CN114805088A - Synthesis method of cyclohexylamine - Google Patents
Synthesis method of cyclohexylamine Download PDFInfo
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- CN114805088A CN114805088A CN202210450296.1A CN202210450296A CN114805088A CN 114805088 A CN114805088 A CN 114805088A CN 202210450296 A CN202210450296 A CN 202210450296A CN 114805088 A CN114805088 A CN 114805088A
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- cyclohexylamine
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- ammonia
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- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 238000001308 synthesis method Methods 0.000 title claims abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 76
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- 239000003054 catalyst Substances 0.000 claims abstract description 55
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000002994 raw material Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 32
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 claims abstract description 29
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 28
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000009471 action Effects 0.000 claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims description 43
- 229910052739 hydrogen Inorganic materials 0.000 claims description 43
- 229910021529 ammonia Inorganic materials 0.000 claims description 31
- 239000007789 gas Substances 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- 238000003746 solid phase reaction Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 abstract description 29
- 230000008901 benefit Effects 0.000 abstract description 7
- 238000009776 industrial production Methods 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- -1 Cyclohexylamine Cyclohexanol Dicyclohexylamine Chemical compound 0.000 description 9
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- UNFUYWDGSFDHCW-UHFFFAOYSA-N monochlorocyclohexane Chemical compound ClC1CCCCC1 UNFUYWDGSFDHCW-UHFFFAOYSA-N 0.000 description 4
- NJNQUTDUIPVROZ-UHFFFAOYSA-N nitrocyclohexane Chemical compound [O-][N+](=O)C1CCCCC1 NJNQUTDUIPVROZ-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 238000005915 ammonolysis reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000004176 ammonification Methods 0.000 description 2
- 239000013064 chemical raw material Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 239000002778 food additive Substances 0.000 description 2
- 235000013373 food additive Nutrition 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- UDIPTWFVPPPURJ-UHFFFAOYSA-M Cyclamate Chemical compound [Na+].[O-]S(=O)(=O)NC1CCCCC1 UDIPTWFVPPPURJ-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 241000772415 Neovison vison Species 0.000 description 1
- 229910021543 Nickel dioxide Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000000625 cyclamic acid and its Na and Ca salt Substances 0.000 description 1
- CBIOJTYADDCUSL-UHFFFAOYSA-N cyclohexanamine;cyclohexanol Chemical class NC1CCCCC1.OC1CCCCC1 CBIOJTYADDCUSL-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229960001462 sodium cyclamate Drugs 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
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
- C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
- C07C209/26—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds by reduction with hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/84—Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method of cyclohexylamine, belonging to the technical field of cyclohexylamine synthesis, comprising the following steps: under the action of a catalyst, obtaining a mixed product by a first raw material, ammonia gas and hydrogen gas, wherein the mixed product comprises cyclohexylamine and dicyclohexylamine, and the first raw material comprises cyclohexanone, cyclohexanol or a combination thereof. The method has the advantages of mild reaction conditions, rich raw material sources, high raw material conversion rate and few byproducts, and can be applied to industrial production.
Description
Technical Field
The invention relates to the technical field of cyclohexylamine preparation, in particular to a synthesis method of 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. Dicyclohexylamine is also an important chemical raw material and a fine chemical intermediate, is mainly used in the fields of synthetic rubber accelerators, metal corrosion inhibitors, surfactants, oilfield chemicals, medicines, pesticides and the like, and is widely applied to industry.
In europe, cyclohexylamine is in a state of shortage because of the limitation of hydrogen feed. The domestic production capacity of the cyclohexylamine is close to 10 ten thousand tons per year. 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: in the 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. Various methods for preparing Ni catalysts are introduced and researched by Mink et al of Hungarian science research institute in the production of cyclohexylamine by aniline catalytic hydrogenation based on sodium hydroxide-promoted or nickel-supported lanthanum oxide (Mink, G., Horv th, L.hydrogenation of aniline to cyclohexylamine on NaOH-promoted or lanthanum supported. DE1975457(Hydrogenation processes and heterocyclic catalysts for the preparation Of mixtures Of cyclohexylamine and dicyclohexylamine from the amines) teaches that the Hydrogenation Of aniline at temperatures Of 100 to 350 ℃ and pressures Of 1 to 40MPa gives very high yields and selectivities. The carrier of the heterogeneous catalyst adopted in the reaction is Al 2 O 3 The 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. The existing methods have the problems of low yield and low selectivity of the cyclohexylamine in the process of synthesizing the cyclohexylamine.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a method for synthesizing cyclohexylamine, which uses cyclohexanol or cyclohexanone as a raw material, has the advantages of mild reaction conditions, abundant raw material sources, high raw material conversion rate and few byproducts, can be applied to industrial production, and can adjust the proportion of the cyclohexylamine and the dicyclohexylamine in the product by adjusting the proportion of ammonia gas and hydrogen gas.
