CN109651164B - Method for synthesizing cyclohexylamine by aniline hydrogenation - Google Patents
Method for synthesizing cyclohexylamine by aniline hydrogenation Download PDFInfo
- Publication number
- CN109651164B CN109651164B CN201710933984.2A CN201710933984A CN109651164B CN 109651164 B CN109651164 B CN 109651164B CN 201710933984 A CN201710933984 A CN 201710933984A CN 109651164 B CN109651164 B CN 109651164B
- Authority
- CN
- China
- Prior art keywords
- cyclohexylamine
- aniline
- catalyst
- carrier
- hydrogenation
- 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
Links
Classifications
-
- 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
- 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
Abstract
The invention relates to a method for synthesizing cyclohexylamine by aniline hydrogenation, which mainly solves the problems of low yield and low selectivity of synthesizing cyclohexylamine by aniline catalytic hydrogenation in the prior art. A method for synthesizing cyclohexylamine by aniline hydrogenation 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 catalyst promoter element comprises at least one metal element selected from alkali metals and IIB group metals, so that the problem is solved well, and the catalyst promoter element can be used in the industrial production of cyclohexylamine.
Description
Technical Field
The invention relates to a method for synthesizing cyclohexylamine by aniline hydrogenation.
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 chemosynthesis catalysts for the preparation of mixtures of unsaturated cyclic and bicyclic-heterocyclic amines) describes a process in the range of 100 to 35The mixture of cyclohexylamine and dicyclohexylamine is prepared by hydrogenating aniline at 0 ℃ under the condition of 1-40 MPa, so that high yield and selectivity can be obtained. 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 synthesizing cyclohexylamine by hydrogenating 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 synthesizing cyclohexylamine by aniline hydrogenation 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 alkali metals and group IIB 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 technical scheme, the content of the phosphorus element in the carrier is preferably 0.10-3.00 g/L, such as but not limited to 0.152, 0.202, 0.302, 0.402, 0.502, 0.602, 0.792, 0.902, 1.02, 1.302, 1.502, 1.602, 1.702, 1.802, 1.902, 2.02, 2.52, 2.92 and the like, and more preferably 0.792-2.02 g/L.
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 0.102 to 10.00, and more specific non-limiting examples of the weight ratio within this range may be 0.202, 0.402, 0.502, 0.602, 0.802, 1.002, 1.202, 1.402, 1.602, 1.802, 2.002, 2.502, 3.002, 3.502, 4.002, 4.502, 5.002, 5.502, 6.002, 6.502, 7.002, 7.502, 8.002, and the like.
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 0.102-10.00, and non-limiting examples of more specific weight ratios within this range may be 0.202, 0.402, 0.502, 0.602, 0.802, 1.002, 1.202, 1.402, 1.602, 1.802, 2.002, 2.502, 3.002, 3.502, 4.002, 4.502, 5.002, 5.502, 6.002, 6.502, 7.002, 7.502, 8.002, and the like.
In the above technical solution, the promoter element preferably includes at least one selected from alkali metal elements and at least one selected from group IIB metal elements at the same time, and at this time, there is a synergistic effect between the metal element in the alkali metal and the metal element in the group IIB metal in the aspect of improving 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, and for example, but not limited to, the weight ratio of the alkali metal element to the group IIB metal element is 0.102 to 10.00, and more specific non-limiting examples of the weight ratio in this range may be 0.202, 0.402, 0.502, 0.602, 0.802, 1.002, 1.202, 1.402, 1.602, 1.802, 2.002, 2.502, 3.002, 3.502, 4.002, 4.502, 5.002, 5.502, 6.002, 6.502, 7.002, 7.502, 8.002, and the like.
