CN109651166B - Method for preparing cyclohexylamine from aniline - Google Patents

Method for preparing cyclohexylamine from aniline Download PDF

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CN109651166B
CN109651166B CN201710934222.4A CN201710934222A CN109651166B CN 109651166 B CN109651166 B CN 109651166B CN 201710934222 A CN201710934222 A CN 201710934222A CN 109651166 B CN109651166 B CN 109651166B
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aniline
cyclohexylamine
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hydrogenation catalyst
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CN109651166A (en
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查晓钟
杨运信
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • C07C209/70—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines
    • C07C209/72—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines by reduction of six-membered aromatic rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8913—Cobalt and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support

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Abstract

The invention relates to a method for preparing cyclohexylamine from aniline, which mainly solves the problems of low yield and low selectivity of synthesizing cyclohexylamine by catalytic hydrogenation of aniline in the prior art. The method for preparing cyclohexylamine by adopting aniline comprises the step of reacting hydrogen and aniline serving as raw materials in the presence of an aniline hydrogenation catalyst to obtain cyclohexylamine, wherein the aniline hydrogenation catalyst comprises a carrier and an active component, and the carrier is phosphorus-modified Al2O3The active component comprises Co element and promoter element; the technical proposal that the promoter element comprises at least one metal element selected from alkaline earth metals and IB group metals better solves the problem and can be used in the industrial production of cyclohexylamine.

Description

Method for preparing cyclohexylamine from aniline
Technical Field
The invention relates to a method for preparing cyclohexylamine from aniline.
Background
Cyclohexylamine, also known as hexahydroaniline and aminocyclohexane, is a colorless transparent liquid, has strong fishy amine smell, and can be mixed and dissolved with water and common organic solvents. It is an important organic chemical raw material and fine chemical intermediate, and is mainly used in rubber auxiliary agent, food additive, anticorrosion, paper-making, plastic processing and textile industry.
Overseas production and application are mainly concentrated in western developed countries and regions, and main manufacturers include unequal-scale manufacturers such as American air products company, Seranies company, Germany Basff company, Bayer company and the like. However, in europe, cyclohexylamine is in a state of shortage because of the limitation of the hydrogen feed. The capacity of producing cyclohexylamine in China is close to 10 ten thousand tons per year, and main manufacturers thereof comprise: qingdao Jintian factories, Hebei Jizhong Weifang Zhenxing and Shandong Hengda. In 2010, the consumption capacity of the cyclohexylamine in China is 7 ten thousand tons per year, and with the rapid development of food additive sodium cyclamate and rubber industries, the consumption of the cyclohexylamine is increased by more than 10 percent every year.
The preparation process of cyclohexylamine has many routes, and mainly comprises aniline catalytic hydrogenation, nitrocyclohexane reduction, chlorocyclohexane catalytic ammonolysis, cyclohexanol vapor phase ammonification and cyclohexanone catalytic ammonolysis.
Reducing nitrocyclohexane: according to the method, nitrocyclohexane and hydrogen are used as raw materials, a reducing agent is used for generating cyclohexylamine, and the nitrocyclohexane raw materials are difficult to obtain, so that the method is basically eliminated. ② catalytic ammonolysis of chlorocyclohexane: the method takes chlorocyclohexane and ammonia as raw materials to carry out catalytic reaction on the chlorocyclohexane and the ammonia. The process route is longer, the selectivity of cyclohexylamine is poorer, and the reaction product contains hydrogen chloride, so the requirement on equipment is high. ③ cyclohexanol vapor phase ammonification method: under the action of a nickel/silicon dioxide catalyst, cyclohexanol and ammonia are subjected to liquid phase hydrogenation to generate cyclohexylamine and dicyclohexylamine, the yield of the product cyclohexylamine and dicyclohexylamine is 3:1, the conversion rate of cyclohexanol is about 70%, and no industrial report is found in China. The aniline catalytic hydrogenation method: the process of producing cyclohexylamine with benzene as material includes two steps of producing aniline directly with one benzene step and catalytic hydrogenation of aniline. The catalytic aniline hydrogenation process has two technological routes of normal pressure and pressurization. Both processes have the advantages of mature process and easily obtained raw materials, but the device has small universality, only can produce single cyclohexylamine, and cannot be used for producing other organic amines; and the process has the defects of low single pass conversion rate of the aniline, poor selectivity of the cyclohexylamine and the like.
However, the aniline catalytic hydrogenation has more operable space from the viewpoints of raw material source, cost advantage and process simplicity advantage and prospect, so the method is favored by domestic and foreign research institutions. A plurality of methods for preparing Ni catalysts are introduced and researched by Mink and the like of Hungarian science research institute in the "Hydrogenation of aniline to cyclic hexylamine amine on NaOH-promoted or Lanthana supported Nickel", and the discovery shows that in the gas phase reaction for preparing cyclohexylamine by catalytic Hydrogenation of aniline, the traditional Ni catalyst is added into a NaOH auxiliary agent, so that the initial selectivity of cyclohexylamine can be improved by about 5%; DE1975457(Hydrogenation and genetic catalysts for the preparation of mixtures of optional suspended cycles)ohexylamine and dicylo-hexamine from the corrmoparing amines) teach that a mixture of cyclohexylamine and dicyclohexylamine can be obtained with high yield and selectivity by hydrogenating aniline at 100-350 ℃ and 1-40 MPa. The carrier of the heterogeneous catalyst adopted in the reaction is Al2O3The active components are 0.50 to 10 percent of Ru and Pd. At present, many research institutions make articles on the aniline catalytic hydrogenation catalyst in an effort, but the effect is not obvious, and the technical barriers and obstacles of the aniline catalytic hydrogenation catalyst are difficult to break successfully. Namely, the prior methods have the problems of low yield and low selectivity of the cyclohexylamine in the process of synthesizing the cyclohexylamine.
Disclosure of Invention
The invention aims to solve the technical problem of low yield and selectivity of cyclohexylamine and provides a novel method for preparing cyclohexylamine from aniline, which has the characteristics of high yield and high selectivity of cyclohexylamine.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the method for preparing cyclohexylamine from aniline comprises the step of reacting hydrogen and aniline serving as raw materials in the presence of an aniline hydrogenation catalyst to obtain cyclohexylamine, wherein the aniline hydrogenation catalyst comprises a carrier and an active component, and the carrier is phosphorus-modified Al2O3The active component comprises Co element and promoter element; the promoter element includes at least one metal element selected from alkaline earth metals and group IB metals.
In the technical scheme, the molar ratio of the hydrogen to the aniline is preferably 20.0-40.0, and more preferably 25.0-35.0.
In the technical scheme, the reaction temperature is preferably 120-300 ℃, and more preferably 185-220 ℃.
In the technical scheme, the preferred volume space velocity of the raw material gas is 1800-3000 h-1More preferably 2100 to 2800h-1。
In the technical scheme, the reaction pressure is preferably 0.05-0.50 MPa.
Unless otherwise specified, the pressures described herein are in terms of gauge pressure.
In the above technical scheme, the modified Al2O3The content of phosphorus element in the carrier is preferably 0.10 to 3.00g/L, such as but not limited to 0.15, 0.20, 0.30, 0.40, 0.50, 0.60, 0.80, 0.90, 1.00, 1.30, 1.50, 1.60, 1.70, 1.80, 1.90, 2.00, 2.50, 2.90 and the like, and more preferably 0.80 to 2.00 g/L.
In the above technical solution, the alkaline earth metal in the hydrogenation catalyst is preferably at least one selected from Be, Mg, Ca, Sr and Ba, and more preferably both Ca and Ba. Ca and Ba have synergistic effect in improving the yield and selectivity of cyclohexylamine. The ratio of Ca and Ba is not particularly limited, for example, but not limited to, the weight ratio of Ca and Ba is 0.10 to 10.00, and non-limiting examples of more specific weight ratios within this range may be 0.20, 0.40, 0.50, 0.60, 0.80, 1.00, 1.20, 1.40, 1.60, 1.80, 2.00, 2.50, 3.00, 3.50, 4.00, 4.50, 5.00, 5.50, 6.00, 6.50, 7.00, 7.50, 8.00, and the like.
