcined at 400 ° C for 4 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20 ° C / hour, and finally reduced at 430 ° C for 3 hours to obtain catalyst A-IV-5.

[0395] Example IV-6 Pseudoboehmite powder (specific surface area 341 m) prepared by the aluminum sulfate method 2 Pseudo-boehmite powder containing phosphorus as a dopant, having a pore volume of 1.11 ml / g, a P content of 4.2 g per 100 g of pseudo-boehmite powder calculated as Al2O3 (in the preparation of the pseudo-boehmite powder, ZSM-5 molecular sieve precursor was first added, so that the mass of Al2O3 derived from the pseudo-boehmite powder in the calcined support accounted for 85% of the total mass of the support), was kneaded with a dilute acid solution containing 5% by volume of nitric acid, extruded into toothed spheres with a diameter of 4 mm, dried at 80°C for 20 hours, and then calcined at 530°C for 6 hours to obtain the desired support.

[0396] The remaining procedures were the same as those described in Example IV-4 to obtain catalyst A-IV-6.

[0397] Example IV-7 Pseudoboehmite powder (specific surface area 288 m) prepared by the aluminum sulfate method 2Pseudo-boehmite powder containing sulfur as a doping element, having a pore volume of 0.93 ml / g, an S content of 0.88 g per 100 g of pseudo-boehmite powder calculated as Al2O3; water glass (i.e., aqueous sodium silicate solution) was first added as an SiO2 precursor. As a result, the mass of SiO2 derived from the SiO2 precursor in the calcined support accounted for 8% of the total mass of the support.) was kneaded with a dilute acid solution containing 5% by volume of nitric acid, extruded into a clover with a diameter of 4 mm, dried at 100°C for 8 hours, and then calcined at 850°C for 4 hours to obtain the desired support.

[0398] 201.6 g of cobalt nitrate hexahydrate (industrial grade, 98% purity), 2.28 g of zinc nitrate hexahydrate (analytical purity), and 8.48 g of copper nitrate trihydrate (analytical purity) were dissolved in water to obtain 146 mL of solution. The solution was supported twice on 100 g of the obtained support by spray impregnation, and after each spray impregnation, it 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 purity) was dissolved in water to obtain 73 mL of solution. The solution was supported on the obtained intermediate product by spray impregnation, dried at 120 ° C for 4 hours, and then calcined at 400 ° C for 4 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20 ° C / hour, and finally reduced at 430 ° C for 3 hours to obtain catalyst A-IV-7.

[0399] Example IV-8 The carrier obtained in Example IV-7 was used.

[0400] 100.8 g of cobalt nitrate hexahydrate (technical grade, 98% purity), 2.28 g of zinc nitrate hexahydrate (analytical purity), and 8.48 g of copper nitrate trihydrate (analytical purity) were dissolved in water to obtain 150 mL of solution. The solution was supported twice on 100 g of the obtained support by spray impregnation, and after each spray impregnation, it was dried at 120 ° C for 4 hours and then calcined at 400 ° C for 4 hours. 2.7 g of ammonium metatungstate (analytical purity) was dissolved in water to obtain 75 mL of solution. The solution was supported on the obtained intermediate product by spray impregnation, dried at 120 ° C for 4 hours, and then calcined at 400 ° C for 4 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20 ° C / hour, and finally reduced at 430 ° C for 3 hours to obtain catalyst A-IV-8.

[0401] Example IV-9 Pseudoboehmite powder (specific surface area 281 m) prepared by the aluminum sulfate method 2 Pseudo-boehmite powder containing a doping element of fluorine, having a pore volume of 0.87 ml / g, a F content of 0.82 g per 100 g of pseudo-boehmite powder calculated as Al2O3; in preparing the pseudo-boehmite powder, water glass (i.e., aqueous sodium silicate solution) was first added as an SiO2 precursor. As a result, the mass of SiO2 derived from the SiO2 precursor in the calcined support accounted for 21% of the total mass of the support.) was kneaded with a dilute acid solution containing 5% by volume of nitric acid, extruded into clover-shaped granules with a thickness of 4 mm, dried at 90°C for 18 hours, and calcined at 770°C for 9 hours to obtain the desired support.

[0402] 176.4 g of cobalt nitrate hexahydrate (technical grade, 98% purity), 2.28 g of zinc nitrate hexahydrate (analytical purity), and 11.3 g of copper nitrate trihydrate (analytical purity) were dissolved in water to obtain 130 mL of solution. The solution was supported twice on 100 g of the obtained support by spray impregnation, and after each spray impregnation, it was dried at 120 ° C for 4 hours and then calcined at 400 ° C for 4 hours. 2.0 g of ammonium metatungstate (analytical purity) was dissolved in water to obtain 65 mL of solution. The solution was supported on the obtained intermediate product by spray impregnation, dried at 120 ° C for 4 hours, and then calcined at 400 ° C for 4 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20 ° C / hour, and finally reduced at 430 ° C for 3 hours to obtain catalyst A-IV-9.