The invention discloses a synthesis method of cyclohexylamine, which comprises the following steps:
under the action of a catalyst, obtaining a mixed product by a first raw material, ammonia gas and hydrogen gas, wherein the mixed product comprises cyclohexylamine and dicyclohexylamine, and the first raw material comprises cyclohexanone, cyclohexanol or a combination thereof.
Preferably, the ratio of the cyclohexylamine to the dicyclohexylamine in the product is adjusted by controlling the ratio of ammonia to hydrogen; the molar ratio of ammonia to hydrogen is 1: when the reaction temperature is 2.5-4.0, the product is mainly dicyclohexylamine; the mol ratio of ammonia to hydrogen is 1.5-4.5: when 1, the product is mainly cyclohexylamine.
Preferably, the dicyclohexylamine is synthesized by the mixed product and the first raw material under the action of hydrogen and a catalyst.
Preferably, the synthesis method adopts gas-solid phase reaction:
feeding the first raw material and cyclohexylamine into a preheating gasifier, mixing the first raw material and the cyclohexylamine with ammonia gas and hydrogen gas, preheating and gasifying to obtain a first mixed gas;
after entering a fixed bed reactor, maintaining the pressure by using hydrogen and ammonia gas, and reacting the first mixed gas under the action of a catalyst to obtain a mixed product;
cooling the mixed product gas, and performing gas-liquid separation to obtain a mixed solution;
and rectifying and purifying the mixed solution to obtain the dicyclohexylamine and the cyclohexylamine.
Preferably, the hydrogen obtained by gas-liquid separation is pressurized by a recycle compressor and returned to the preheating gasifier for recycling.
Preferably, the catalyst comprises:
0-50 wt% of Co, 0-55 wt% of Ni, 0-35 wt% of Mg, 0-60 wt% of Cu, 0-45 wt% of Zn and a carrier, wherein the carrier comprises alumina, silicon dioxide or a combination of the alumina and the silicon dioxide.
Preferably, the catalyst comprises: 0-40 wt% of Co, 5-50 wt% of Ni, 3-21 wt% of Mg, 5-30 wt% of Cu and 5-40 wt% of Zn;
the preparation method of the catalyst comprises the following steps:
mixing Al (OH) 3 Preparing sodium metaaluminate solution by NaOH;
neutralizing and precipitating sodium metaaluminate solution with nitric acid, aging, filtering, washing, rolling ball molding, drying, and roasting to obtain spherical Al with diameter of 3-20mm 2 O 3 A carrier;
preparing mixed solution of nitrates of Co, Ni, Mg, Cu and Zn according to a certain proportion, and adding Al 2 O 3 Impregnating the carrier;
impregnating Al 2 O 3 Drying the carrier and then roasting at high temperature to obtain a crude catalyst;
and (3) carrying out hydrogen reduction on the crude catalyst to obtain the catalyst.
Preferably, the reduction conditions for the crude catalyst are:
hydrogen gas under 0.05MPa pressure, 460 ℃ temperature and airspeed of 1000h -1 Reducing for 24 hours under the condition.
Preferably, the first feedstock feed rate is in the range of 45 to 90 ml/hour per liter of catalyst.
Preferably, the synthesis conditions are: ammonia and hydrogen are used for maintaining the pressure of 0.05-3 Mpa and the temperature of 150-300 ℃.
