CN109647452B - Hydrogenation catalyst for preparing cyclohexylamine - Google Patents

Hydrogenation catalyst for preparing cyclohexylamine Download PDF

Info

Publication number
CN109647452B
CN109647452B CN201710933983.8A CN201710933983A CN109647452B CN 109647452 B CN109647452 B CN 109647452B CN 201710933983 A CN201710933983 A CN 201710933983A CN 109647452 B CN109647452 B CN 109647452B
Authority
CN
China
Prior art keywords
catalyst
cyclohexylamine
hydrogenation catalyst
carrier
aniline
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201710933983.8A
Other languages
Chinese (zh)
Other versions
CN109647452A (en
Inventor
查晓钟
杨运信
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Original Assignee
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Shanghai Research Institute of Petrochemical Technology filed Critical China Petroleum and Chemical Corp
Priority to CN201710933983.8A priority Critical patent/CN109647452B/en
Publication of CN109647452A publication Critical patent/CN109647452A/en
Application granted granted Critical
Publication of CN109647452B publication Critical patent/CN109647452B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
    • 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
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • 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
    • B01J37/08—Heat treatment
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to a hydrogenation catalyst for preparing cyclohexylamine, which mainly solves the problems of low yield and low selectivity of synthesizing cyclohexylamine by catalytic hydrogenation of aniline in the prior art. The hydrogenation catalyst for preparing cyclohexylamine comprises a carrier and an active component, wherein the carrier is phosphorus modified Al2O3The active component comprises Co element and promoter element; the cocatalyst element comprises at least one metal element selected from IIB group metals, so that the problem is well solved, and the catalyst can be used in the industrial production of cyclohexylamine.