In the technical scheme, the content of Co in the hydrogenation catalyst is preferably 1.00-8.00 g/L, such as but not limited to 1.492g/L, 2.002g/L, 2.502g/L, 3.002g/L, 3.502g/L, 4.002g/L, 4.502g/L, 5.002g/L, 5.502g/L, 6.002g/L, 6.502g/L, 7.002g/L, 7.502g/L and the like, and more preferably 1.492-5.01 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 0.702g/L, 0.802g/L, 0.982g/L, 1.502g/L, 2.002g/L, 2.502g/L, 3.002g/L, 3.502g/L, 4.002g/L, 4.502g/L, 5.002g/L, 5.502g/L, 6.002g/L, 6.502g/L, 7.002g/L, 7.502g/L, 8.002g/L, 8.502g/L, 9.002g/L, 9.502g/L and the like; more preferably 0.982 to 6.02 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 technical solution, as a non-limiting example, when the specific compound corresponding to the alkali metal element in the step (i) is preferably at least one selected from the group consisting of alkali metal oxide, alkali metal hydroxide, alkali metal chloride, alkali metal sulfate, alkali group 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 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 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:
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 91.56%, 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:
charging into a microreactorAnd (2) testing leakage of 35ml of catalyst by adopting nitrogen, ensuring that a system has no leakage point, then feeding aniline into a vaporizer through a metering pump for vaporization, 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, and mixing the hydrogen and the aniline by the vaporizer to obtain a feed gas, wherein the molar ratio of the hydrogen to the 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 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 theThe feed gas is fed 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) 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) 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/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 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) Mixing the carrierRoasting the precursor I for 5 hours at the temperature of 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 g2O3Standing for 24h, and drying at 110 ℃ for 4h to obtain the carrierBody 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 g2O3In the above-mentioned manner,standing for 24h, and drying at 110 ℃ for 4h 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 0.92cm3Per g, specific surface area of200cm2Al 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 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. The mixed gas after reaction enters into the reactor from the bottom for condensationThe vessel was condensed and the product was 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 is adopted for leakage test, aniline enters a vaporizer for vaporization through a metering pump after no leakage point of the system is ensured, and control is carried outThe vaporization temperature of the vaporizer is 190 ℃, hydrogen enters the vaporizer along the direction vertical to the flow direction of aniline, and the hydrogen/aniline in the feed gas is 30.0/1.0 (molar ratio) after being mixed by the vaporizer. 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) containing 1.48g PPhosphoric acid (H)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 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:
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 84.45% 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 the micro-reactor, nitrogen is adopted for leakage test, after the system is ensured to have 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 and the aniline are mixed through the vaporizer to obtain a feed gas, wherein the molar ratio of the hydrogen to the 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 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
TABLE 2
Claims (8)
1. The process for synthesizing cyclohexylamine by hydrogenating aniline includes reaction between hydrogen and catalystReacting aniline serving as a raw material 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 elements comprise Li and Na in alkali metals and Zn and Cd in IIB group metals.
2. The method for synthesizing cyclohexylamine by hydrogenating aniline according to claim 1, wherein the molar ratio of hydrogen to aniline is 20.0 to 40.0.
3. The method for synthesizing cyclohexylamine by aniline hydrogenation according to claim 1, wherein the reaction temperature is 120-300 ℃.
4. The method for synthesizing cyclohexylamine by aniline hydrogenation according to claim 1, wherein the volume space velocity of the raw material gas is preferably 1800-3000 h-1。
5. The method for synthesizing cyclohexylamine by hydrogenating aniline according to claim 1, wherein the reaction pressure is 0.05 to 0.50 MPa.
6. The method for synthesizing cyclohexylamine through aniline hydrogenation according to claim 1, wherein the content of phosphorus element in the hydrogenation catalyst carrier is 0.10-3.00 g/L.
7. The method for synthesizing cyclohexylamine through aniline hydrogenation according to claim 1, characterized in that the Co element content in the hydrogenation catalyst is 1.00-8.00 g/L.