Compared with the prior art, the invention has the beneficial effects that: the reaction condition is mild, the raw material source is rich, the raw material conversion rate is high, the byproducts are few, the purification is convenient, and the method can be applied to industrial production; the ratio of cyclohexylamine to dicyclohexylamine in the product can be adjusted by adjusting the ratio of ammonia to hydrogen.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The invention is described in further detail below:
a method for synthesizing cyclohexylamine, the method comprising:
under the action of catalyst, the first material, ammonia gas and hydrogen gas are mixed to obtain mixed product, said mixed product includes cyclohexylamine and dicyclohexylamine,
wherein the first feedstock comprises cyclohexanone, cyclohexanol, or a combination thereof.
Reaction formula 1 is cyclohexanol (C) 6 H 12 O) reaction with ammonia gas:
C 6 H 12 O+NH 3 →C 6 H 13 N+H 2 O+C 12 H 24 N (1)
in the reaction formula 1, hydrogen and ammonia are used as the holding gas.
Reaction formula 2 is cyclohexanone (C) 6 H 10 O) reaction with ammonia and hydrogen:
C 6 H 10 O+H 2 +NH 3 →C 6 H 13 N+H 2 O+C 12 H 24 N (2)
in the reaction formula 2, hydrogen gas is used as a pressure maintaining gas and participates in the reaction.
The method has the advantages of mild reaction conditions, rich raw material sources, high raw material conversion rate, few byproducts, convenience in purification and applicability to industrial production; the ratio of cyclohexylamine to dicyclohexylamine in the product can be adjusted by adjusting the ratio of ammonia to hydrogen.
The composition ratio before and after the reaction is not limited in equations 1 and 2. The invention can adjust the ratio of the cyclohexylamine to the dicyclohexylamine in the product by controlling the ratio of the ammonia to the hydrogen: the molar ratio of ammonia to hydrogen is 1: when the reaction temperature is 2.5-4.0, the product is mainly dicyclohexylamine; the mol ratio of ammonia to hydrogen is 1.5-4.5: when 1, the product is mainly cyclohexylamine.
The mixed product and the first raw material can be further synthesized into dicyclohexylamine under the action of hydrogen and a catalyst, and the reaction mode is as follows:
C 6 H 12 O+C 6 H 13 N→H 2 O+C 12 H 23 N (3)
C 6 H 10 O+H 2 +C 6 H 13 N→H 2 O+C 12 H 23 N (4)
namely, the cyclohexylamine in the mixed product is further synthesized into the dicyclohexylamine, and the output ratio of the dicyclohexylamine is improved.
Wherein the components of the catalyst comprise Co, Ni, Mg, Cu, Zn and a carrier, and the carrier comprises alumina, silica or a combination thereof. Specifically, the catalyst comprises: 0-50 wt% of Co, 0-55 wt% of Ni, 0-35 wt% of Mg, 0-60 wt% of Cu, 0-45 wt% of Zn and the balance of a carrier. Preferably, the catalyst comprises: 0-40 wt% of Co, 5-50 wt% of Ni, 3-21 wt% of Mg, 5-30 wt% of Cu and 5-40 wt% of Zn. In one particular application, the feed rate of feedstock per liter of catalyst is from 45 to 90 ml/hour. The catalyst is simultaneously suitable for the reaction of cyclohexanol or cyclohexanone and cyclohexylamine.
The preparation method of the catalyst comprises the following steps:
step 201: mixing Al (OH) 3 Preparing sodium metaaluminate solution by NaOH;
step 202: neutralizing and precipitating sodium metaaluminate solution with nitric acid, aging, filtering, washing, rolling ball molding, drying, and roasting to obtain spherical Al with diameter of 3-20mm 2 O 3 A carrier, preferably 3 mm;
step 203: preparing mixed solution of nitrates of Co, Ni, Mg, Cu and Zn according to a certain proportion, and adding Al 2 O 3 Impregnating the carrier;
step 204: impregnating Al 2 O 3 Drying the carrier and then roasting at high temperature to obtain a crude catalyst;
step 205: and (3) reducing the crude catalyst by hydrogen to obtain the catalyst. Specifically, the reduction conditions of the crude catalyst are as follows: ammonia gas and hydrogen gas are used under the pressure of 0.05MPa, the temperature of 460 ℃ and the space velocity of 1000h -1 Under the condition ofThe original 24 hours, but not limited thereto.
In one specific application, the synthesis employs a gas-solid phase reaction method:
step 301: the first raw material and cyclohexylamine are quantitatively pumped into a preheating gasifier through a pump and a flowmeter, and are mixed with hydrogen and ammonia gas and then preheated and gasified to obtain a first mixed gas.