Description

Hydrogenation catalyst for preparing cyclohexylamine
Technical Field
The invention relates to a hydrogenation catalyst for preparing cyclohexylamine.
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 processes and chemo-amino catalysts for the preparation of mixtures of cyclohexylamine and dicyclohexylamine by Hydrogenation of aniline at 100-350 ℃ and 1-40 MPa describes the preparation of mixtures of cyclohexylamine and dicyclohexylamine with very high yields and selectivities. 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 catalyst for catalytic hydrogenation of aniline, but the effect is not obvious, and the catalytic hydrogenation of aniline is difficult to break successfullyTechnical barriers and obstacles to catalysts. 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
One of the technical problems to be solved by the invention is the problem that the yield and the selectivity of the cyclohexylamine are low, and the invention provides a novel hydrogenation catalyst for preparing the cyclohexylamine, which has the characteristics of high yield and high selectivity of the cyclohexylamine.
The second technical problem to be solved by the invention is the preparation method of the hydrogenation catalyst.
The third technical problem to be solved by the invention is the application of the hydrogenation catalyst.
In order to solve one of the above technical problems, the technical solution adopted by the present invention is as follows: the hydrogenation catalyst for preparing cyclohexylamine comprises a carrier and an active component, wherein 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 group IIB metals.
In the above technical solution, the content of phosphorus element in the carrier is preferably 0.10 to 3.00g/L, for example, but not limited to, 0.15, 0.20, 0.30, 0.40, 0.50, 0.60, 0.90, 1.0, 1.30, 1.50, 1.60, 1.70, 1.80, 1.90, 2.0, 2.5, 2.9, and the like, and more preferably 0.80 to 2.00 g/L.
In the above technical solution, the group IIB metal in the hydrogenation catalyst is preferably at least one of Zn, Cd and Hg, and more preferably both Zn and Cd. Zn and Cd have synergistic effect in improving the yield of cyclohexylamine and the selectivity of cyclohexylamine. The ratio of Zn to Cd is not particularly limited, for example, but not limited to, the weight ratio of Zn to Cd 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 may further include at least one selected from alkali metal elements, and at this time, a synergistic effect is provided between the metal element in the alkali metal and the metal element in the group IIB 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, lithium in conjunction with cadmium, lithium in conjunction with zinc, and the like. In this case, the ratio of the alkali metal element to the group IIB metal element is not particularly limited, but is not limited to, for example, 0.10 to 10.00 by weight, and more specific non-limiting examples of the weight ratio 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 alkali metal in the hydrogenation catalyst is preferably at least one selected from Li, Na, K, Rb and Cs, and more preferably both Na and Li. Na and Li have synergistic effect in improving the yield and selectivity of cyclohexylamine. The ratio of Na to Li is not particularly limited, for example, but not limited to, the weight ratio of Na to Li 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 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) to contain phosphorusPreparation of the Compound (II) into an aqueous solution impregnating 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.
To solve the second technical problem, the technical solution of the present invention is as follows:
the method for preparing a hydrogenation catalyst according to any of the preceding technical problems, comprising the steps of:
(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 technical solution, as a non-limiting example, the specific compound corresponding to the group IIB metal element in step (i) is preferably at least one selected from zinc citrate, zinc gluconate, zinc acetate, zinc nitrate, cadmium acetate, cadmium chloride, cadmium nitrate, mercury acetate, mercurous nitrate, and mercury sulfate; more preferably at least one of zinc citrate and cadmium acetate.
In the above-mentioned technical solution, as a non-limiting example, when the cocatalyst in step (i) further comprises an alkali metal, in this case, the specific compound corresponding to the alkali metal element is preferably at least one selected from the group consisting of alkali metal oxide, alkali metal hydroxide, alkali metal chloride, alkali metal sulfate, alkali metal nitrate and alkali metal acetate; more preferably at least one of an alkali metal acetate; most preferably at least one selected from the group consisting of sodium acetate and lithium acetate.
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.
To solve the third technical problem, the technical scheme of the invention is as follows:
the use of a catalyst according to any of the preceding technical solutions for the synthesis of cyclohexylamine.
The key to the present invention is the choice of catalyst, which can be reasonably determined by one skilled in the art for the specific process conditions to be applied and without inventive effort.
For example, the specific application method may be:
according to the synthesis method of the cyclohexylamine, in the presence of the hydrogenation catalyst in any one of the technical schemes in one of the technical problems, hydrogen and aniline react to obtain the cyclohexylamine.
In the above technical scheme, the raw material ratio is preferably: the molar ratio of hydrogen to aniline is (20.0 to 40.0)/1.0, and the most preferable raw material ratio is (25.0 to 35.0)/1.0.
In the technical scheme, the temperature of the hydrogenation reaction is preferably 120-300 ℃, and more preferably 185-220 ℃.
In the technical scheme, the preferred volume space velocity of the hydrogenation reaction is 1800-3000 h-1More preferably 2100 to 2800h-1。