[0403] Example IV-10 Pseudoboehmite powder (specific surface area 274 m) prepared by the aluminum sulfate method 2 The pseudo-boehmite powder containing sulfur as a doping element was prepared, having a pore volume of 0.85 ml / g, a pore volume of 0.85 ml / g, and an S content of 0.95 g per 100 g of pseudo-boehmite powder calculated as Al2O3; in preparing the pseudo-boehmite powder, water glass (i.e., aqueous sodium silicate solution) was first added as an SiO2 precursor. As a result, the mass of SiO2 derived from the SiO2 precursor in the calcined support accounted for 25% of the total mass of the support. The pseudo-boehmite powder was kneaded with a dilute acid solution containing 5% by volume of nitric acid, extruded into clover-shaped granules with a diameter of 3.5 mm, dried at 150°C for 6 hours, and then calcined at 930°C for 6 hours to obtain the desired support.

[0404] 227.5 g of nickel nitrate hexahydrate (technical grade, 98% purity), 2.28 g of zinc nitrate hexahydrate (analytical purity), and 1.10 g of silver nitrate (analytical purity) were dissolved in water to obtain 156 mL of solution. The solution was supported on 100 g of the obtained support by spray impregnation three times, and after each spray impregnation, it was dried at 120 ° C for 4 hours and then calcined at 400 ° C for 4 hours. 5.4 g of ammonium metatungstate (analytical purity) was dissolved in 52 mL of water, and the solution was supported on the obtained intermediate product by spray impregnation. The solution was dried at 120 ° C for 4 hours and then calcined at 400 ° C for 4 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20 ° C / hour, and finally reduced at 430 ° C for 3 hours to obtain catalyst A-IV-10.

[0405] Example IV-11 Pseudoboehmite powder (specific surface area 265 m) prepared by the aluminum sulfate method 2 Pseudo-boehmite powder containing phosphorus as a dopant, having a pore volume of 0.81 ml / g, a P content of 3.1 g per 100 g of pseudo-boehmite powder calculated as Al2O3; in preparing the pseudo-boehmite powder, water glass (i.e., aqueous sodium silicate solution) was first added as an SiO2 precursor. As a result, the mass of SiO2 derived from the SiO2 precursor in the calcined support accounted for 28% of the total mass of the support.) was kneaded with a dilute acid solution containing 5% by volume of nitric acid, extruded into clover-shaped granules with a diameter of 3 mm, dried at 100°C for 8 hours, and calcined at 1020°C for 5 hours to obtain the desired support.

[0406] 141.1 g of cobalt nitrate hexahydrate (technical grade, 98% purity), 2.28 g of zinc nitrate hexahydrate (analytical purity), and 2.20 g of silver nitrate (analytical purity) were dissolved in water to obtain 144 mL of solution. The solution was supported on 100 g of the obtained support by spray impregnation three times, and after each spray impregnation, it was dried at 120 ° C for 4 hours and then calcined at 400 ° C for 4 hours. Next, 5.4 g of ammonium metatungstate (analytical purity) was dissolved in 48 mL of water, and the solution was supported on the obtained intermediate product by spray impregnation. It was dried at 120 ° C for 4 hours and then calcined at 400 ° C for 4 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20 ° C / hour, and finally reduced at 430 ° C for 3 hours to obtain catalyst A-IV-11.

[0407] Example IV-12 The pseudo-boehmite powder used had a doping element P content of 1.33 g per 100 g of pseudo-boehmite powder calculated as Al2O3, and a content of 375 m 2 A catalyst was prepared as described in Example IV-1, except that the catalyst had a specific surface area of ​​0.98 ml / g and a pore volume of 0.98 ml / g, to obtain catalyst A-IV-12.

[0408] Comparative example IV-1 The pseudo-boehmite powder used did not contain any doping elements and had a viscosity of 391 m 2 / g and a pore volume of 1.06 ml / g, and a catalyst was prepared as described in Example IV-2, except that zinc nitrate hexahydrate was not present in the solution used in the spray impregnation, to obtain catalyst D-IV-1.

[0409] Comparative example IV-2 The pseudo-boehmite powder used did not contain any doping elements and had a viscosity of 349 m 2 / g and a pore volume of 1.17 ml / g, and a catalyst was prepared as described in Example IV-8, except that copper nitrate trihydrate was not present in the solution used in the spray impregnation, to obtain catalyst D-IV-2.

[0410] Comparative example IV-3 The pseudo-boehmite powder used did not contain any doping elements and had a viscosity of 391 m 2 / g specific surface area and pore volume of 1.06 ml / g, and a catalyst was prepared as described in Example IV-2, except that zinc nitrate hexahydrate was replaced with 16.03 g of magnesium nitrate hexahydrate (analytically pure), to obtain catalyst D-IV-3.

[0411] Comparative example IV-4 The pseudo-boehmite powder used did not contain any doping elements and had a viscosity of 391 m 2 / g specific surface area and pore volume of 1.06 ml / g, a catalyst was prepared as described in Example IV-2, except that ammonium molybdate was not added and zinc nitrate hexahydrate was replaced with 8.84 g of calcium nitrate tetrahydrate, to obtain catalyst D-IV-4.