8. The method for synthesizing cyclohexylamine through aniline hydrogenation according to claim 1, wherein the content of the promoter element in the hydrogenation catalyst is 0.50-10.00 g/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710933984.2A CN109651164B (en) | 2017-10-10 | 2017-10-10 | Method for synthesizing cyclohexylamine by aniline hydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710933984.2A CN109651164B (en) | 2017-10-10 | 2017-10-10 | Method for synthesizing cyclohexylamine by aniline hydrogenation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109651164A CN109651164A (en) | 2019-04-19 |
| CN109651164B true CN109651164B (en) | 2021-11-30 |
Family
ID=66108583
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710933984.2A Active CN109651164B (en) | 2017-10-10 | 2017-10-10 | Method for synthesizing cyclohexylamine by aniline hydrogenation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109651164B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111889097B (en) * | 2020-07-28 | 2022-07-12 | 万华化学集团股份有限公司 | Aniline hydrogenation catalyst, preparation method and application |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU114260A1 (en) * | 1957-07-31 | 1957-11-30 | З.Г. Лаптева | The method of producing cyclohexylamine |
| CN1043699A (en) * | 1987-06-24 | 1990-07-11 | 新日本理化株式会社 | The production method of cyclohexylamines |
| CN102633649A (en) * | 2012-03-29 | 2012-08-15 | 山东潍焦集团有限公司 | Method for synthesizing cyclohexylamine with aniline by means of gas-phase catalytic hydrogenation |
| CN105237434A (en) * | 2015-10-29 | 2016-01-13 | 中石化南京工程有限公司 | Method for producing cyclohexanone oxime |
| CA2980525A1 (en) * | 2015-03-31 | 2016-10-06 | Daikin Industries, Ltd. | Composition and laminated body |
| WO2017042828A3 (en) * | 2015-09-10 | 2017-04-27 | Megafine Pharma (P) Ltd. | Process for the preparation of selexipag |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2905273B1 (en) * | 2014-02-05 | 2018-06-06 | Covestro Deutschland AG | Process for hydrogenating aromatic di- and polyamines |
| CN105498849B (en) * | 2014-09-25 | 2017-12-22 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and its application |
-
2017
- 2017-10-10 CN CN201710933984.2A patent/CN109651164B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU114260A1 (en) * | 1957-07-31 | 1957-11-30 | З.Г. Лаптева | The method of producing cyclohexylamine |
| CN1043699A (en) * | 1987-06-24 | 1990-07-11 | 新日本理化株式会社 | The production method of cyclohexylamines |
| CN102633649A (en) * | 2012-03-29 | 2012-08-15 | 山东潍焦集团有限公司 | Method for synthesizing cyclohexylamine with aniline by means of gas-phase catalytic hydrogenation |
| CA2980525A1 (en) * | 2015-03-31 | 2016-10-06 | Daikin Industries, Ltd. | Composition and laminated body |
| WO2017042828A3 (en) * | 2015-09-10 | 2017-04-27 | Megafine Pharma (P) Ltd. | Process for the preparation of selexipag |
| CN105237434A (en) * | 2015-10-29 | 2016-01-13 | 中石化南京工程有限公司 | Method for producing cyclohexanone oxime |
Non-Patent Citations (2)
| Title |
|---|
| 活性氧化铝载体的研究进展;唐国旗，等;《化工进展》;20111231;第30卷(第8期);第1756页左栏第1段倒数第2行至右栏第1段，第1758页左栏最后1段至右栏第1行 * |
| 苯胺催化加氢制环己胺的技术概况;谢祥，等;《化学工业与工程技术》;20100228;第31卷(第1期);第33页左栏倒数第1-2行 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109651164A (en) | 2019-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6033231B2 (en) | Method for producing 3-aminomethyl-3,5,5-trimethylcyclohexylamine | |
| CN106881132B (en) | Catalyst for synthesizing ammonia | |
| 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 | |
| CN109651164B (en) | Method for synthesizing cyclohexylamine by aniline hydrogenation | |
| CN109647456B (en) | Hydrogenation catalyst for synthesizing cyclohexylamine | |
| CN109651165B (en) | Method for producing cyclohexylamine by aniline hydrogenation | |
| CN109651172B (en) | Method for preparing cyclohexylamine by aniline hydrogenation | |
| CN109647452B (en) | Hydrogenation catalyst for preparing cyclohexylamine | |
| CN109651169B (en) | Process for preparing cyclohexylamine | |
| CN109647453B (en) | Hydrogenation catalyst for producing cyclohexylamine | |
| CN109647454B (en) | Hydrogenation catalyst for preparing cyclohexylamine from aniline | |
| CN109651167B (en) | Hydrogenation catalyst for producing cyclohexylamine | |
| CN109647450B (en) | Hydrogenation catalyst for synthesizing cyclohexylamine | |
| CN109651162B (en) | Method for producing cyclohexylamine from aniline | |
| CN109651163B (en) | Process for producing cyclohexylamine | |
| CN109647455B (en) | Hydrogenation catalyst for producing cyclohexylamine from aniline | |
| CN109651168B (en) | Method for synthesizing cyclohexylamine | |
| CN109647451B (en) | Hydrogenation catalyst for preparing cyclohexylamine | |
| CN107628957A (en) | A kind of new method research of the direct ammonification synthesizing cyclohexane 1 amine of cyclohexene | |
| CN110627743A (en) | Method for preparing morpholine and monoethylamine by using N-ethyl morpholine | |
| CN117946030A (en) | Method for synthesizing hexamethylenediamine and co-producing cyclohexylimine | |
| Skripov et al. | Effect of the nature of a solvent on properties of Pd–P catalysts in hydrogenation of ortho-chloronitrobenzene | |
| CN111495383B (en) | Method and catalyst for preparing hexamethylene diamine from hexanediol and ammonia gas | |
| GB731819A (en) | Improvements in or relating to the production of hexamethylene diamine and salts thereof |
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 |