In the technical scheme, the pressure of the hydrogenation reaction is preferably 0.05-0.50 MPa.
Unless otherwise specified, the pressures described herein are in terms of gauge pressure.
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 BDA0001429401260000051
Figure BDA0001429401260000052
compared with the prior art, the hydrogenation catalyst provided by the invention improves the yield and selectivity of cyclohexylamine.
Experimental results show that when the method is adopted, the yield of the cyclohexylamine reaches 81.55%, the selectivity reaches 91.56%, 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 alkali metals and at least one metal element selected from group IIB metals, more outstanding technical effects are obtained. 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 1.48g 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 1.48g/L as determined by ICP.
Preparation of hydrogenation catalyst:
(i) cobalt ammonium sulfate ((NH) containing 2.18g of Co4)2Co(SO4)2·6H2O) and an aqueous solution of 1.88g Li-containing lithium acetate (LiOAc) 200ml were 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 2.18g/L and a Li content of 1.88g/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 30.0/1.0 (molar ratio). Then, the feed gas is used for 2400h-1The reaction temperature is 187 ℃, and the reaction pressure (gauge pressure) is 0.28 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 91.56%, 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.
[ example 2 ]
Modified support P/Al2O3The preparation of (1):
(1) phosphoric acid (H) containing 1.48g 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 1.48g/L as determined by ICP.
Preparation of hydrogenation catalyst:
(i) cobalt ammonium sulfate ((NH) containing 2.18g of Co4)2Co(SO4)2·6H2O) and zinc citrate containing 1.88g Zn (Zn)3(C6H5O7)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 2.18g/L and a Zn content of 1.88g/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 30.0/1.0 (molar ratio). Then, the feed gas is used for 2400h-1The reaction temperature is 187 ℃, and the reaction pressure (gauge pressure) is 0.28 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 81.32% and the selectivity 91.74%, 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.
[ COMPARATIVE EXAMPLE 1 ]
Are comparative examples of [ example 1 ] and [ example 2 ].
Preparation of hydrogenation catalyst:
(i) cobalt ammonium sulfate ((NH) containing 2.18g of Co4)2Co(SO4)2·6H2O) 200ml of the aqueous solution 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 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 2.18 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 30.0/1.0 (molar ratio). Then, the feed gas is used for 2400h-1The reaction temperature is 187 ℃, and the reaction pressure (gauge pressure) is 0.28 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 70.18% and the selectivity 83.21%, 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.
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 Li and Co and Zn better than the catalyst containing Co, shows that the active components of the hydrogenation catalyst simultaneously contain Co and at least one metal element selected from alkali metals and IIB group metals, is favorable for improving the activity and stability of the hydrogenation catalyst, and has 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 1.48g 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) Baking the carrier precursor I at 630 ℃ in a nitrogen gas atmosphereFiring for 5 hours to obtain the modified carrier P/Al2O3。
The P content in the carrier was 1.48g/L as determined by ICP.
Preparation of hydrogenation catalyst:
(i) cobalt ammonium sulfate ((NH) containing 2.18g 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 2.18 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 30.0/1.0 (molar ratio). Then, the feed gas is used for 2400h-1The reaction temperature is 187 ℃, and the reaction pressure (gauge pressure) is 0.28 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 72.69% and the selectivity 85.34%, 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.
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/Al2O3Preparation of：
(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 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 determined to be 0.80g/L by ICP.
Preparation of hydrogenation catalyst:
(i) cobalt ammonium sulfate ((NH) containing 2.18g of Co4)2Co(SO4)2·6H2O) and 200ml of an aqueous solution containing 1.88g K potassium acetate (KOAc) were 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 2.18g/L and a K content of 1.88g/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 30.0/1.0 (molar ratio). Then, the feed gas is used for 2400h-1The reaction temperature is 187 ℃, and the reaction pressure (gauge pressure) is 0.28 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 81.45% 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 2.18g of Co4)2Co(SO4)2·6H2O) and an aqueous solution of 1.88g Rb of rubidium acetate (RbOAc) 200ml were 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 2.18g/L and an Rb content of 1.88g/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 30.0/1.0 (molar ratio). Then, the feed gas is used for 2400h-1The reaction temperature is 187 ℃, and the reaction pressure (gauge pressure) is 0.28 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 81.46% 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 5 ]
Modified support P/Al2O3The preparation of (1):
(1) phosphoric acid (H) containing 1.48g 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 1.48g/L as determined by ICP.
Preparation of hydrogenation catalyst:
(i) cobalt ammonium sulfate ((NH) containing 2.18g of Co4)2Co(SO4)2·6H2O) and an aqueous solution 200ml of rubidium acetate (CsOAc) containing 1.88g Cs were 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 is 2.18g/L and the Cs content is 1.88g/L through ICP measurement.