In the above technical solution, the group IB metal in the hydrogenation catalyst is preferably at least one selected from Cu, Ag and Au, and more preferably both Cu and Au. Cu and Au have synergistic effect on the aspects of improving the yield of the cyclohexylamine and the selectivity of the cyclohexylamine. The ratio of Cu and Au is not particularly limited, for example, but not limited to, the weight ratio of Cu and Au is 0.10 to 10.00, and non-limiting examples of more specific weight ratios within this range may be 0.20, 0.40, 0.50, 0.60, 0.80, 1.00, 1.20, 1.40, 1.60, 1.80, 2.00, 2.50, 3.00, 3.50, 4.00, 4.50, 5.00, 5.50, 6.00, 6.50, 7.00, 7.50, 8.00, and the like.
In the above technical solution, the promoter element preferably includes at least one selected from alkaline earth metal elements and at least one selected from group IB metal elements, and in this case, there is a synergistic effect between the metal element in the alkaline earth metal and the metal element in the group IB metal in the aspect of increasing the yield of cyclohexylamine and the selectivity of cyclohexylamine. By way of non-limiting example, such as but not limited to calcium in combination with copper, calcium in combination with gold, and the like. In this case, the ratio of the alkaline earth metal element to the group IB metal element is not particularly limited, but is, for example, not limited to, 0.10 to 10.00 in terms of weight ratio, and more specific non-limiting examples within this range may be 0.20, 0.40, 0.50, 0.60, 0.80, 1.00, 1.20, 1.40, 1.60, 1.80, 2.00, 2.50, 3.00, 3.50, 4.00, 4.50, 5.00, 5.50, 6.00, 6.50, 7.00, 7.50, 8.00, and the like.
In the technical scheme, the content of Co in the hydrogenation catalyst is preferably 1.00-8.00 g/L, for example, but not limited to, 1.50g/L, 2.00g/L, 2.50g/L, 3.00g/L, 3.50g/L, 4.00g/L, 4.50g/L, 5.00g/L, 5.50g/L, 6.00g/L, 6.50g/L, 7.00g/L, 7.50g/L and the like, and more preferably 1.50-5.00 g/L.
In the technical scheme, the content of the promoter element in the hydrogenation catalyst is preferably 0.50-10.00 g/L, such as but not limited to 0.70g/L, 0.80g/L, 1.00g/L, 1.50g/L, 2.00g/L, 2.50g/L, 3.00g/L, 3.50g/L, 4.00g/L, 4.50g/L, 5.00g/L, 5.50g/L, 6.00g/L, 6.50g/L, 7.00g/L, 7.50g/L, 8.00g/L, 8.50g/L, 9.00g/L, 9.50g/L and the like; more preferably 1.00 to 6.00 g/L.
In the above technical solution, the vector is preferably obtained by a method comprising the following steps:
(1) preparing the compound containing phosphorus into an aqueous solution to impregnate Al2O3Drying to obtain the carrier precursor I;
(2) and roasting the carrier precursor I in a reducing and/or inert atmosphere to obtain the modified carrier.
In the above technical solution, the phosphorus-containing compound is preferably selected from phosphoric acid and ammonium phosphate ((NH)4)3PO4) Diammonium hydrogen phosphate ((NH)4)2HPO4And phosphorus pentoxide. Wherein the phosphoric acid is preferably at least one selected from hypophosphorous acid, phosphorous acid, orthophosphoric acid, pyrophosphoric acid and polyphosphoric acid, and preferably at least one selected from orthophosphoric acid, pyrophosphoric acid and polyphosphoric acid.
In the technical scheme, the drying temperature in the step (1) is preferably 100-120 ℃, such as but not limited to 105 ℃, 110 ℃ and 115 ℃; the drying time in step (1) is preferably 3 to 10 hours, such as but not limited to 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours and the like.
In the above technical solution, the gas in the step (2) is not particularly required, the inert atmosphere may be an inert gas (at least one of helium, neon and argon) of group 0 of the periodic table of elements and/or nitrogen, and the reducing gas may be hydrogen.
In the above technical scheme, the baking temperature in the step (2) is preferably 500-700 ℃, for example, but not limited to 550 ℃, 600 ℃, 650 ℃, and the like. The time for calcination is preferably 3 to 10 hours, such as but not limited to 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, and the like.
In the above technical scheme, the hydrogenation catalyst can be prepared by a method comprising the following steps:
(i) mixing a solution containing cobalt element and promoter element with a carrier according to the composition of the catalyst to obtain a catalyst precursor;
(ii) drying to obtain the catalyst.
In the above-mentioned technical solution, as a non-limiting example, the specific compound corresponding to the cobalt element in the step (i) is preferably at least one selected from cobalt acetate, cobalt ammonium sulfate, cobalt chloride, cobalt nitrate, cobalt oxalate, cobalt sulfate, cobalt carbonate and cobalt phosphate; more preferably cobalt ammonium sulfate.
In the above-mentioned technical solution, as a non-limiting example, when the promoter element in the step (i) includes an alkaline earth metal element, a specific compound corresponding to the alkaline earth metal element is preferably at least one selected from the group consisting of an alkaline earth metal oxide, an alkaline earth metal hydroxide, an alkaline earth metal chloride, an alkaline earth metal sulfate, an alkaline earth metal nitrate and an alkaline earth metal acetate; more preferably at least one of an alkaline earth metal acetate; most preferably at least one selected from calcium acetate and barium acetate.
In the above technical solution, as a non-limiting example, when the promoter element in step (i) includes a group IB metal element, the specific compound corresponding to the group IB metal element is preferably at least one selected from copper citrate, copper acetate, copper nitrate, copper chloride, copper sulfate, silver acetate, silver nitrate, silver lactate, silver tetrafluoroborate, chloroauric acid, gold oxide, and ammonium tetrachloroaurate; more preferably at least one selected from copper acetate and ammonium tetrachloroaurate.
In the above technical scheme, the drying temperature in step (ii) is preferably 30 to 120 ℃, for example, but not limited to, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, more preferably 80 to 120 ℃; the drying time in step (ii) is preferably 1 to 5 hours, such as but not limited to 1.5 hours, 2.0 hours, 2.5 hours, 3.0 hours, 3.5 hours, 4.0 hours, 4.5 hours, and the like.
Aniline is commercially available or can be synthesized by ammoxidation of benzene. In the method for synthesizing cyclohexylamine according to the present invention, it is well known to those skilled in the art to select a suitable catalyst for the ammoxidation reaction of benzene and to determine a suitable reaction temperature, time and material ratio. For example, but not limited to, the active component of the catalyst is mainly Ni or Cu, and Ti, Cr and the like are added as auxiliary components. The carrier used can be activated carbon, alumina gel, silica gel or molecular sieve.
Ni-Ti/SiO is preferred in the present invention2Is a catalyst for direct ammoniation and oxidation reaction of benzene by one-step method. Suitable Ni-Ti/SiO2The content of the nickel element in the catalyst is preferably 2.50-5.00 g/L, and more preferably 3.00-4.50 g/L; the content of titanium element is preferably 0.50 to 3.00g/L, more preferably 1.00 to 2.00 g/L. The temperature of the appropriate ammoniation oxidation reaction is preferably 80-350 ℃; the pressure of the ammoniation oxidation reaction is preferably 8.0-50.0 MPa; the time of the ammoniation oxidation reaction is preferably 0.5-5 h; the molar ratio of benzene to hydroxylamine hydrochloride is preferably 0.5 to 3.0. After the benzene amination and oxidation reaction is finished, the mixture of the benzene amination and oxidation reaction can be separated to obtain the target product aniline, and then catalytic hydrogenation is carried out, or the aniline is generated by benzene amination and oxidation and then catalytic hydrogenation is directly carried out without separation. However, in order to eliminate other impurities to cause the system to be complicated and convenient for comparison, the specific embodiment of the invention adopts pure aniline for catalytic hydrogenation.
The product mixture of the hydrogenation reaction can be separated to obtain the target product cyclohexylamine.
The product after hydrogenation reaction is analyzed by a gas chromatography-MASS spectrometer (GC-MASS), and the yield and selectivity of cyclohexylamine are calculated according to the following formula:
Figure BDA0001429443460000051
Figure BDA0001429443460000052
compared with the prior art, the method improves the yield and the selectivity of the cyclohexylamine.
Experimental results show that when the method is adopted, the yield of the cyclohexylamine reaches 81.55%, the selectivity reaches 91.50%, and a better technical effect is achieved. Particularly, when the hydrogenation catalyst carrier is modified by phosphorus, and the active component of the hydrogenation catalyst simultaneously comprises cobalt, at least one metal element selected from alkaline earth metals and at least one metal element selected from IB group metals, more outstanding technical effects are achieved. The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
Modified support P/Al2O3The preparation of (1):
(1) phosphoric acid (H) containing 1.50g P3PO4) 180ml of the aqueous solution (A) was immersed in 1L of a solution having a diameter of 6mm and a pore volume of 0.92cm3A specific surface area of 200 cm/g2Al in g2O3Then, the mixture is kept still for 24 hours and dried for 4 hours at 110 ℃ to obtain the carrier precursor I.
(2) Roasting the carrier precursor I for 5h at 630 ℃ in the atmosphere of nitrogen gas to obtain the modified carrier P/Al2O3。
The P content in the carrier was 1.50g/L as determined by ICP.
Preparation of hydrogenation catalyst:
(i) cobalt ammonium sulfate ((NH) containing 2.28g of Co4)2Co(SO4)2·6H2O) and calcium acetate (Ca (OAc) containing 1.66g of Ca2·H2O) 200ml of an aqueous solution was immersed in P/Al2O3Obtaining a catalyst precursor I;
(ii) drying at 110 ℃ for 4 hours to obtain the catalyst.
The catalyst had a Co content of 2.28g/L and a Ca content of 1.66g/L as determined by ICP.
Synthesis of cyclohexylamine:
35ml of catalyst is filled in a micro reactor, nitrogen leakage test is adopted, after no leakage point of the system is ensured, aniline enters a vaporizer through a metering pump to be vaporized, the vaporization temperature of the vaporizer is controlled to be 190 ℃, hydrogen enters the vaporizer along the direction vertical to the flow direction of the aniline, and the aniline and the hydrogen are mixed through the vaporizer to obtain feed gas, wherein the hydrogen/aniline in the feed gas is 31.0/1.0 (molar ratio). Then, the feed gas is used for 2400h-1The reaction temperature is 186 ℃, and the reaction pressure (gauge pressure) is 0.29 MPa. And the reacted mixed gas enters a condenser from the bottom of the reactor for condensation, and the product is analyzed.
The yield of cyclohexylamine was analytically calculated to be 81.55% and the selectivity 91.50%, and for convenience of illustration and comparison, the support modification of the hydrogenation catalyst, the preparation of the hydrogenation catalyst, the reaction conditions, the feed amount, the cyclohexylamine yield and selectivity are shown in tables 1 and 2, respectively.
[ example 2 ]
Modified support P/Al2O3The preparation of (1):
(1) phosphoric acid (H) containing 1.50g P3PO4) 180ml of the aqueous solution (A) was immersed in 1L of a solution having a diameter of 6mm and a pore volume of 0.92cm3A specific surface area of 200 cm/g2Al in g2O3Then, the mixture is kept still for 24 hours and dried for 4 hours at 110 ℃ to obtain the carrier precursor I.
(2) Roasting the carrier precursor I for 5h at 630 ℃ in the atmosphere of nitrogen gas to obtain the modified carrier P/Al2O3。
The P content in the carrier was 1.50g/L as determined by ICP.
Preparation of hydrogenation catalyst:
(i) cobalt ammonium sulfate ((NH) containing 2.28g of Co4)2Co(SO4)2·6H2O) and ammonium tetrachloroaurate containing 1.66g of Au ((NH)4)AuCl4·3H2O) 200ml of an aqueous solution was immersed in P/Al2O3Obtaining a catalyst precursor I;
(ii) drying at 110 ℃ for 4 hours to obtain the catalyst.
The catalyst had a Co content of 2.28g/L and an Au content of 1.66g/L as determined by ICP.
Synthesis of cyclohexylamine:
35ml of catalyst is filled in a micro reactor, nitrogen leakage test is adopted, after no leakage point of the system is ensured, aniline enters a vaporizer through a metering pump to be vaporized, the vaporization temperature of the vaporizer is controlled to be 190 ℃, hydrogen enters the vaporizer along the direction vertical to the flow direction of the aniline, and the aniline and the hydrogen are mixed through the vaporizer to obtain feed gas, wherein the hydrogen/aniline in the feed gas is 31.0/1.0 (molar ratio). Then, the feed gas is used for 2400h-1The reaction temperature is 186 ℃, and the reaction pressure (gauge pressure) is 0.29 MPa. And the reacted mixed gas enters a condenser from the bottom of the reactor for condensation, and the product is analyzed.
The yield of cyclohexylamine was analytically calculated to be 81.42% and the selectivity 91.71%, and for ease of illustration and comparison, the support modification of the hydrogenation catalyst, the preparation of the hydrogenation catalyst, the reaction conditions, the feed rates, the cyclohexylamine yield and selectivity are shown in tables 1 and 2, respectively.
[ COMPARATIVE EXAMPLE 1 ]
Are comparative examples of [ example 1 ] and [ example 2 ].
Preparation of hydrogenation catalyst:
(i) cobalt ammonium sulfate ((NH) containing 2.28g of Co4)2Co(SO4)2·6H2O) 200ml of aqueous solution, 1L of which has a diameter of 6mm and a pore volume of 0.92cm3A specific surface area of 200 cm/g2Al in g2O3To obtain a catalyst precursor I;
(ii) drying at 110 ℃ for 4 hours to obtain the catalyst.
The Co content of the catalyst was determined by ICP to be 2.28 g/L.
Synthesis of cyclohexylamine:
filling 35ml of catalyst into a micro-reactor, adopting nitrogen leakage test to ensure that no leakage point exists in the system, introducing aniline into a vaporizer through a metering pump to vaporize, controlling the vaporization temperature of the vaporizer to be 190 ℃, and mixing hydrogen with the vaporAniline flows in a vertical direction into a vaporizer, and the aniline enters the vaporizer to be mixed to obtain a feed gas, wherein the molar ratio of hydrogen to aniline in the feed gas is 31.0/1.0. Then, the feed gas is used for 2400h-1The reaction temperature is 186 ℃, and the reaction pressure (gauge pressure) is 0.29 MPa. And the reacted mixed gas enters a condenser from the bottom of the reactor for condensation, and the product is analyzed.
The yield of cyclohexylamine was analytically calculated to be 70.03% and the selectivity 83.24%, and for convenience of illustration and comparison, the support modification of the hydrogenation catalyst, the preparation of the hydrogenation catalyst, the reaction conditions, the feed amount, the cyclohexylamine yield and selectivity are shown in tables 1 and 2, respectively.
Compared with the examples 1-2, the catalyst which adopts the phosphorus-containing compound to modify the carrier and hydrogenate has the active components containing Co and Ca simultaneously and the active components containing Co and Au simultaneously, has better performance than the catalyst containing Co only, and shows that the active components of the hydrogenation catalyst simultaneously contain at least one metal element containing Co and selected from alkaline earth metals and IB group metals, thereby being beneficial to improving the activity and stability of the hydrogenation catalyst and having high yield and selectivity of cyclohexylamine.
[ COMPARATIVE EXAMPLE 2 ]
Comparative example [ comparative example 1 ].
Modified support P/Al2O3The preparation of (1):
(1) phosphoric acid (H) containing 1.50g P3PO4) 180ml of the aqueous solution (A) was immersed in 1L of a solution having a diameter of 6mm and a pore volume of 0.92cm3A specific surface area of 200 cm/g2Al in g2O3Then, the mixture is kept still for 24 hours and dried for 4 hours at 110 ℃ to obtain the carrier precursor I.
(2) Roasting the carrier precursor I for 5h at 630 ℃ in the atmosphere of nitrogen gas to obtain the modified carrier P/Al2O3。
The P content in the carrier was 1.50g/L as determined by ICP.
Preparation of hydrogenation catalyst:
(i) cobalt ammonium sulfate ((NH) containing 2.28g of Co4)2Co(SO4)2·6H2O) 200ml of an aqueous solution, immersed in P/Al2O3Obtaining a catalyst precursor I;
(ii) drying at 110 ℃ for 4 hours to obtain the catalyst.
The Co content of the catalyst was determined by ICP to be 2.28 g/L.
Synthesis of cyclohexylamine:
35ml of catalyst is filled in a micro reactor, nitrogen leakage test is adopted, after no leakage point of the system is ensured, aniline enters a vaporizer through a metering pump to be vaporized, the vaporization temperature of the vaporizer is controlled to be 190 ℃, hydrogen enters the vaporizer along the direction vertical to the flow direction of the aniline, and the aniline and the hydrogen are mixed through the vaporizer to obtain feed gas, wherein the hydrogen/aniline in the feed gas is 31.0/1.0 (molar ratio). Then, the feed gas is used for 2400h-1The reaction temperature is 186 ℃, and the reaction pressure (gauge pressure) is 0.29 MPa. And the reacted mixed gas enters a condenser from the bottom of the reactor for condensation, and the product is analyzed.
The yield of cyclohexylamine was analytically calculated to be 72.71% and the selectivity 85.15%, and for convenience of illustration and comparison, the support modification of the hydrogenation catalyst, the preparation of the hydrogenation catalyst, the reaction conditions, the feed amount, the yield of cyclohexylamine and the selectivity are shown in tables 1 and 2, respectively.
As can be seen from comparison with comparative example 1, the present invention employs phosphorus-modified Al2O3The prepared hydrogenation catalyst is more than that of directly using Al2O3The performance of the prepared hydrogenation catalyst is better, which indicates that P/Al is used2O3Is beneficial to the catalytic hydrogenation of aniline, and has high yield and selectivity of cyclohexylamine.
[ example 3 ]
Modified support P/Al2O3The preparation of (1):
(1) ammonium phosphate (NH) containing 0.80g P4)3PO4) 180ml of the aqueous solution (A) was immersed in 1L of a solution having a diameter of 6mm and a pore volume of 0.92cm3A specific surface area of 200 cm/g2Al in g2O3Standing for 24h, and drying at 110 ℃ for 4h to obtain theA support precursor I.
(2) Roasting the carrier precursor I for 5h at 630 ℃ in the atmosphere of nitrogen gas to obtain the modified carrier P/Al2O3。
The P content in the carrier was determined to be 0.80g/L by ICP.
Preparation of hydrogenation catalyst:
(i) cobalt ammonium sulfate ((NH) containing 2.28g of Co4)2Co(SO4)2·6H2O) and beryllium acetate containing 1.66g of Be (OAc)2·H2O) was dissolved in hot water to obtain 200ml of an immersion liquid and was immersed in P/Al2O3Obtaining a catalyst precursor I;
(ii) drying at 110 ℃ for 4 hours to obtain the catalyst.
The catalyst had a Co content of 2.28g/L and a Be content of 1.66g/L as determined by ICP.
Synthesis of cyclohexylamine:
35ml of catalyst is filled in a micro reactor, nitrogen leakage test is adopted, after no leakage point of the system is ensured, aniline enters a vaporizer through a metering pump to be vaporized, the vaporization temperature of the vaporizer is controlled to be 190 ℃, hydrogen enters the vaporizer along the direction vertical to the flow direction of the aniline, and the aniline and the hydrogen are mixed through the vaporizer to obtain feed gas, wherein the hydrogen/aniline in the feed gas is 31.0/1.0 (molar ratio). Then, the feed gas is used for 2400h-1The reaction temperature is 186 ℃, and the reaction pressure (gauge pressure) is 0.29 MPa. And the reacted mixed gas enters a condenser from the bottom of the reactor for condensation, and the product is analyzed.
The yield of cyclohexylamine was analytically calculated to be 81.52% and the selectivity 91.48%, and for convenience of illustration and comparison, the support modification of the hydrogenation catalyst, the preparation of the hydrogenation catalyst, the reaction conditions, the feed amount, the cyclohexylamine yield and selectivity are shown in tables 1 and 2, respectively.
[ example 4 ]
Modified support P/Al2O3The preparation of (1):
(1) diammonium hydrogen phosphate ((NH) containing 2.00g P4)2HPO4) 180ml of the aqueous solution (A) was immersed in 1L of a solution having a diameter of 6mm and a pore volume of 0.92cm3A specific surface area of 200 cm/g2Al in g2O3Then, the mixture is kept still for 24 hours and dried for 4 hours at 110 ℃ to obtain the carrier precursor I.
(2) Roasting the carrier precursor I for 5h at 630 ℃ in the atmosphere of nitrogen gas to obtain the modified carrier P/Al2O3。
The P content in the carrier was 2.00g/L as determined by ICP.
Preparation of hydrogenation catalyst:
(i) cobalt ammonium sulfate ((NH) containing 2.28g of Co4)2Co(SO4)2·6H2O) and magnesium acetate (Mg (OAc) containing 1.66g Mg2·4H2O) 200ml of an aqueous solution was immersed in P/Al2O3Obtaining a catalyst precursor I;
(ii) drying at 110 ℃ for 4 hours to obtain the catalyst.
The catalyst had a Co content of 2.28g/L and a Mg content of 1.66g/L as determined by ICP.
Synthesis of cyclohexylamine:
35ml of catalyst is filled in a micro reactor, nitrogen leakage test is adopted, after no leakage point of the system is ensured, aniline enters a vaporizer through a metering pump to be vaporized, the vaporization temperature of the vaporizer is controlled to be 190 ℃, hydrogen enters the vaporizer along the direction vertical to the flow direction of the aniline, and the aniline and the hydrogen are mixed through the vaporizer to obtain feed gas, wherein the hydrogen/aniline in the feed gas is 31.0/1.0 (molar ratio). Then, the feed gas is used for 2400h-1The reaction temperature is 186 ℃, and the reaction pressure (gauge pressure) is 0.29 MPa. And the reacted mixed gas enters a condenser from the bottom of the reactor for condensation, and the product is analyzed.
The yield of cyclohexylamine was analytically calculated to be 81.52% and the selectivity 91.51%, and for convenience of illustration and comparison, the support modification of the hydrogenation catalyst, the preparation of the hydrogenation catalyst, the reaction conditions, the feed amount, the cyclohexylamine yield and selectivity are shown in tables 1 and 2, respectively.
[ example 5 ]
Modified support P/Al2O3The preparation of (1):
(1) phosphoric acid containing 1.50g P(H3PO4) 180ml of the aqueous solution (A) was immersed in 1L of a solution having a diameter of 6mm and a pore volume of 0.92cm3A specific surface area of 200 cm/g2Al in g2O3Then, the mixture is kept still for 24 hours and dried for 4 hours at 110 ℃ to obtain the carrier precursor I.
(2) Roasting the carrier precursor I for 5h at 630 ℃ in the atmosphere of nitrogen gas to obtain the modified carrier P/Al2O3。
The P content in the carrier was 1.50g/L as determined by ICP.
Preparation of hydrogenation catalyst:
(i) cobalt ammonium sulfate ((NH) containing 2.28g of Co4)2Co(SO4)2·6H2O) and barium acetate containing 1.66g of Ba (OAc)2·H2O) 200ml of an aqueous solution was immersed in P/Al2O3Obtaining a catalyst precursor I;
(ii) drying at 110 ℃ for 4 hours to obtain the catalyst.
The catalyst had a Co content of 2.28g/L and a Ba content of 1.66g/L as determined by ICP.
Synthesis of cyclohexylamine:
35ml of catalyst is filled in a micro reactor, nitrogen leakage test is adopted, after no leakage point of the system is ensured, aniline enters a vaporizer through a metering pump to be vaporized, the vaporization temperature of the vaporizer is controlled to be 190 ℃, hydrogen enters the vaporizer along the direction vertical to the flow direction of the aniline, and the aniline and the hydrogen are mixed through the vaporizer to obtain feed gas, wherein the hydrogen/aniline in the feed gas is 31.0/1.0 (molar ratio). Then, the feed gas is used for 2400h-1The reaction temperature is 186 ℃, and the reaction pressure (gauge pressure) is 0.29 MPa. And the reacted mixed gas enters a condenser from the bottom of the reactor for condensation, and the product is analyzed.
The yield of cyclohexylamine was analytically calculated to be 81.55% and the selectivity 91.57%, and for convenience of illustration and comparison, the support modification of the hydrogenation catalyst, the preparation of the hydrogenation catalyst, the reaction conditions, the feed amount, the cyclohexylamine yield and selectivity are shown in tables 1 and 2, respectively.
[ example 6 ]
Modified support P/Al2O3The preparation of (1):
(1) phosphoric acid (H) containing 1.50g P3PO4) 180ml of the aqueous solution (A) was immersed in 1L of a solution having a diameter of 6mm and a pore volume of 0.92cm3A specific surface area of 200 cm/g2Al in g2O3Then, the mixture is kept still for 24 hours and dried for 4 hours at 110 ℃ to obtain the carrier precursor I.
(2) Roasting the carrier precursor I for 5h at 630 ℃ in the atmosphere of nitrogen gas to obtain the modified carrier P/Al2O3。
The P content in the carrier was 1.50g/L as determined by ICP.
Preparation of hydrogenation catalyst:
(i) cobalt ammonium sulfate ((NH) containing 2.28g of Co4)2Co(SO4)2·6H2O) and strontium acetate (Sr (OAc) containing 1.66g of Sr2·0.5H2O) 200ml of an aqueous solution was immersed in P/Al2O3Obtaining a catalyst precursor I;
(ii) drying at 110 ℃ for 4 hours to obtain the catalyst.
The catalyst had a Co content of 2.28g/L and a Sr content of 1.66g/L as determined by ICP.
Synthesis of cyclohexylamine:
35ml of catalyst is filled in a micro reactor, nitrogen leakage test is adopted, after no leakage point of the system is ensured, aniline enters a vaporizer through a metering pump to be vaporized, the vaporization temperature of the vaporizer is controlled to be 190 ℃, hydrogen enters the vaporizer along the direction vertical to the flow direction of the aniline, and the aniline and the hydrogen are mixed through the vaporizer to obtain feed gas, wherein the hydrogen/aniline in the feed gas is 31.0/1.0 (molar ratio). Then, the feed gas is used for 2400h-1The reaction temperature is 186 ℃, and the reaction pressure (gauge pressure) is 0.29 MPa. And the reacted mixed gas enters a condenser from the bottom of the reactor for condensation, and the product is analyzed.
The yield of cyclohexylamine was analytically calculated to be 81.50% and the selectivity 91.47%, and for convenience of illustration and comparison, the support modification of the hydrogenation catalyst, the preparation of the hydrogenation catalyst, the reaction conditions, the feed amount, the cyclohexylamine yield and selectivity are shown in tables 1 and 2, respectively.
[ example 7 ]
Modified support P/Al2O3The preparation of (1):
(1) phosphoric acid (H) containing 1.5g P3PO4) 180ml of the aqueous solution (A) was immersed in 1L of a solution having a diameter of 6mm and a pore volume of 0.92cm3A specific surface area of 200 cm/g2Al in g2O3Then, the mixture is kept still for 24 hours and dried for 4 hours at 110 ℃ to obtain the carrier precursor I.
(2) Roasting the carrier precursor I for 5h at 630 ℃ in the atmosphere of nitrogen gas to obtain the modified carrier P/Al2O3。
The P content in the carrier was 1.5g/L as determined by ICP.
Preparation of hydrogenation catalyst:
(i) cobalt ammonium sulfate ((NH) containing 2.28g of Co4)2Co(SO4)2·6H2O) and copper acetate containing 1.66g of Cu (OAc)2·H2O) aqueous solution 200ml was immersed in P/Al2O3Obtaining a catalyst precursor I;
(ii) drying at 110 ℃ for 4 hours to obtain the catalyst.
The catalyst had a Co content of 2.28g/L and a Cu content of 1.66g/L as determined by ICP.
Synthesis of cyclohexylamine:
35ml of catalyst is filled in a micro reactor, nitrogen leakage test is adopted, after no leakage point of the system is ensured, aniline enters a vaporizer through a metering pump to be vaporized, the vaporization temperature of the vaporizer is controlled to be 190 ℃, hydrogen enters the vaporizer along the direction vertical to the flow direction of the aniline, and the aniline and the hydrogen are mixed through the vaporizer to obtain feed gas, wherein the hydrogen/aniline in the feed gas is 31.0/1.0 (molar ratio). Then, the feed gas is used for 2400h-1The reaction temperature is 186 ℃, and the reaction pressure (gauge pressure) is 0.29 MPa. And the reacted mixed gas enters a condenser from the bottom of the reactor for condensation, and the product is analyzed.
The yield of cyclohexylamine was analytically calculated to be 81.44% and the selectivity 91.69%, and for convenience of illustration and comparison, the support modification of the hydrogenation catalyst, the preparation of the hydrogenation catalyst, the reaction conditions, the feed amount, the cyclohexylamine yield and selectivity are shown in tables 1 and 2, respectively.
[ example 8 ]
Modified support P/Al2O3The preparation of (1):
(1) phosphoric acid (H) containing 1.50g P3PO4) 180ml of the aqueous solution (A) was immersed in 1L of a solution having a diameter of 6mm and a pore volume of 0.92cm3A specific surface area of 200 cm/g2Al in g2O3Then, the mixture is kept still for 24 hours and dried for 4 hours at 110 ℃ to obtain the carrier precursor I.
(2) Roasting the carrier precursor I for 5h at 630 ℃ in the atmosphere of nitrogen gas to obtain the modified carrier P/Al2O3。
The P content in the carrier was 1.50g/L as determined by ICP.
Preparation of hydrogenation catalyst:
(i) cobalt ammonium sulfate ((NH) containing 1.50g of Co4)2Co(SO4)2·6H2O) and silver nitrate (AgNO) containing 1.00g Ag3) 200ml of the aqueous solution of (1) was immersed in P/Al2O3Obtaining a catalyst precursor I;
(ii) drying at 110 ℃ for 4 hours to obtain the catalyst.
The catalyst had a Co content of 1.50g/L and an Ag content of 1.00g/L as determined by ICP.
Synthesis of cyclohexylamine:
35ml of catalyst is filled in a micro reactor, nitrogen leakage test is adopted, after no leakage point of the system is ensured, aniline enters a vaporizer through a metering pump to be vaporized, the vaporization temperature of the vaporizer is controlled to be 190 ℃, hydrogen enters the vaporizer along the direction vertical to the flow direction of the aniline, and the aniline and the hydrogen are mixed through the vaporizer to obtain feed gas, wherein the hydrogen/aniline in the feed gas is 31.0/1.0 (molar ratio). Then, the feed gas is used for 2400h-1The reaction temperature is 185 ℃ and the reaction pressure (gauge pressure) is 0.29 MPa. And the reacted mixed gas enters a condenser from the bottom of the reactor for condensation, and the product is analyzed.
The yield of cyclohexylamine was analytically calculated to be 79.96% and the selectivity 90.87%, and for convenience of illustration and comparison, the support modification of the hydrogenation catalyst, the preparation of the hydrogenation catalyst, the reaction conditions, the feed amount, the cyclohexylamine yield and selectivity are shown in tables 1 and 2, respectively.
[ example 9 ]
Modified support P/Al2O3The preparation of (1):
(1) phosphoric acid (H) containing 1.50g P3PO4) 180ml of the aqueous solution (A) was immersed in 1L of a solution having a diameter of 6mm and a pore volume of 0.92cm3A specific surface area of 200 cm/g2Al in g2O3Then, the mixture is kept still for 24 hours and dried for 4 hours at 110 ℃ to obtain the carrier precursor I.
(2) Roasting the carrier precursor I for 5h at 630 ℃ in the atmosphere of nitrogen gas to obtain the modified carrier P/Al2O3。
The P content in the carrier was 1.50g/L as determined by ICP.
Preparation of hydrogenation catalyst:
(i) cobalt ammonium sulfate ((NH) containing 5.00g of Co4)2Co(SO4)2·6H2O) and copper nitrate (Cu (NO) containing 6.00g of Cu3)2·2H2O) 200ml of an aqueous solution was immersed in P/Al2O3Obtaining a catalyst precursor I;
(ii) drying at 110 ℃ for 4 hours to obtain the catalyst.
The catalyst had a Co content of 3.00g/L and a Cu content of 6.00g/L as determined by ICP.
Synthesis of cyclohexylamine:
35ml of catalyst is filled in a micro reactor, nitrogen leakage test is adopted, after no leakage point of the system is ensured, aniline enters a vaporizer through a metering pump to be vaporized, the vaporization temperature of the vaporizer is controlled to be 190 ℃, hydrogen enters the vaporizer along the direction vertical to the flow direction of the aniline, and the aniline and the hydrogen are mixed through the vaporizer to obtain feed gas, wherein the hydrogen/aniline in the feed gas is 31.0/1.0 (molar ratio). Then, the feed gas is used for 2400h-1The reaction temperature is 220 ℃, and the reaction pressure (gauge pressure) is 0.29 MPa. And the reacted mixed gas enters a condenser from the bottom of the reactor for condensation, and the product is analyzed.
The yield of cyclohexylamine was analytically calculated to be 81.14% and the selectivity 90.21%, and for convenience of illustration and comparison, the support modification of the hydrogenation catalyst, the preparation of the hydrogenation catalyst, the reaction conditions, the feed amount, the cyclohexylamine yield and selectivity are shown in tables 1 and 2, respectively.
[ example 10 ]
Modified support P/Al2O3The preparation of (1):
(1) phosphoric acid (H) containing 1.50g P3PO4) 180ml of the aqueous solution (A) was immersed in 1L of a solution having a diameter of 6mm and a pore volume of 0.92cm3A specific surface area of 200 cm/g2Al in g2O3Then, the mixture is kept still for 24 hours and dried for 4 hours at 110 ℃ to obtain the carrier precursor I.
(2) Roasting the carrier precursor I for 5h at 630 ℃ in the atmosphere of nitrogen gas to obtain the modified carrier P/Al2O3。
The P content in the carrier was 1.50g/L as determined by ICP.
Preparation of hydrogenation catalyst:
(i) cobalt ammonium sulfate ((NH) containing 2.28g of Co, 0.84g of Au and 0.82g of Cu4)2Co(SO4)2·6H2O), ammonium tetrachloroaurate ((NH)4)AuCl4·3H2O) and copper acetate (Cu (OAc)2·H2O) 200ml of an aqueous solution was immersed in P/Al2O3Obtaining a catalyst precursor I;
(ii) drying at 110 ℃ for 4 hours to obtain the catalyst.
The catalyst had a Co content of 2.28g/L, an Au content of 0.84g/L and a Cu content of 0.82g/L as determined by ICP.
Synthesis of cyclohexylamine:
35ml of catalyst is filled in a micro reactor, nitrogen leakage test is adopted, after no leakage point of the system is ensured, aniline enters a vaporizer through a metering pump to be vaporized, the vaporization temperature of the vaporizer is controlled to be 190 ℃, hydrogen enters the vaporizer along the direction vertical to the flow direction of the aniline, and the aniline and the hydrogen are mixed through the vaporizer to obtain feed gas, wherein the hydrogen/aniline in the feed gas is 31.0/1.0 (molar ratio). Then, the feed gas is used for 2400h-1The reaction temperature is 186 ℃ after the volume space velocity of the reaction mixture enters the reactorThe reaction pressure (gauge pressure) was 0.29 MPa. And the reacted mixed gas enters a condenser from the bottom of the reactor for condensation, and the product is analyzed.
The yield of cyclohexylamine was analytically calculated to be 82.17% and the selectivity 92.25%, and for ease of illustration and comparison, the support modification of the hydrogenation catalyst, the preparation of the hydrogenation catalyst, the reaction conditions, the feed rates, the cyclohexylamine yield and selectivity are shown in tables 1 and 2, respectively.
From the comparison between example 10 and examples 2 and 7, it can be seen that in the hydrogenation catalyst used in the present invention, the metal element Au and the metal element Cu in the IB group metal have a better synergistic effect in increasing the yield and selectivity of cyclohexylamine.
[ example 11 ]
Modified support P/Al2O3The preparation of (1):
(1) phosphoric acid (H) containing 1.50g P3PO4) 180ml of the aqueous solution (A) was immersed in 1L of a solution having a diameter of 6mm and a pore volume of 0.92cm3A specific surface area of 200 cm/g2Al in g2O3Then, the mixture is kept still for 24 hours and dried for 4 hours at 110 ℃ to obtain the carrier precursor I.
(2) Roasting the carrier precursor I for 5h at 630 ℃ in the atmosphere of nitrogen gas to obtain the modified carrier P/Al2O3。
The P content in the carrier was 1.50g/L as determined by ICP.
Preparation of hydrogenation catalyst:
(i) cobalt ammonium sulfate ((NH) containing 2.28g of Co, 0.89g of Ca and 0.77g of Ba4)2Co(SO4)2·6H2O), calcium acetate (Ca (OAc)2·H2O) and barium acetate (Ba (OAc)2·H2O) 200ml of an aqueous solution was immersed in P/Al2O3Obtaining a catalyst precursor I;
(ii) drying at 110 ℃ for 4 hours to obtain the catalyst.
The catalyst has a Co content of 2.28g/L, a Ca content of 0.89g/L and a Ba content of 0.77g/L determined by ICP.
Synthesis of cyclohexylamine:
35ml of catalyst is filled in a micro reactor, nitrogen leakage test is adopted, after no leakage point of the system is ensured, aniline enters a vaporizer through a metering pump to be vaporized, the vaporization temperature of the vaporizer is controlled to be 190 ℃, hydrogen enters the vaporizer along the direction vertical to the flow direction of the aniline, and the aniline and the hydrogen are mixed through the vaporizer to obtain feed gas, wherein the hydrogen/aniline in the feed gas is 31.0/1.0 (molar ratio). Then, the feed gas is used for 2400h-1The reaction temperature is 186 ℃, and the reaction pressure (gauge pressure) is 0.29 MPa. And the reacted mixed gas enters a condenser from the bottom of the reactor for condensation, and the product is analyzed.
The yield of cyclohexylamine was analytically calculated to be 82.34% and the selectivity 92.11%, and for convenience of illustration and comparison, the support modification of the hydrogenation catalyst, the preparation of the hydrogenation catalyst, the reaction conditions, the feed amount, the cyclohexylamine yield and selectivity are shown in tables 1 and 2, respectively.
From the comparison between example 11 and examples 1 and 5, it can be seen that in the hydrogenation catalyst used in the present invention, the metal element Ca and the metal element Ba in the alkaline earth metal have a better synergistic effect in increasing the yield and selectivity of cyclohexylamine.
[ example 12 ]
Modified support P/Al2O3The preparation of (1):
(1) phosphoric acid (H) containing 1.50g P3PO4) 180ml of the aqueous solution (A) was immersed in 1L of a solution having a diameter of 6mm and a pore volume of 0.92cm3A specific surface area of 200 cm/g2Al in g2O3Then, the mixture is kept still for 24 hours and dried for 4 hours at 110 ℃ to obtain the carrier precursor I.
(2) Roasting the carrier precursor I for 5h at 630 ℃ in the atmosphere of nitrogen gas to obtain the modified carrier P/Al2O3。
The P content in the carrier was 1.50g/L as determined by ICP.
Preparation of hydrogenation catalyst:
(i) cobalt ammonium sulfate ((NH) containing 2.28g of Co, 0.82g of Ca and 0.84g of Au4)2Co(SO4)2·6H2O), calcium acetate (Ca (OAc)2·H2O) and tetrachloroAmmonium aurate ((NH)4)AuCl4·3H2O) 200ml of an aqueous solution was immersed in P/Al2O3Obtaining a catalyst precursor I;
(ii) drying at 110 ℃ for 4 hours to obtain the catalyst.
The catalyst had a Co content of 2.28g/L, a Ca content of 0.82g/L and an Au content of 0.84g/L as determined by ICP.
Synthesis of cyclohexylamine:
35ml of catalyst is filled in a micro reactor, nitrogen leakage test is adopted, after no leakage point of the system is ensured, aniline enters a vaporizer through a metering pump to be vaporized, the vaporization temperature of the vaporizer is controlled to be 190 ℃, hydrogen enters the vaporizer along the direction vertical to the flow direction of the aniline, and the aniline and the hydrogen are mixed through the vaporizer to obtain feed gas, wherein the hydrogen/aniline in the feed gas is 31.0/1.0 (molar ratio). Then, the feed gas is used for 2400h-1The reaction temperature is 186 ℃, and the reaction pressure (gauge pressure) is 0.29 MPa. And the reacted mixed gas enters a condenser from the bottom of the reactor for condensation, and the product is analyzed.
The yield of cyclohexylamine was analytically calculated to be 83.05% and the selectivity 92.69%, and for convenience of illustration and comparison, the support modification of the hydrogenation catalyst, the preparation of the hydrogenation catalyst, the reaction conditions, the feed amount, the yield of cyclohexylamine and the selectivity are shown in tables 1 and 2, respectively.
From the comparison between example 12 and examples 1 and 2, it can be seen that in the hydrogenation catalyst used in the present invention, the metal element Au in the IB group metal and the metal element Ca in the alkaline earth metal have better synergistic effect in increasing the yield and selectivity of cyclohexylamine.
[ example 13 ]
Modified support P/Al2O3The preparation of (1):
(1) phosphoric acid (H) containing 1.50g P3PO4) 180ml of the aqueous solution (A) was immersed in 1L of a solution having a diameter of 6mm and a pore volume of 0.92cm3A specific surface area of 200 cm/g2Al in g2O3Then, the mixture is kept still for 24 hours and dried for 4 hours at 110 ℃ to obtain the carrier precursor I.
(2) Subjecting the support precursor I to a nitrogen atmosphereRoasting at 630 ℃ for 5h to obtain the modified carrier P/Al2O3。
The P content in the carrier was 1.50g/L as determined by ICP.
Preparation of hydrogenation catalyst:
(i) cobalt ammonium sulfate ((NH) containing 2.28g of Co, 0.82g of Ca and 0.84g of Cu4)2Co(SO4)2·6H2O), calcium acetate (Ca (OAc)2·H2O) and copper acetate (Cu (OAc)2·H2O) 200ml of an aqueous solution was immersed in P/Al2O3Obtaining a catalyst precursor I;
(ii) drying at 110 ℃ for 4 hours to obtain the catalyst.
The catalyst had a Co content of 2.28g/L, a Ca content of 0.82g/L and a Cu content of 0.84g/L as determined by ICP.
Synthesis of cyclohexylamine:
35ml of catalyst is filled in a micro reactor, nitrogen leakage test is adopted, after no leakage point of the system is ensured, aniline enters a vaporizer through a metering pump to be vaporized, the vaporization temperature of the vaporizer is controlled to be 190 ℃, hydrogen enters the vaporizer along the direction vertical to the flow direction of the aniline, and the aniline and the hydrogen are mixed through the vaporizer to obtain feed gas, wherein the hydrogen/aniline in the feed gas is 31.0/1.0 (molar ratio). Then, the feed gas is used for 2400h-1The reaction temperature is 186 ℃, and the reaction pressure (gauge pressure) is 0.29 MPa. And the reacted mixed gas enters a condenser from the bottom of the reactor for condensation, and the product is analyzed.
The yield of cyclohexylamine was analytically calculated to be 83.11% and the selectivity 92.62%, and for ease of illustration and comparison, the support modification of the hydrogenation catalyst, the preparation of the hydrogenation catalyst, the reaction conditions, the feed rates, the cyclohexylamine yield and selectivity are shown in tables 1 and 2, respectively.
From the comparison between example 13 and examples 1 and 7, it can be seen that the hydrogenation catalyst used in the present invention has a better synergistic effect of the metal element Cu in the group IB metal and the metal element Ca in the alkaline earth metal in increasing the yield and selectivity of cyclohexylamine.
[ example 14 ]
Modified support P/Al2O3The preparation of (1):
(1) phosphoric acid (H) containing 1.50g P3PO4) 180ml of the aqueous solution (A) was immersed in 1L of a solution having a diameter of 6mm and a pore volume of 0.92cm3A specific surface area of 200 cm/g2Al in g2O3Then, the mixture is kept still for 24 hours and dried for 4 hours at 110 ℃ to obtain the carrier precursor I.
(2) Roasting the carrier precursor I for 5h at 630 ℃ in the atmosphere of nitrogen gas to obtain the modified carrier P/Al2O3。
The P content in the carrier was 1.50g/L as determined by ICP.
Preparation of hydrogenation catalyst:
(i) cobalt ammonium sulfate ((NH) containing 2.28g of Co, 0.82g of Ca, 0.43g of Au and 0.41g of Cu4)2Co(SO4)2·6H2O), calcium acetate (Ca (OAc)2·H2O), ammonium tetrachloroaurate ((NH)4)AuCl4·3H2O) and copper acetate (Cu (OAc)2·H2O) 200ml of an aqueous solution was immersed in P/Al2O3Obtaining a catalyst precursor I;
(ii) drying at 110 ℃ for 4 hours to obtain the catalyst.
The catalyst has a Co content of 2.28g/L, a Ca content of 0.82g/L, an Au content of 0.43g/L and a Cu content of 0.41g/L, which are measured by ICP.