Step 302: and after entering the fixed bed reactor, maintaining the pressure by using hydrogen and ammonia gas, and reacting the first mixed gas under the action of the catalyst to obtain a mixed product. The method comprises the steps of using hydrogen and ammonia as circulating gases, keeping the pressure at 0.05-3 Mpa, the reaction temperature at 50-300 ℃, and feeding 45ml of raw materials per 1L of catalyst.
Step 303: and cooling and carrying out gas-liquid separation on the mixed product to obtain a mixed solution. Wherein, the hydrogen obtained by gas-liquid separation is pressurized by a circulating compressor and then returns to the preheating gasifier for recycling.
Step 304: and the mixed solution is rectified and purified by an azeotropic rectifying tower to obtain dicyclohexylamine and cyclohexylamine. The product is rectified and purified to meet the requirements of enterprise standards, and a small amount of excessive unreacted raw materials are returned to a feeding system. And biochemically treating the rectified reaction product water to discharge standard. The preparation process system realizes closed cycle, and the excessive and unreacted materials can be recycled.
The cyclohexanol produced by using cyclohexanone as the first raw material can be mixed with cyclohexanone in any ratio and returned to the reaction system for continuous reaction.
Example 1
2000ml of catalyst was prepared according to the preparation method of catalyst, the components of catalyst were: 25% of Co, 15% of Ni, 3% of Mg, 15% of Cu, 10% of Zn and the balance of Al 2 O 3 。
The following 9 reaction conditions were set:
the reaction conditions 1 are as follows: the molar ratio of ammonia to hydrogen is 3:1, as circulating gas, the pressure is kept at 0.7Mpa, the reaction temperature is 150 ℃, the feeding amount is 90ml/h, and the obtained experimental data are as follows:
| water (W) | Cyclohexylamine | Cyclohexanol | Dicyclohexylamine |
| 18.12 | 80.28 | 0.29 | 1.27 |
The reaction conditions 2 are as follows: the molar ratio of ammonia to hydrogen is 3:1, as a circulating gas, keeping the pressure at 0.7Mpa, the reaction temperature at 190 ℃, the feeding amount at 90ml/h, and obtaining experimental data as follows:
| water (W) | Cyclohexylamine | Cyclohexanol | Dicyclohexylamine |
| 18.10 | 80.18 | 0.26 | 1.42 |
The reaction conditions 3 are as follows: the molar ratio of ammonia to hydrogen is 3:1, as circulating gas, the pressure is kept at 0.7Mpa, the reaction temperature is 270 ℃, the feeding amount is 90ml/h, and the obtained experimental data are as follows:
| water (W) | Cyclohexylamine | Cyclohexanol | Dicyclohexylamine |
| 18.11 | 80.17 | 0.28 | 1.40 |
The reaction conditions 4 are as follows: the molar ratio of ammonia to hydrogen was 2.5: 1, as circulating gas, the pressure is kept at 0.7Mpa, the reaction temperature is 270 ℃, the feeding amount is 90ml/h, and the obtained experimental data are as follows:
| water (W) | Cyclohexylamine | Cyclohexanol | Dicyclohexylamine |
| 18.09 | 80.21 | 0.27 | 1.41 |
The reaction conditions 5 are as follows: the molar ratio of ammonia to hydrogen was 2.5: 1, as circulating gas, the pressure is kept at 0.3Mpa, the reaction temperature is 270 ℃, the feeding amount is 90ml/h, and the obtained experimental data are as follows:
| water (W) | Cyclohexylamine | Cyclohexanol derivatives | Dicyclohexylamine |
| 18.13 | 80.18 | 0.24 | 1.43 |
The reaction conditions 6 are as follows: the molar ratio of ammonia to hydrogen was 2.5: 1, as a circulating gas, keeping the pressure at 1.8Mpa, the reaction temperature at 270 ℃, the feeding amount at 90ml/h, and obtaining experimental data as follows:
| water (I) | Cyclohexylamine | Cyclohexanol | Dicyclohexylamine |
| 18.11 | 80.19 | 0.27 | 1.45 |
The reaction conditions 7 were: the molar ratio of ammonia to hydrogen is 1: 3.5, as the circulating gas, the pressure is kept at 1.8Mpa, the reaction temperature is 270 ℃, the feeding amount is 90ml/h, and the obtained experimental data are as follows:
| water (W) | Cyclohexylamine | Cyclohexanol | Dicyclohexylamine |
| 18.11 | 1.32 | 0.34 | 80.21 |
The reaction conditions 8 were: the molar ratio of ammonia to hydrogen is 1: 3.5, as the circulating gas, the pressure is kept at 1.8Mpa, the reaction temperature is 220 ℃, the feeding amount is 90ml/h, and the obtained experimental data are as follows:
| water (W) | Cyclohexylamine | Cyclohexanol | Dicyclohexylamine |
| 18.09 | 1.31 | 0.33 | 80.26 |
The reaction conditions 9 were: the molar ratio of ammonia to hydrogen is 1: 3.5, as the circulating gas, the pressure is kept at 1.2Mpa, the reaction temperature is 150 ℃, the feeding amount is 90ml/h, and the obtained experimental data are as follows:
| water (W) | Cyclohexylamine | Cyclohexanol | Dicyclohexylamine |
| 18.10 | 1.33 | 0.30 | 80.25 |
Wherein, the experimental effect is not changed much after the cyclohexanol in the raw material is changed into cyclohexanone, the conversion rate of cyclohexylamine is more than 97%, and cyclohexanone is completely converted into cyclohexanol in the reaction.
Example 2
The catalyst comprises the following components: 40% of Co, 5% of Ni, 13% of Mg, 15% of Cu, 10% of Zn and the balance of Al 2 O 3 The reaction conditions 1 of example 1 were repeated, and the conversion of cyclohexylamine was 97% or more.
Example 3
The catalyst comprises the following components: 3% of Co, 50% of Ni, 13% of Mg, 10% of Cu, 15% of Zn and the balance of Al 2 O 3 The reaction conditions 1 of example 1 were repeated, and the conversion of cyclohexylamine was 97% or more.
Example 4
The catalyst comprises the following components: 5% of Co, 5% of Ni, 13% of Mg, 35% of Cu, 20% of Zn and the balance of Al 2 O 3 The reaction conditions 1 of example 1 were repeated, and the conversion of cyclohexylamine was 97% or more.
Example 5
The catalyst comprises the following components: 10% of Co, 5% of Ni, 13% of Mg, 5% of Cu and 40% of Zn, the reaction conditions 1 in example 1 were repeated, and the conversion of cyclohexylamine was 97% or more.
Example 6
The catalyst comprises the following components: 0% of Co, 15% of Ni, 21% of Mg, 35% of Cu, 5% of Zn and the balance of Al 2 O 3 The reaction conditions 1 of example 1 were repeated, and the conversion of cyclohexylamine was 97% or more.
Example 7
The mixed product (mainly cyclohexylamine) of the reaction condition 1 in example 1 is mixed with cyclohexanol as a second raw material, wherein the molar ratio of cyclohexylamine to cyclohexanol is 1.1: 1, under the action of hydrogen and a catalyst (the same as the catalyst in example 1), the pressure of the circulating gas is kept at 3Mpa, the reaction temperature is 120 ℃, the feeding amount is 90ml/h, and the obtained experimental data are as follows:
| water (W) | Cyclohexylamine | Cyclohexanol | Dicyclohexylamine |
| 26.20 | 0.91 | 5.70 | 67.19 |
Therefore, the mixed product and the first raw material are further synthesized into the dicyclohexylamine under the action of the hydrogen and the catalyst. But not limited to cyclohexanol, cyclohexanone may also be used as the first starting material,
from examples 1 to 6, the conversion rate of the prepared cyclohexylamine, whether cyclohexanol or cyclohexanone is used as a raw material, is more than 96% by applying the cyclohexylamine preparation method of the present invention; the product proportion of the cyclohexylamine and the dicyclohexylamine is adjusted by the proportion of ammonia gas and hydrogen gas, and the selectivity of the cyclohexylamine and the dicyclohexylamine is over 96 percent.
The continuous operation of the examples 1 to 7 for 720 hours proves that the catalyst prepared by the process has longer service life and is suitable for industrial production, and the conversion rate of raw materials and the selectivity of products are not changed greatly.