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 30.0/1.0 (molar ratio). Then, the feed gas is used for 2400h-1The reaction temperature is 187 ℃, and the reaction pressure (gauge pressure) is 0.28 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 81.40% 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 6 ]
Modified support P/Al2O3The preparation of (1):
(1) phosphoric acid (H) containing 1.48g 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 1.48g/L as determined by ICP.
Preparation of hydrogenation catalyst:
(i) cobalt ammonium sulfate ((NH) containing 2.18g of Co4)2Co(SO4)2·6H2O) and an aqueous solution of 1.88g of Na rubidium acetate (NaOAc) 200ml were 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 2.18g/L and a Na content of 1.88g/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 30.0/1.0 (molar ratio). Then, the feed gas is used for 2400h-1The reaction temperature is 187 ℃, and the reaction pressure (gauge pressure) is 0.28 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 81.43% and the selectivity 91.59%, 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 1.48g 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 1.48g/L as determined by ICP.
Preparation of hydrogenation catalyst:
(i) cobalt ammonium sulfate ((NH) containing 2.18g of Co4)2Co(SO4)2·6H2O) and cadmium acetate (Cd (OA) containing 1.88g of CdC)2·2H2O) was dissolved in an aqueous solution of acetic acid having a concentration of 10 wt% to obtain 200ml of an immersion liquid 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 2.18g/L and a Cd content of 1.88g/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 30.0/1.0 (molar ratio). Then, the feed gas is used for 2400h-1The reaction temperature is 187 ℃, and the reaction pressure (gauge pressure) is 0.28 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 81.35% 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 1.48g 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 1.48g/L as determined by ICP.
Preparation of hydrogenation catalyst:
(i) cobalt ammonium sulfate ((NH) containing 1.50g of Co4)2Co(SO4)2·6H2O) and mercury acetate (Hg (OA) containing 1.00g HgC)2·2H2O) was dissolved in cold water to obtain 200ml of an immersion liquid and the immersion liquid 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 Hg 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 30.0/1.0 (molar ratio). Then, the feed gas is used for 2400h-1The reaction temperature is 187 ℃, and the reaction pressure (gauge pressure) is 0.28 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 79.95% and the selectivity 90.89%, 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 9 ]
Modified support P/Al2O3The preparation of (1):
(1) phosphoric acid (H) containing 1.48g 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 1.48g/L as determined by ICP.
Preparation of hydrogenation catalyst:
(i) cobalt ammonium sulfate ((NH) containing 5.00g of Co4)2Co(SO4)2·6H2O) and Zinc acetate containing 6.00g Zn (OA)C)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 Zn 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 30.0/1.0 (molar ratio). Then, the feed gas is used for 2400h-1The reaction temperature is 187 ℃, and the reaction pressure (gauge pressure) is 0.28 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 81.17% and the selectivity 90.20%, 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 1.48g 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 1.48g/L as determined by ICP.
Preparation of hydrogenation catalyst:
(i) cobalt ammonium sulfate ((NH) containing 2.18g of Co, 0.98g of Zn and 0.90g of Cd4)2Co(SO4)2·6H2O), zinc citrate (Zn)3(C6H5O7)2·2H2O) and cadmium acetate (Cd (OA)C)2·2H2O) was dissolved in an aqueous solution of acetic acid having a concentration of 10 wt% to obtain 200ml of an immersion liquid 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 2.18g/L, a Zn content of 0.98g/L and a Cd content of 0.90g/L determined by ICP.
Synthesis of cyclohexylamine:
35ml of catalyst was charged in a microreactor and leak-tested with nitrogen to ensure systemAfter the system has no leakage point, 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 hydrogen/aniline in the feed gas is mixed by the vaporizer to obtain the feed gas, wherein the molar ratio of the hydrogen/aniline in the feed gas is 30.0/1.0. Then, the feed gas is used for 2400h-1The reaction temperature is 187 ℃, and the reaction pressure (gauge pressure) is 0.28 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 82.28% and the selectivity 92.39%, 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 the comparison between example 10 and examples 2 and 7, in the hydrogenation catalyst used in the present invention, the metal element Zn and the metal element Cd in the group IIB 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 1.48g 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 1.48g/L as determined by ICP.
Preparation of hydrogenation catalyst:
(i) cobalt ammonium sulfate ((NH) containing 2.18g of Co, 1.02g of Li and 0.86g of Na4)2Co(SO4)2·6H2200ml of an aqueous solution of O), lithium acetate (LiOAc) and sodium acetate (NaOAc) 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 2.18g/L, a Li content of 1.02g/L and a Na content of 0.86g/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 30.0/1.0 (molar ratio). Then, the feed gas is used for 2400h-1The reaction temperature is 187 ℃, and the reaction pressure (gauge pressure) is 0.28 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 82.48% and the selectivity 92.16%, 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 6, it can be seen that in the hydrogenation catalyst used in the present invention, the metallic element Li and the metallic element Na in the alkali 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 1.48g 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 1.48g/L as determined by ICP.
Preparation of hydrogenation catalyst:
(i) cobalt ammonium sulfate ((NH) containing 2.18g of Co, 0.92g of Li and 0.96g of Zn)4)2Co(SO4)2·6H2O), lithium acetate (LiOAc) and zinc citrate (Zn)3(C6H5O7)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 has a Co content of 2.18g/L, a Li content of 0.92g/L and a Zn content of 0.96g/L as 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 30.0/1.0 (molar ratio). Then, the feed gas is used for 2400h-1The reaction temperature is 187 ℃, and the reaction pressure (gauge pressure) is 0.28 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 92.79%, 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 12 and examples 1 and 2, it can be seen that in the hydrogenation catalyst used in the present invention, the metallic element Zn in the group IIB metal and the metallic element Li in the alkali metal have a 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 1.48g 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 1.48g/L as determined by ICP.
Preparation of hydrogenation catalyst:
(i) cobalt ammonium sulfate ((NH) containing 2.18g of Co, 0.92g of Li and 0.96g of Cd4)2Co(SO4)2·6H2O), lithium acetate (LiOAc) and cadmium acetate (Cd (OA)C)2·2H2O) was dissolved in an aqueous solution of acetic acid having a concentration of 10 wt% to obtain 200ml of an immersion liquid 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 2.18g/L, a Li content of 0.92g/L and a Cd content of 0.96g/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 30.0/1.0 (molar ratio). Then, the feed gas is used for 2400h-1The reaction temperature is 187 ℃, and the reaction pressure (gauge pressure) is 0.28 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 83.21% and the selectivity 92.67%, 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 is shown that in the hydrogenation catalyst used in the present invention, the metallic element Cd in the group IIB metal and the metallic element Li in the alkali metal have a better synergistic effect in increasing the yield and selectivity of cyclohexylamine.
[ example 14 ]
Modified support P/Al2O3The preparation of (1):
(1) phosphoric acid (H) containing 1.48g 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 1.48g/L as determined by ICP.
Preparation of hydrogenation catalyst:
(i) cobalt ammonium sulfate ((NH) containing 2.18g of Co, 0.92g of Li, 0.54g of Zn and 0.42g of Cd4)2Co(SO4)2·6H2O), lithium acetate (LiOAc), zinc citrate (Zn)3(C6H5O7)2·2H2O) and cadmium acetate (Cd (OA)C)2·2H2O) was dissolved in an aqueous solution of acetic acid having a concentration of 10 wt% to obtain 200ml of an immersion liquid 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 2.18g/L, a Li content of 0.92g/L, a Zn content of 0.54g/L and a Cd content of 0.42g/L determined by ICP.
Synthesis of cyclohexylamine:
filling 35ml of catalyst into a micro-reactor, adopting nitrogen leakage test to ensure that the system has no leakage point, then feeding aniline into a vaporizer through a metering pump to vaporize, controlling the vaporization temperature of the vaporizer to be 190 ℃, feeding hydrogen into the vaporizer along the direction vertical to the flow direction of the aniline, mixing the hydrogen and the aniline through the vaporizerA feed gas was obtained in which the hydrogen/aniline ratio was 30.0/1.0 (molar ratio). Then, the feed gas is used for 2400h-1The reaction temperature is 187 ℃, and the reaction pressure (gauge pressure) is 0.28 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 84.45% and the selectivity 93.76%, 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 14 and examples 12 and 13, it can be seen that in the hydrogenation catalyst used in the present invention, the metallic elements Zn and Cd in the group IIB metal and the metallic element Li in the alkali metal have a better synergistic effect in increasing the yield and selectivity of cyclohexylamine.
[ example 15 ]
Modified support P/Al2O3The preparation of (1):
(1) phosphoric acid (H) containing 1.48g 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 1.48g/L as determined by ICP.
Preparation of hydrogenation catalyst:
(i) cobalt ammonium sulfate ((NH) containing 2.18g of Co, 0.92g of Na, 0.54g of Zn and 0.42g of Cd4)2Co(SO4)2·6H2O), sodium acetate (NaOAc), zinc citrate (Zn)3(C6H5O7)2·2H2O) and cadmium acetate (Cd (OA)C)2·2H2O) was dissolved in an aqueous solution of acetic acid having a concentration of 10 wt% to obtain 200ml of an immersion liquid 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 2.18g/L, a Na content of 0.92g/L, a Zn content of 0.54g/L and a Cd content of 0.42g/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 30.0/1.0 (molar ratio). Then, the feed gas is used for 2400h-1The reaction temperature is 187 ℃, and the reaction pressure (gauge pressure) is 0.28 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 84.54% and the selectivity 93.54%, 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 16 ]
Modified support P/Al2O3The preparation of (1):
(1) phosphoric acid (H) containing 1.48g 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 1.48g/L as determined by ICP.
Preparation of hydrogenation catalyst:
(i) cobalt ammonium sulfate ((NH) containing 2.18g of Co, 0.48g of Li, 0.44g of Na, 0.54g of Zn and 0.42g of Cd4)2Co(SO4)2·6H2O), lithium acetate (LiOAc), sodium acetate (NaOAc), zinc citrate (Zn)3(C6H5O7)2·2H2O) and cadmium acetate (Cd (OA)C)2·2H2O) was dissolved in an aqueous solution of acetic acid having a concentration of 10 wt% to obtain 200ml of an immersion liquid 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 2.18g/L, a Li content of 0.48g/L, a Na content of 0.44g/L, a Zn content of 0.54g/L and a Cd content of 0.42g/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 30.0/1.0 (molar ratio). Then, the feed gas is used for 2400h-1The reaction temperature is 187 ℃, and the reaction pressure (gauge pressure) is 0.28 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 85.18% and the selectivity 94.33%, 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 16 and examples 14 and 15, it is shown that in the hydrogenation catalyst used in the present invention, the metallic elements Zn and Cd in group IIB metals and the metallic elements Li and Na in alkali metals have a good synergistic effect in increasing the yield and selectivity of cyclohexylamine.
TABLE 1
Figure BDA0001429401260000211
TABLE 2
Figure BDA0001429401260000221