Synthesis of cyclohexylamine:
35ml of catalyst is filled in a micro reactor, nitrogen leakage test is adopted, after no leakage point of the system is ensured, aniline enters a vaporizer through a metering pump to be vaporized, the vaporization temperature of the vaporizer is controlled to be 190 ℃, hydrogen enters the vaporizer along the direction vertical to the flow direction of the aniline, and the aniline and the hydrogen are mixed through the vaporizer to obtain feed gas, wherein the hydrogen/aniline in the feed gas is 31.0/1.0 (molar ratio). Then, the feed gas is used for 2400h-1The reaction temperature is 186 ℃, and the reaction pressure (gauge pressure) is 0.29 MPa. And the reacted mixed gas enters a condenser from the bottom of the reactor for condensation, and the product is analyzed.
The yield of cyclohexylamine was analytically calculated to be 84.29% and the selectivity 93.47%, and for convenience of illustration and comparison, the support modification of the hydrogenation catalyst, the preparation of the hydrogenation catalyst, the reaction conditions, the feed amount, the cyclohexylamine yield and selectivity are shown in tables 1 and 2, respectively.
From the comparison between example 14 and examples 12 and 13, it can be seen that the hydrogenation catalyst used in the present invention has a better synergistic effect of the metal elements Au and Cu in the group IB metals and the metal element Ca in the alkaline earth metals in terms of increasing the yield and selectivity of cyclohexylamine.
[ example 15 ]
Modified support P/Al2O3The preparation of (1):
(1) phosphoric acid (H) containing 1.50g P3PO4) 180ml of the aqueous solution (A) was immersed in 1L of a solution having a diameter of 6mm and a pore volume of 0.92cm3A specific surface area of 200 cm/g2Al in g2O3Then, the mixture is kept still for 24 hours and dried for 4 hours at 110 ℃ to obtain the carrier precursor I.
(2) Roasting the carrier precursor I for 5h at 630 ℃ in the atmosphere of nitrogen gas to obtain the modified carrier P/Al2O3。
The P content in the carrier was 1.50g/L as determined by ICP.
Preparation of hydrogenation catalyst:
(i) cobalt ammonium sulfate ((NH) containing 2.28g of Co, 0.82g of Ba, 0.43g of Au and 0.41g of Cu4)2Co(SO4)2·6H2O), barium acetate (Ba (OAc)2·H2O), ammonium tetrachloroaurate ((NH)4)AuCl4·3H2O) and copper acetate (Cu (OAc)2·H2O) 200ml of an aqueous solution was immersed in P/Al2O3Obtaining a catalyst precursor I;
(ii) drying at 110 ℃ for 4 hours to obtain the catalyst.
The catalyst has a Co content of 2.28g/L, a Ba content of 0.82g/L, an Au content of 0.43g/L and a Cu content of 0.41g/L as measured by ICP.
Synthesis of cyclohexylamine:
35ml of catalyst is filled in a microreactor, leakage test is carried out by adopting nitrogen, and aniline is added after no leakage point of a system is ensuredThe raw material gas is mixed by a vaporizer, and the hydrogen/aniline in the raw material gas is 31.0/1.0 (molar ratio). Then, the feed gas is used for 2400h-1The reaction temperature is 186 ℃, and the reaction pressure (gauge pressure) is 0.29 MPa. And the reacted mixed gas enters a condenser from the bottom of the reactor for condensation, and the product is analyzed.
The yield of cyclohexylamine was analytically calculated to be 84.35% and the selectivity 93.38%, and for convenience of illustration and comparison, the support modification of the hydrogenation catalyst, the preparation of the hydrogenation catalyst, the reaction conditions, the feed amount, the yield of cyclohexylamine and the selectivity are shown in tables 1 and 2, respectively.
[ example 16 ]
Modified support P/Al2O3The preparation of (1):
(1) phosphoric acid (H) containing 1.50g P3PO4) 180ml of the aqueous solution (A) was immersed in 1L of a solution having a diameter of 6mm and a pore volume of 0.92cm3A specific surface area of 200 cm/g2Al in g2O3Then, the mixture is kept still for 24 hours and dried for 4 hours at 110 ℃ to obtain the carrier precursor I.
(2) Roasting the carrier precursor I for 5h at 630 ℃ in the atmosphere of nitrogen gas to obtain the modified carrier P/Al2O3。
The P content in the carrier was 1.50g/L as determined by ICP.
Preparation of hydrogenation catalyst:
(i) cobalt ammonium sulfate ((NH) containing 2.28g of Co, 0.43g of Ca, 0.39g of Ba, 0.43g of Au and 0.41g of Cu4)2Co(SO4)2·6H2O), calcium acetate (Ca (OAc)2·H2O), barium acetate (Ba (OAc)2·H2O), ammonium tetrachloroaurate ((NH)4)AuCl4·3H2O) and copper acetate (Cu (OAc)2·H2O) 200ml of an aqueous solution was immersed in P/Al2O3Obtaining a catalyst precursor I;
(ii) drying at 110 ℃ for 4 hours to obtain the catalyst.
The catalyst has a Co content of 2.282g/L, a Ca content of 0.43g/L, a Ba content of 0.39g/L, an Au content of 0.43g/L and a Cu content of 0.41g/L through ICP determination.
Synthesis of cyclohexylamine:
35ml of catalyst is filled in a micro reactor, nitrogen leakage test is adopted, after no leakage point of the system is ensured, aniline enters a vaporizer through a metering pump to be vaporized, the vaporization temperature of the vaporizer is controlled to be 190 ℃, hydrogen enters the vaporizer along the direction vertical to the flow direction of the aniline, and the aniline and the hydrogen are mixed through the vaporizer to obtain feed gas, wherein the hydrogen/aniline in the feed gas is 31.0/1.0 (molar ratio). Then, the feed gas is used for 2400h-1The reaction temperature is 186 ℃, and the reaction pressure (gauge pressure) is 0.29 MPa. And the reacted mixed gas enters a condenser from the bottom of the reactor for condensation, and the product is analyzed.
The yield of cyclohexylamine was analytically calculated to be 85.02% and the selectivity 94.19%, and for convenience of illustration and comparison, the support modification of the hydrogenation catalyst, the preparation of the hydrogenation catalyst, the reaction conditions, the feed amount, the cyclohexylamine yield and selectivity are shown in tables 1 and 2, respectively.
From the comparison between example 16 and examples 14 and 15, it can be seen that the hydrogenation catalyst used in the present invention has a better synergistic effect of the metal elements Au and Cu in the group IB metals and the metal elements Ca and Ba in the alkaline earth metals in terms of increasing the yield and selectivity of cyclohexylamine.
TABLE 1
Figure BDA0001429443460000201
TABLE 2
Figure BDA0001429443460000211

Claims (8)

1. The process of preparing cyclohexylamine with aniline as material includes the reaction of hydrogen and aniline in the presence of aniline hydrogenating catalyst to obtain cyclohexaneAmine, wherein the aniline hydrogenation catalyst comprises a carrier and an active component, and the carrier is phosphorus modified Al2O3The active component comprises Co element and promoter element; the promoter elements include Au, Cu of alkaline earth metals Ca, Ba and IB group metals.
2. The method for preparing cyclohexylamine from aniline according to claim 1, wherein the molar ratio of hydrogen to aniline is 20.0-40.0.
3. The method for preparing cyclohexylamine from aniline according to claim 1, wherein the reaction temperature is 120-300 ℃.
4. The method for preparing cyclohexylamine from aniline according to claim 1, wherein the volume space velocity of the raw material gas is preferably 1800-3000 h-1。
5. The method for preparing cyclohexylamine from aniline according to claim 1, wherein the reaction pressure is 0.05-0.50 MPa.
6. The method for preparing cyclohexylamine from aniline according to claim 1, characterized in that the content of phosphorus element in the hydrogenation catalyst carrier is 0.10-3.00 g/L.
7. The method for preparing cyclohexylamine from aniline according to claim 1, characterized in that the content of Co element in the hydrogenation catalyst is 1.00-8.00 g/L.
8. The method for preparing cyclohexylamine from aniline according to claim 1, characterized in that the content of promoter element in the hydrogenation catalyst is 0.50-10.00 g/L.
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