When the catalyst carriers of examples 1 to 7 were replaced with silica and alumina silica mixed in an arbitrary ratio, the conversion ratio of the raw material and the selectivity of the product were not greatly changed.
Referring to the reaction formulas 1 and 2, in the present invention, the reaction amount of ammonia is adjusted by adjusting the ratio of ammonia to hydrogen, and it can be seen that the generation rate of cyclohexylamine is relatively high when the ratio of ammonia is relatively high.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for synthesizing cyclohexylamine, which is characterized in that the method comprises the following steps:
under the action of catalyst, the first material, ammonia gas and hydrogen gas are mixed to obtain mixed product, said mixed product includes cyclohexylamine and dicyclohexylamine,
wherein the first feedstock comprises cyclohexanone, cyclohexanol, or a combination thereof.
2. The synthesis method according to claim 1, characterized in that the ratio of cyclohexylamine and dicyclohexylamine in the product is adjusted by controlling the ratio of ammonia to hydrogen;
the molar ratio of ammonia to hydrogen is 1: when the reaction temperature is 2.5-4.0, the product is mainly dicyclohexylamine;
the mol ratio of ammonia to hydrogen is 1.5-4.5: when 1, the product is mainly cyclohexylamine.
3. The method of synthesis according to claim 1,
and synthesizing the mixed product and the first raw material into the dicyclohexylamine under the action of hydrogen and a catalyst.
4. The method of synthesis according to claim 1, characterized in that it uses a gas-solid phase reaction:
feeding the first raw material and cyclohexylamine into a preheating gasifier, mixing the first raw material and the cyclohexylamine with ammonia gas and hydrogen gas, preheating and gasifying to obtain a first mixed gas;
after entering a fixed bed reactor, maintaining the pressure by using hydrogen and ammonia gas, and reacting the first mixed gas under the action of a catalyst to obtain a mixed product;
cooling the mixed product gas, and performing gas-liquid separation to obtain a mixed solution;
and rectifying and purifying the mixed solution to obtain the dicyclohexylamine and the cyclohexylamine.
5. The synthesis method according to claim 4, characterized in that the hydrogen obtained by gas-liquid separation is pressurized by a recycle compressor and returned to the preheated gasifier for recycling.
6. The synthesis method according to claim 1, characterized in that the catalyst comprises:
0-50 wt% of Co, 0-55 wt% of Ni, 0-35 wt% of Mg, 0-60 wt% of Cu, 0-45 wt% of Zn and a carrier, wherein the carrier comprises alumina, silicon dioxide or a combination of the alumina and the silicon dioxide.
7. The synthesis method according to claim 6, characterized in that the catalyst comprises: 0-40 wt% of Co, 5-50 wt% of Ni, 3-21 wt% of Mg, 5-30 wt% of Cu and 5-40 wt% of Zn;
the preparation method of the catalyst comprises the following steps:
mixing Al (OH) 3 Preparing sodium metaaluminate solution by NaOH;
neutralizing and precipitating sodium metaaluminate solution with nitric acid, aging, filtering, washing, rolling ball molding, drying, and roasting to obtain spherical Al with diameter of 3-20mm 2 O 3 A carrier;
preparing mixed solution of nitrates of Co, Ni, Mg, Cu and Zn according to a certain proportion, and adding Al 2 O 3 Impregnating the carrier;
impregnating Al 2 O 3 Drying the carrier and then roasting at high temperature to obtain a crude catalyst;
and (3) carrying out hydrogen reduction on the crude catalyst to obtain the catalyst.
8. The synthesis process of claim 7, wherein the crude catalyst is reduced under the following conditions:
hydrogen gas under 0.05MPa pressure, 460 ℃ temperature and airspeed of 1000h -1 Reducing for 24 hours under the condition.
9. A synthesis process according to any one of claims 1 to 8, characterised in that the first feedstock feed is in the range 45 to 90 ml/hour per litre of catalyst.
10. The synthesis method according to claim 1, wherein the synthesis conditions are as follows: ammonia and hydrogen are used for maintaining the pressure of 0.05-3 Mpa and the temperature of 150-300 ℃.
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| CN116836064A (en) * | 2023-05-15 | 2023-10-03 | 湖南师范大学 | Novel method for synthesizing cyclohexylamine by directly hydroamination of cyclohexyl acetate |
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