Claims (9)

1. The hydrogenation catalyst for preparing cyclohexylamine comprises a carrier and an active component, wherein the carrier is phosphorus modified Al2O3The active component comprises Co element and promoter element; the promoter element includes at least one selected from alkali metals and Zn and Cd in group IIB metals.
2. The hydrogenation catalyst according to claim 1, wherein the carrier contains 0.10 to 3.00g/L of phosphorus.
3. The hydrogenation catalyst of claim 1 wherein the alkali metal in the hydrogenation catalyst is selected from at least one of Li, Na, K, Rb and Cs.
4. The hydrogenation catalyst according to claim 1, wherein the content of Co element in the hydrogenation catalyst is 1.00-8.00 g/L.
5. The hydrogenation catalyst according to claim 1, wherein the content of the promoter element in the hydrogenation catalyst is 0.50 to 10.00 g/L.
6. The hydrogenation catalyst according to claim 1, wherein the support is obtained by a process comprising the steps of:
(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.
7. The hydrogenation catalyst of claim 6 wherein the phosphorus-containing compound is selected from at least one of phosphoric acid, ammonium phosphate, diammonium phosphate, and phosphorus pentoxide.
8. A process for preparing a hydrogenation catalyst as claimed in claim 1, comprising the steps of:
(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.
9. Use of the hydrogenation catalyst according to any one of claims 1 to 7 or the hydrogenation catalyst prepared by the preparation method according to claim 8 in the synthesis of cyclohexylamine.
CN201710933983.8A 2017-10-10 2017-10-10 Hydrogenation catalyst for preparing cyclohexylamine Active CN109647452B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710933983.8A CN109647452B (en) 2017-10-10 2017-10-10 Hydrogenation catalyst for preparing cyclohexylamine