[0412] Test Example IV-1 The elemental composition of the support and catalyst was analyzed by plasma emission spectroscopy, the content of doping elements was expressed by weight relative to 100 g of matrix, and the content of active metal components and metal promoters was expressed by weight relative to 100 g of matrix; the support obtained was characterized by NH3-TPD, BET nitrogen adsorption-desorption method. The results are shown in Table IV-1.

[0413] [Table 14]

[0414] Test Example IV-2 This example illustrates a process for producing 1,6-hexanediamine by hydroamination of 1,6-hexanediol using a catalyst according to a fourth type of embodiment of the present application.

[0415] 100 mL of the catalyst obtained in each of the examples and comparative examples was measured and placed in a fixed-bed reactor. It was activated using hydrogen at 220°C for 2 hours. The mixture was then cooled to 165°C, and the system pressure was increased to 11 MPa using hydrogen. Ammonia was metered into the reaction system via a metering pump, preheated to 125°C, and delivered to the top of the reactor. Melted 1,6-hexanediol was supplied to the top of the reactor via a metering pump, and hydrogen was steadily introduced via a gas mass flow meter. The molar ratio of hydrogen to ammonia to 1,6-hexanediol was 2:12:1, and the liquid-phase volumetric space velocity of 1,6-hexanediol was 0.35 h / min. -1 The catalytic amination reaction was carried out in a reactor at a reaction temperature of 170°C and a reaction pressure of 11 MPa. After 20 hours of reaction, the reaction solution was sampled and analyzed. The analytical results are shown in Table IV-2.

[0416] Samples were analyzed by gas chromatography and calibrated using the correction factors of formulated standards.

[0417] The conversion and selectivity were calculated based on the molar content of each component in the reaction solution, using the same calculation method as described in Test Example I-2.

[0418] [Table 15]

[0419] Test Example IV-3 This example illustrates a process for producing n-propylamine by hydroamination of n-propanol using a catalyst according to a fourth type of embodiment of the present application.

[0420] 100 ml of catalyst A-IV-3 obtained in Example IV-3 was measured and placed in a fixed-bed reactor and activated with hydrogen at 220°C for 2 hours. The reactor was then cooled to 140°C, and the system pressure was increased to 2 MPa using hydrogen. Ammonia was metered into the reaction system via a metering pump, preheated to 110°C, and delivered to the top of the reactor. n-Propanol was supplied to the top of the reactor via a metering pump, and hydrogen was steadily introduced via a gas mass flow meter. The molar ratio of hydrogen, ammonia, and n-propanol was 3:6:1, and the liquid phase volumetric space velocity of propanol was 0.5 h / s . -1 The catalytic amination reaction was carried out in the reactor. After the reaction stabilized, the reaction solution was sampled and analyzed (the analytical conditions and the calculation methods of conversion and selectivity were the same as those in Test Example IV-2). The analytical results are shown in Table IV-3.

[0421] [Table 16]

[0422] Test Example IV-4 Catalysts A-IV-1, A-IV-4, D-IV-1, D-IV-2, and D-IV-3 were each placed in a fixed-bed reactor under the same conditions as in Test Example IV-2, with the only difference being the extended reaction time. Tests were conducted for 400 hours. The reaction solution after initial stabilization, i.e., after 20 hours of reaction (analysis conditions, and calculation methods for conversion and selectivity were the same as in Test Example IV-2), and the reaction solution after 400 hours of reaction (analysis conditions, and calculation methods for conversion and selectivity were the same as in Test Example IV-2) were analyzed and compared. The analytical results are shown in Table IV-4.

[0423] [Table 17]

[0424] As can be seen from the above table, after the catalysts A-IV-1 and A-IV-4 were tested for 400 hours, the activity and selectivity of the catalysts did not decrease substantially (i.e., the reduction value was less than 2%), while the activity and selectivity of the catalysts D-IV-1 to D-IV-4 decreased significantly, and more by-products were produced, indicating that the catalysts of the present application have higher stability.

[0425] Example V Series The fifth type of embodiment of the present application will be further described in detail below with reference to examples in Example Series V. In the following examples in Example Series V, the pseudoboehmite powder used had an (Al2O3) content of 70 wt % on a dry basis; the titanium white powder was prepared by titanyl sulfate-ammonia hydrolysis with a sulfate content of 2.5 wt % and a TiO2 content of 95 wt %, and was commercially available under the trade name SA-100 from Shandong Dongjia Chemical Company.

[0426] Example V-1 820 g of pseudoboehmite powder (produced by the nitric acid method, specific surface area 380 m 2 The desired support was obtained by uniformly mixing 300 g of titanium white powder (wt. / g, pore volume 0.96 mL / g) in a mixer, kneading with 790 mL of a dilute aqueous acid solution containing 5% by volume of nitric acid, extruding the mixture into strips with a diameter of 5 mm, cutting the strips into 4 mm lengths, drying the strips overnight at 120°C, and calcining them at 800°C for 4 hours.

[0427] 126 g of cobalt nitrate hexahydrate (technical grade, 98% purity) was dissolved in water to obtain 150 mL of solution, which was then spray-impregnated twice onto 100 g of the obtained support, dried at 120°C for 4 hours after each spray impregnation, then calcined at 400°C for 4 hours, and then reduced with hydrogen at a temperature gradually increasing at a rate of 20°C / hour, and finally reduced at 430°C for 3 hours to obtain catalyst AV-1.

[0428] Example V-2 780 g of pseudoboehmite powder (produced by carbonization method, specific surface area 405 m 2 / g, pore volume 1.01 mL / g) and 220 g of titanium white powder were homogeneously mixed in a mixer, kneaded with 775 mL of a dilute aqueous acid solution containing 7% by volume of acetic acid, extruded into clover-shaped granules with a thickness of 3 mm, dried at 120 °C overnight, and calcined at 850 °C for 3 hours to obtain the desired support.

[0429] 140.4 g of nickel nitrate hexahydrate (technical grade, 98% purity) was dissolved in water to obtain 144 mL of solution, which was then spray-impregnated twice onto 100 g of the obtained support, dried at 120°C for 4 hours after each spray-impregnation, then calcined at 390°C for 4 hours, and then reduced with hydrogen at a temperature gradually increasing at a rate of 20°C / hour, and finally reduced at 440°C for 3 hours to obtain catalyst AV-2.

[0430] Example V-3 820 g of pseudoboehmite powder (produced by the aluminum sulfate method, specific surface area 380 m 2 The desired support was obtained by uniformly mixing 180 g of titanium white powder (wt. / g, pore volume 1.26 mL / g) in a mixer, kneading with 785 mL of a dilute aqueous acid solution containing 5% by volume of nitric acid, extruding the mixture into toothed spheres with a diameter of 4 mm, drying overnight at 120°C, and then calcining at 820°C for 3 hours.

[0431] 134.4 g of cobalt nitrate hexahydrate (technical grade, 98% purity) and 43.4 g of 50 wt % manganese nitrate solution were dissolved in water to obtain 155 mL of solution. The solution was supported on 100 g of the obtained support twice by spray impregnation, and after each spray impregnation, it was dried at 120 ° C for 4 hours, then calcined at 400 ° C for 4 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20 ° C / hour, and finally reduced at 430 ° C for 3 hours to obtain catalyst AV-3.

[0432] Example V-4 1000g of pseudoboehmite powder (produced by the nitric acid method, specific surface area 380m 2The desired support was obtained by uniformly mixing 200 g of titanium white powder (wt. / g, pore volume 0.96 mL / g) in a mixer, kneading with 785 mL of a dilute aqueous acid solution containing 5% by volume of nitric acid, extruding the mixture into strips with a diameter of 5 mm, cutting them into strips with a length of 4 mm, drying them at 120°C overnight, and then calcining them at 800°C for 4 hours.

[0433] 129.2 g of cobalt nitrate hexahydrate (technical grade, 98% purity) and 4.0 g of silver nitrate (analytical purity) were dissolved in water to obtain 162 mL of solution, which was then spray-impregnated twice onto 100 g of the obtained support, dried at 120°C for 4 hours after each spray impregnation, then calcined at 400°C for 4 hours, and then reduced with hydrogen at a gradual temperature increase rate of 20°C / hour, and finally reduced at 430°C for 3 hours to obtain catalyst AV-4.

[0434] Example V-5 1500 g of pseudoboehmite powder (produced by carbonization method, specific surface area 405 m 2 / g, pore volume 1.01 mL / g) and 250 g of titanium white powder were homogeneously mixed in a mixer, kneaded with 777 mL of a dilute aqueous acid solution containing 5% by volume of nitric acid, extruded into clover-shaped granules with a thickness of 3 mm, dried overnight at 120 °C, and then calcined at 820 °C for 3.5 hours to obtain the desired support.

[0435] 132.6 g of nickel nitrate hexahydrate (technical grade, 98% purity) and 7.7 g of ammonium perrhenate were dissolved in water to obtain 140 mL of solution. The solution was supported on 100 g of the obtained support twice by spray impregnation, and after each spray impregnation, it was dried at 120 ° C for 4 hours, then calcined at 390 ° C for 4 hours, and then reduced with hydrogen while gradually increasing the temperature at a rate of 20 ° C / hour, and finally reduced at 440 ° C for 3 hours to obtain catalyst AV-5.

[0436] Example V-6 950 g of pseudoboehmite powder (produced by the aluminum sulfate method, specific surface area 380 m 2 / g, pore volume 0.96 mL / g) and 320 g of titanium white powder were uniformly mixed in a mixer, kneaded with 767 mL of a dilute acid aqueous solution containing 5 vol% nitric acid and 2 vol% sulfuric acid, extruded into toothed spheres with a diameter of 4 mm, dried overnight at 120 °C, and then calcined at 820 °C for 5 hours to obtain the desired support.

[0437] 182.6 g of cobalt nitrate hexahydrate (technical grade, 98% purity) was dissolved in water to obtain 170 mL of solution. 16 g of ammonium molybdate tetrahydrate (analytical pure) was dissolved in water to obtain 138 mL of solution. The cobalt nitrate solution was supported twice on 100 g of the obtained support by spray impregnation, and then the ammonium molybdate solution was supported once on the obtained support by spray impregnation. The support was then dried at 120°C for 4 hours, calcined at 400°C for 4 hours, reduced with hydrogen while gradually increasing the temperature at a rate of 20°C / hour, and finally reduced at 430°C for 3 hours to obtain catalyst AV-6.

[0438] Example V-7 1000g of pseudoboehmite powder (produced by the aluminum sulfate method, specific surface area 380m 2 / g, pore volume 0.96 mL / g) and 150 g of titanium white powder were homogeneously mixed in a mixer, kneaded with 770 mL of a dilute aqueous acid solution containing 5 vol% nitric acid and 2 vol% sulfuric acid, extruded into toothed spheres with a diameter of 4 mm, dried at 120 °C overnight, and calcined at 820 °C for 3.5 hours to obtain the desired support.

[0439] 177.4 g of cobalt nitrate hexahydrate (technical grade, 98% purity) and 15.9 g of copper nitrate trihydrate (analytical purity) were dissolved in water to obtain 140 mL of solution, which was then spray-impregnated twice onto 100 g of the obtained support, dried at 120°C for 4 hours after each spray-impregnation, then calcined at 400°C for 4 hours, and then reduced with hydrogen at a gradual temperature increase rate of 20°C / hour, and finally reduced at 430°C for 3 hours to obtain catalyst AV-7.

[0440] Example V-8 780 g of pseudoboehmite powder (produced by the aluminum sulfate method, specific surface area 380 m 2 / g, pore volume 0.96 mL / g) and 220 g of titanium white powder were homogeneously mixed in a mixer, kneaded with 782 mL of a dilute acid aqueous solution containing 5 vol% nitric acid, 2 vol% hydrofluoric acid, and 0.5 wt% lanthanum nitrate, extruded into toothed spheres with a diameter of 4 mm, dried overnight at 120 °C, and calcined at 820 °C for 4 hours to obtain the desired support.

[0441] 134.4 g of cobalt nitrate hexahydrate (technical grade, 98% purity) and 30.3 g of zinc nitrate hexahydrate (analytical purity) were dissolved in water to obtain 160 mL of solution, which was then spray-impregnated twice onto 100 g of the obtained support, dried at 120°C for 4 hours after each spray impregnation, then calcined at 400°C for 4 hours, and then reduced with hydrogen at a gradual temperature increase rate of 20°C / hour, and finally reduced at 430°C for 3 hours to obtain catalyst AV-8.

[0442] Comparative example V-1 A catalyst was prepared as described in Example V-3, except that the amount of pseudoboehmite powder used was 500 g, the amount of titanium white powder used was 500 g, and 12.8 g of KNO was added during the kneading process, to obtain catalyst DV-1.

[0443] Comparative example V-2 A catalyst was prepared as described in Example V-2, except that the amount of pseudoboehmite powder used was 900 g and the amount of titanium white powder used was 100 g, to obtain catalyst DV-2.

[0444] Test Example V-1 The elemental composition of the catalyst was analyzed by plasma emission spectroscopy, and the results showed that all the sulfur in the titanium white powder was retained in the support, and the contents of other elements were essentially the same as those in the feed; the catalyst obtained was characterized by NH3-TPD, CO2-TPD, and BET nitrogen adsorption-desorption methods. The results are shown in Table V-1.

[0445] [Table 18]

[0446] Test Example V-2 The resulting catalysts AV-1 to AV-8 and the resulting catalysts DV-1 and DV-2 were each measured, placed in a fixed-bed reactor, and activated with hydrogen at 220°C for 2 hours. The system was then cooled to 168°C, and the system pressure was increased to 12.5 MPa using hydrogen. Ammonia was metered into the reaction system via a metering pump, preheated to 150°C, and sent to the reactor. Heated and melted 1,6-hexanediol was fed to the reactor via a metering pump, and hydrogen was steadily introduced via a gas mass flow meter. The molar ratio of hydrogen to ammonia to 1,6-hexanediol was 3:12:1, and the liquid-phase volumetric space velocity of 1,6-hexanediol was 0.4 h / min. -1 The catalytic amination reaction was carried out in a reactor at a reaction temperature of 175°C and a reaction pressure of 12.5 MPa. After the reaction conditions were stabilized for 2 hours, the reaction solution was sampled and analyzed. The analytical results are shown in Table V-2.

[0447] Samples were analyzed by gas chromatography and calibrated using the correction factors of formulated standards.

[0448] The conversion and selectivity were calculated based on the molar content of each component in the reaction solution, using the same calculation method as described in Test Example I-2.

[0449] [Table 19]

[0450] As can be seen from the data in the above table, the "other" content, i.e., the content of impurities, of catalysts DV-1 and DV-2 is significantly higher than that of the other catalysts, and the conversion rates of these catalysts are much lower.

[0451] After 196 hours of evaluation, each catalyst was discharged for characterization. The specific surface area and pore volume of catalysts AV-1 to AV-8 remained essentially unchanged, and no significant carbon deposition was observed. Meanwhile, the specific surface area and pore volume of catalysts DV-1 and DV-2 decreased by 7% and 9%, respectively, and their carbon deposition was 5.6% and 6.7% by weight, respectively. This indicates that the present catalysts have more stable catalytic performance, can accelerate reaction rates, reduce carbon deposition, and delay pore channel blockage.

[0452] Test Example V-3 100 mL of the resulting catalyst was measured and placed in a fixed-bed reactor and activated with hydrogen at 220°C for 2 hours. The mixture was then cooled to 168°C, and the system pressure was increased to 8 MPa using hydrogen. Ammonia was metered into the reaction system via a metering pump, preheated to 150°C, and delivered to the top of the reactor. A mixed solution of hexanediol, hexamethyleneimine, and 6-amino-1-hexanol (50 wt% hexanediol, 32 wt% hexamethyleneimine, and 18 wt% 6-amino-1-hexanol) was supplied to the top of the reactor via a metering pump, and hydrogen was steadily introduced via a gas mass flow meter. The molar ratio of hydrogen, ammonia, and the mixed solution was 3:18:1, and the liquid phase volumetric space velocity of the mixed solution was 0.5 h / min. -1 The catalytic amination reaction was carried out in a reactor at a reaction temperature of 185°C and a reaction pressure of 8 MPa. After the reaction state was stabilized for 2 hours, the reaction solution was sampled and analyzed (the analytical conditions and the calculation methods for conversion and selectivity were the same as in Test Example V-2). The analytical results are shown in Table V-3.

[0453] [Table 20]

[0454] As can be seen from the data in the preceding table, the present catalysts can provide higher hexanediol conversion and higher hexanediamine selectivity compared to catalysts DV-1 and DV-2.

[0455] Although the present application has been described in detail above with reference to preferred embodiments, it is not intended to be limited to these embodiments. Various modifications can be made in accordance with the inventive concept of the present application, and these modifications are within the scope of the present application.

[0456] It should be noted that the various technical features described in the foregoing embodiments can be combined in any suitable manner without contradiction, and in order to avoid unnecessary repetition, the present application does not describe various possible combinations, but such combinations also fall within the scope of the present application.

[0457] Furthermore, various embodiments of the present application can be arbitrarily combined without departing from the spirit of the present application, and such combined embodiments should be considered as the disclosure of the present application.

Claims

1. 1. A catalyst useful for producing organic amines by catalytic amination, comprising: The catalyst comprises an inorganic porous carrier containing aluminum and / or silicon, and an active metal component supported on the carrier; the active metal component comprises at least one metal selected from the group consisting of Group VIII metals and Group IB metals; The carrier is NH ３ - an ammonia adsorption capacity of 0.25 to 0.65 mmol / g, as measured by the TPD test; further comprising a metal promoter supported on the support; the metal co-catalyst 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, calculated as elemental metals, is from 0.05 to 15:1; or the metal co-catalyst 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, calculated as elemental metals, is from 0.2 to 20:1; or the metal co-catalyst 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 to the Group IB metal to the Group IIB metal, calculated as elemental metals, is 0.1-10:0.1-10:1; The catalyst wherein the Group VIIB metal is selected from manganese, rhenium, or a combination thereof, the Group IB metal is selected from copper, silver, gold, or a combination thereof, the Group IIB metal is zinc, and the Group VIB metal is selected from molybdenum, tungsten, or a combination thereof.

2. the support comprises a matrix and a doping element, the matrix comprises a first support component, the first support component is selected from alumina, silica, molecular sieve, aluminosilicate, or a combination thereof; and The doping element is selected from a metal element, a non-metal element, or a combination thereof, and does not include sodium or chlorine, and the metal element is selected from calcium, magnesium, potassium, bismuth, strontium, barium, lanthanum, or a combination thereof; and the non-metal element is selected from boron, fluorine, phosphorus, sulfur, selenium, or a combination thereof; 2. The catalyst of claim 1, wherein the doping elements in the support are derived from metal cations and / or acid radical ions, but do not include sodium ions or chloride ions; the metal cations are selected from calcium ions, magnesium ions, potassium ions, bismuth ions, strontium ions, barium ions, lanthanum ions, or combinations thereof; and the acid radical ions are selected from borate ions, fluoride ions, phosphate ions, sulfate ions, selenate ions, or combinations thereof.

3. A catalyst as described in claim 1 or 2, wherein the support further comprises a second support component, the second support component being selected from diatomaceous earth and titania.

4. 3. The catalyst of claim 2, wherein the support has at least one of the following characteristics: The support has a carbon dioxide adsorption capacity of 0.05 to 0.3 mmol / g; the doping element is present in the support in an amount of 0.03 to 6% by weight, relative to the total weight of the matrix; The carrier is 120 to 210 m ２ / g specific surface area; The support has a pore volume of 0.45 to 1.1 ml / g; The ratio of the pore volume of pores having a pore diameter in the range of 7 to 27 nm to the pore volume of the support is 70 to 90%, and the ratio of the pore volume of pores having a pore diameter of less than 7 nm to the pore volume of the support is 0 to 10%; The matrix in the support comprises a combination of alumina and titania in a weight ratio of 1.5 to 5:1; and The alumina content in the support is 70% by weight or more, based on the total weight of the matrix.

5. 5. The catalyst of any one of claims 1 to 4, wherein the active metal component is present in an amount of from 10 g to 42 g, calculated as elemental metal, per 100 g of the matrix.

6. The catalyst of claim 1, wherein the metal promoter is present in an amount of 0 to 10 g per 100 g of the matrix.

7. The weight ratio of said Group VIIB metal to said Group IB metal, calculated as elemental metal, is 0.1 to 12:1; the weight ratio of said Group VIIB metal to said Group IIB metal, calculated as elemental metal, is 0.3 to 6:1; 7. The catalyst of claim 6, wherein the weight ratio of the Group VIB metal to the Group IB metal to the Group IIB metal, calculated as elemental metal, is 0.2-8:0.2-8:

1.

8. A method for producing the catalyst according to any one of claims 1 to 7, comprising the following steps 1) to 3): 1) NH ３ - providing an inorganic porous carrier containing aluminum and / or silicon, which has an ammonia adsorption capacity of 0.25 to 0.65 mmol / g as measured by the TPD test; 2) supporting the active metal component and the metal promoter on the support; and 3) A step of subjecting the material obtained in step 2) to a heat treatment and a reduction treatment to obtain the catalyst.

9. The "step of providing an inorganic porous support containing aluminum and / or silicon" in step 1) includes a step of successively molding, drying and calcining a mixture containing a doping element and a matrix or a precursor thereof to obtain the support; The matrix comprises a first support component, the first support component being selected from alumina, silica, molecular sieve, aluminosilicate, or a combination thereof, and the precursor of the first support component is 250 to 410 m ２ / g and a specific surface area of ​​0.7 to 1.3 ml / g; 9. The method of claim 8, wherein the doping elements are selected from metal elements, non-metal elements, or combinations thereof, and do not include sodium or chlorine, and the metal elements are selected from calcium, magnesium, potassium, bismuth, strontium, barium, lanthanum, or combinations thereof; and the non-metal elements are selected from boron, fluorine, phosphorus, sulfur, selenium, or combinations thereof.

10. The method of claim 9, wherein the carrier further comprises a second carrier component, the second carrier component being selected from diatomaceous earth and titania.

11. The doping element is provided using a carrier modifier comprising at least one compound capable of providing a cation and / or anion, wherein the cation is selected from calcium ions, magnesium ions, potassium ions, bismuth ions, strontium ions, barium ions, lanthanum ions, or a combination thereof; 10. The method of claim 9, wherein the anions are selected from borate, fluoride, phosphate, sulfate, selenate, or combinations thereof.

12. 12. The method according to claim 8, wherein the supporting step in step 2) comprises impregnating the support with a solution containing a precursor of the active metal component and a precursor of the metal promoter.

13. A catalyst useful for producing organic amines by catalytic amination, comprising: The catalyst comprises an inorganic porous carrier containing aluminum and / or silicon, and an active metal component supported on the carrier; the active metal component is selected from the group consisting of Group VIII metals and Group IB metals; the support has an ammonia adsorption capacity of 0.25 to 0.65 mmol / g as measured by the NH 3 -TPD test; the support comprises a matrix and a doping element, the matrix comprises a first support component, the first support component is selected from alumina, silica, molecular sieve, aluminosilicate, or a combination thereof; The doping elements are selected from a combination of metal elements and non-metal elements, and do not include sodium or chlorine, and the metal elements are selected from calcium, magnesium, potassium, bismuth, strontium, barium, lanthanum, or combinations thereof; and the non-metal elements are selected from boron, fluorine, phosphorus, sulfur, selenium, or combinations thereof; Catalyst, wherein the doping elements in the support are derived from metal cations and / or acid radical ions, but do not include sodium ions or chloride ions; the metal cations are selected from calcium ions, magnesium ions, potassium ions, bismuth ions, strontium ions, barium ions, lanthanum ions, or combinations thereof; and the acid radical ions are selected from borate ions, fluoride ions, phosphate ions, sulfate ions, selenate ions, or combinations thereof.

14. The method of claim 13, wherein the carrier further comprises a second carrier component, the second carrier component being selected from diatomaceous earth and titania.

15. The catalyst of claim 13 or 14, wherein the support has at least one of the following characteristics: The support has a carbon dioxide adsorption capacity of 0.05 to 0.3 mmol / g; the doping element is present in the support in an amount of 0.03 to 6% by weight, relative to the total weight of the matrix; The support has a specific surface area of ​​120 to 210 m 2 / g; The support has a pore volume of 0.45 to 1.1 ml / g; The ratio of the pore volume of pores having a pore diameter in the range of 7 to 27 nm to the pore volume of the support is 70 to 90%, and the ratio of the pore volume of pores having a pore diameter of less than 7 nm to the pore volume of the support is 0 to 10%; The matrix in the support comprises a combination of alumina and titania in a weight ratio of 1.5 to 5:1; and The alumina content in the support is 70% by weight or more, based on the total weight of the matrix.

16. A catalyst according to any one of claims 13 to 15, wherein the active metal component is present in an amount of from 10 g to 42 g, calculated as elemental metal, per 100 g of the matrix.

17. A method for producing the catalyst according to any one of claims 13 to 16, comprising the following steps 1) to 3): 1) providing an inorganic porous carrier containing aluminum and / or silicon, which has an ammonia adsorption capacity of 0.25 to 0.65 mmol / g as measured by the NH 3 -TPD test; 2) supporting the active metal component on the support; and 3) A step of subjecting the material obtained in step 2) to a heat treatment and a reduction treatment to obtain the catalyst.

18. The "step of providing an inorganic porous carrier containing aluminum and / or silicon" in step 1) comprises a step of successively shaping, drying and calcining a mixture containing a doping element and a matrix or a precursor thereof to obtain the carrier; The matrix comprises a first support component, the first support component being selected from alumina, silica, molecular sieve, aluminosilicate or a combination thereof, and the precursor of the first support component is pseudoboehmite having a specific surface area of ​​250-410 m 2 / g and a specific surface area of ​​0.7-1.3 ml / g; 18. The method of claim 17, wherein the doping elements are selected from metal elements, non-metal elements, or combinations thereof, and do not include sodium or chlorine, and the metal elements are selected from calcium, magnesium, potassium, bismuth, strontium, barium, lanthanum, or combinations thereof; and the non-metal elements are selected from boron, fluorine, phosphorus, sulfur, selenium, or combinations thereof.

19. The method of claim 17, wherein the carrier further comprises a second carrier component, the second carrier component being selected from diatomaceous earth and titania.

20. The doping element is provided by means of a carrier modifier comprising at least one compound capable of providing cations and / or anions, wherein the cations are selected from calcium ions, magnesium ions, potassium ions, bismuth ions, strontium ions, barium ions, lanthanum ions, or combinations thereof; 19. The method of claim 18, wherein the anions are selected from borate, fluoride, phosphate, sulfate, selenate, or combinations thereof.

21. A method according to any one of claims 17 to 20, wherein the supporting step in step 2) includes a step of impregnating the support with a solution containing a precursor of the active metal component.

22. For an amination reaction, the method comprises contacting a starting material for amination and an aminating agent with the catalyst according to any one of claims 1 to 7 and 13 to 16 in the presence of hydrogen to obtain an organic amine; The amination raw material may be ethanol, acetaldehyde, n-propanol, propionaldehyde, isopropanol, n-butanol, butyraldehyde, isobutanol, isobutyraldehyde, 2-ethylhexanol, 2-ethylhexaldehyde, octanol, octanal, dodecanol, dodecanal, hexadecanol, hexadecanal, cyclopentanol, cyclohexanol, cyclooctanol, cyclododecanol, benzyl alcohol, benzaldehyde, phenethyl alcohol, phenylacetaldehyde, or 1,4-butane. diol, 1,4-butanedial, 1,5-pentanediol, 1,5-glutaraldehyde, 1,6-hexanediol, 1,6-hexanedial, 1,8-octanediol, 1,8-octanedial, 1,12-dodecanediol, 1,12-dodecanedialdehyde, ethanolamine, propanolamine, isopropanolamine, 6-aminohexanol, diethanolamine, diisopropanolamine, dimethylethanolamine, acetone, ethylene glycol, 1,3-propanediol, or combinations thereof; 1. A process for producing an organic amine, wherein the aminating agent is selected from ammonia, a C1-C12 primary amine, a C2-C12 secondary amine, or a combination thereof.

23. The amination conditions are as follows: a molar ratio of hydrogen to the aminating agent to the aminating raw material is 1 to 5:2 to 35:1; a temperature is 105 to 220°C; a pressure is 0.8 to 25 MPa; and a liquid phase volumetric space velocity of the aminating raw material is 0.06 to 1 m ３ / (m ３ 23. The process of claim 22, comprising: h).

24. When the amination raw material is a monohydric alcohol, the amination conditions are a molar ratio of hydrogen to the aminating agent to the amination raw material of 1 to 4:2 to 8:1, a temperature of 130 to 210°C, a pressure of 1 to 4 MPa, and a liquid phase volumetric space velocity of the amination raw material of 0.1 to 0.8 m ３ / (m ３ h) including When the amination raw material is a ketone or an aldehyde, the amination conditions are such that the molar ratio of hydrogen to the aminating agent to the amination raw material is 1 to 4:2 to 6:1, the temperature is 105 to 180°C, the pressure is 0.7 to 3.5 MPa, and the liquid phase volumetric space velocity of the amination raw material is 0.1 to 1 m ３ / (m ３ h) including When the amination raw material is an alcohol amine, the amination conditions are a molar ratio of hydrogen to the aminating agent to the amination raw material of 1 to 4:3 to 20:1, a temperature of 130 to 200°C, a pressure of 1 to 18 MPa, and a liquid phase volumetric space velocity of the amination raw material of 0.06 to 0.8 m ３ / (m ３ h) including When the amination raw material is a dihydric alcohol, the amination conditions are a molar ratio of hydrogen to the aminating agent to the amination raw material of 1 to 4:3 to 35:1, a temperature of 130 to 220°C, a pressure of 4 to 25 MPa, and a liquid phase volumetric space velocity of the amination raw material of 0.06 to 0.8 m ３ / (m ３ 24. The process of claim 23, comprising: h).

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