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710933983.8A CN109647452B (en) 2017-10-10 2017-10-10 Hydrogenation catalyst for preparing cyclohexylamine

Publications (2)

Publication Number Publication Date
CN109647452A CN109647452A (en) 2019-04-19
CN109647452B true CN109647452B (en) 2022-04-05

Family

ID=66108275

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710933983.8A Active CN109647452B (en) 2017-10-10 2017-10-10 Hydrogenation catalyst for preparing cyclohexylamine

Country Status (1)

Country Link
CN (1) CN109647452B (en)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1098916C (en) * 2000-01-04 2003-01-15 中国石油化工集团公司 Medium oil type hydrocracking catalyst and its preparing process
DE10050709A1 (en) * 2000-10-13 2002-04-25 Basf Ag Structured catalyst support, useful for the hydrogenation of aromatic compounds, contains a promoter comprising a Group I, II or IV metal or Group I-IV or VI metal and sulfur, selenium and carbon
CN101161631A (en) * 2006-10-10 2008-04-16 汉能科技有限公司 Preparation method of cyclohexylamine
CN103182310B (en) * 2011-12-28 2015-07-22 中国石油天然气股份有限公司 Preparation method of distillate oil hydrotreating catalyst
CN102633649B (en) * 2012-03-29 2013-08-21 山东潍焦集团有限公司 Method for synthesizing cyclohexylamine with aniline by means of gas-phase catalytic hydrogenation

Also Published As

Publication number Publication date
CN109647452A (en) 2019-04-19

Similar Documents

Publication Publication Date Title
CN105198755B (en) Method for preparing the trimethyl cyclohexylamine of 3 aminomethyl 3,5,5
CN113649062B (en) Catalyst for synthesizing 6-aminocapronitrile, preparation method thereof, and method for synthesizing 6-aminocapronitrile using same
CN109651166B (en) Method for preparing cyclohexylamine from aniline
CN109647456B (en) Hydrogenation catalyst for synthesizing cyclohexylamine
CN109651164B (en) Method for synthesizing cyclohexylamine by aniline hydrogenation
CN109651165B (en) Method for producing cyclohexylamine by aniline hydrogenation
CN109647452B (en) Hydrogenation catalyst for preparing cyclohexylamine
CN109651172B (en) Method for preparing cyclohexylamine by aniline hydrogenation
CN109651169B (en) Process for preparing cyclohexylamine
CN109647454B (en) Hydrogenation catalyst for preparing cyclohexylamine from aniline
CN109647453B (en) Hydrogenation catalyst for producing cyclohexylamine
CN109651167B (en) Hydrogenation catalyst for producing cyclohexylamine
CN109647450B (en) Hydrogenation catalyst for synthesizing cyclohexylamine
CN109651163B (en) Process for producing cyclohexylamine
CN109647455B (en) Hydrogenation catalyst for producing cyclohexylamine from aniline
CN109651162B (en) Method for producing cyclohexylamine from aniline
CN109647451B (en) Hydrogenation catalyst for preparing cyclohexylamine
CN109651168B (en) Method for synthesizing cyclohexylamine
CN109926091B (en) Heteropolyacid ammonium salt catalyst and preparation method thereof
CN111495383B (en) Method and catalyst for preparing hexamethylene diamine from hexanediol and ammonia gas
CN107628957A (en) A kind of new method research of the direct ammonification synthesizing cyclohexane 1 amine of cyclohexene
CN114433088A (en) Catalyst and carrier with function of catalyzing alcohol to generate organic amine through hydroamination, and preparation method and application thereof
CN117946030A (en) Method for synthesizing hexamethylenediamine and co-producing cyclohexylimine
JPH02202855A (en) Production of secondary amine
CN112313239B (en) Immobilized ruthenium-TRIPHOS catalysts for selective hydrogenation of amides

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant