CN114805119B - Method for preparing 6-aminocapronitrile by liquid-phase ammoniation and dehydration of caprolactam - Google Patents
Method for preparing 6-aminocapronitrile by liquid-phase ammoniation and dehydration of caprolactam Download PDFInfo
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- CN114805119B CN114805119B CN202210566567.XA CN202210566567A CN114805119B CN 114805119 B CN114805119 B CN 114805119B CN 202210566567 A CN202210566567 A CN 202210566567A CN 114805119 B CN114805119 B CN 114805119B
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- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 title claims abstract description 128
- KBMSFJFLSXLIDJ-UHFFFAOYSA-N 6-aminohexanenitrile Chemical compound NCCCCCC#N KBMSFJFLSXLIDJ-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000006297 dehydration reaction Methods 0.000 title claims abstract description 18
- 239000007791 liquid phase Substances 0.000 title claims abstract description 17
- 230000018044 dehydration Effects 0.000 title claims abstract description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000003054 catalyst Substances 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 33
- 239000002608 ionic liquid Substances 0.000 claims abstract description 11
- 239000012071 phase Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 20
- 239000003085 diluting agent Substances 0.000 claims description 7
- 238000004176 ammonification Methods 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 5
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ISBHMJZRKAFTGE-UHFFFAOYSA-N pent-2-enenitrile Chemical compound CCC=CC#N ISBHMJZRKAFTGE-UHFFFAOYSA-N 0.000 description 1
- PMOIAJVKYNVHQE-UHFFFAOYSA-N phosphanium;bromide Chemical compound [PH4+].[Br-] PMOIAJVKYNVHQE-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 239000011829 room temperature ionic liquid solvent Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Other In-Based Heterocyclic Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for preparing 6-aminocapronitrile by liquid-phase ammoniation dehydration of caprolactam, which comprises the steps of reacting liquid-phase caprolactam with ammonia in the presence of a quaternary phosphine-phosphotungstic acid ionic liquid catalyst, and carrying out ammoniation dehydration to obtain 6-aminocapronitrile. Compared with the gas-phase ammoniation dehydration reaction of caprolactam, the invention reduces the reaction temperature, improves the reaction pressure and can improve the production capacity of the reactor by 3-5 times in unit volume; the single pass conversion rate of caprolactam reaches 50% -60%, the selectivity of 6-aminocapronitrile reaches more than 98%, and the catalyst can be recycled.
Description
Technical Field
The invention belongs to the technical field of organic chemical industry, and relates to a method for preparing 6-aminocapronitrile by liquid-phase ammoniation and dehydration of caprolactam.
Background
6-aminocapronitrile is an important chemical intermediate that can be used to produce 1, 6-hexamethylenediamine by complete hydrogenation, while 1, 6-hexamethylenediamine can be used to produce polymeric nylon 66. The preparation of 6-aminocapronitrile is currently mainly obtained by partial hydrogenation of 1, 6-adiponitrile, as in patent CN 1238334C, CN 101309897B, or by hydroformylation of pentenenitrile, as in patent CN1100752C.
CN107739318A provides a method and apparatus for preparing 6-aminocapronitrile by using a caprolactam liquid phase method, wherein the method for preparing 6-aminocapronitrile by using a caprolactam liquid phase method uses caprolactam as a raw material, and comprises the following steps: s1: mixing caprolactam, an organic solvent and a catalyst according to a certain mass ratio to obtain a mixed solution, adding the mixed solution into a reaction kettle, and stirring and heating the mixed solution; s2: when the mixed solution in the step S1 reaches a certain temperature, introducing ammonia gas into the mixed solution for reaction; s3: and (2) rectifying and purifying the reaction product after the reaction in the step (S2) to obtain the pure 6-aminocapronitrile. However, this method is not practical because of poor reproducibility. And phosphoric acid or phosphate is used as a catalyst and adiponitrile is used as a solvent, equipment corrosion is easy to cause, the catalyst cannot be recycled, and the post-treatment process is long.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a method for preparing 6-aminocapronitrile by liquid-phase ammonia dehydration of caprolactam.
The technical scheme of the invention is as follows: a method for preparing 6-aminocapronitrile by liquid-phase ammoniation dehydration of caprolactam comprises the steps of reacting liquid-phase caprolactam with ammonia in the presence of a quaternary phosphine-phosphotungstic acid ionic liquid catalyst, and carrying out ammoniation dehydration to obtain 6-aminocapronitrile.
The quaternary phosphine-phosphotungstic acid ionic liquid is [ P (C) n H 2n+1 )(C m H 2m+1 ) 3 ］ x -H 3-x P 12 W 12 O 40 Or [ P (C) m H 2m+1 ) 4 ］ x -H 3-x P 12 W 12 O 40 Where n=10-20, m=4-8,x =1-3, preferably [ P (C) n H 2n+1 )(C m H 2m+1 ) 3 ］ 2 -HP 12 W 12 O 40 Or [ P (C) n H 2n+1 )(C m H 2m+1 ) 3 ］-H 2 P 12 W 12 O 40 More preferably [ P (C) n H 2n+1 )(C m H 2m+1 ) 3 ］-H 2 P 12 W 12 O 40 Wherein n=8-14, m=4-6, and the mass ratio of catalyst to caprolactam in the reaction system is (0.01-0.03): 1.
the ammonification dehydration reaction process conditions are as follows: the reaction temperature is 200-300 ℃, preferably 250-280 ℃; the reaction pressure is 0MPa to 1.0 MPa, preferably 0.3MPa to 0.5 MPa; the stirring speed is 500-1500r/min.
The reaction can be carried out by adding a diluent, wherein the diluent can be nitrile substances, the diluent is preferably 6-aminocapronitrile, and the mass ratio of 6-aminocapronitrile to caprolactam is= (1-5): 1, preferably (2-3): 1.
the ammonia enters the reactor in a gas phase mode, the gas ammonia is added in a continuous mode, caprolactam, a diluent and a catalyst are mixed and then are also added in a continuous mode, and the molar ratio of the ammonia to the caprolactam is= (2-20): 1, preferably (5-8): 1, the residence time of the reactants in the reactor is 30min-300min.
The caprolactam, the diluent and the catalyst are added at one time, ammonia continuously enters the reactor in a gas phase mode, and the gas ammonia adding speed is controlled to be 20-200 min.
The ionic liquid is used as an emerging environment-friendly solvent and catalyst with wide application prospect, has the characteristics of non-volatilization and stability to water and air, and the preparation method has the advantages of low reaction temperature, cyclic utilization of the catalyst and the like by taking the quaternary phosphine-phosphotungstic acid room-temperature ionic liquid as the catalyst and taking caprolactam as the raw material liquid phase method for preparing the 6-aminocapronitrile.
The preparation of the ionic liquid catalyst can refer to a synthesis method in the 'application chemistry' 31 st volume 4 th phase 'of the ionic liquid at room temperature for synthesizing quaternary phosphine-phosphotungstic acid and photocatalytic degradation rhodamine B', the quaternary phosphine salt (10 mL of methanol is dissolved) and the phosphotungstic acid (10 mL of water is dissolved), after the quaternary phosphine salt and the phosphotungstic acid are completely dissolved, the phosphotungstic acid solution is slowly dripped into the quaternary phosphine salt solution according to the corresponding molar ratio (1:1, 2:1 and 3:1), white precipitate is gradually generated, and stirring is carried out for 2h, so that the precipitate is complete. The precipitate is obtained by filtration, washed 3 times with methanol and deionized water respectively, dried for 5 hours at 40 ℃ and characterized. The compounds are named by the means of quaternary phosphonium salts + phosphotungstates, such as using tetradecyltriahexyl phosphine bromide ([ P (C) 14 H 29 )(C 6 H 13 ) 3 Br) and phosphotungstic acid (H) 3 PW 12 O 40 ) The particle liquid prepared in a molar ratio of 3:1 was designated [ P (C) 14 H 29 )(C 6 H 13 ) 3 ］ 3 -PW 12 O 40 Other ionic liquids are similarly named.
Features and effects of the invention
1. According to the invention, the quaternary phosphine-phosphotungstic acid ionic liquid is used as a catalyst, and the caprolactam is subjected to liquid-phase ammoniation dehydration to prepare the 6-aminocapronitrile, so that compared with the caprolactam subjected to gas-phase ammoniation dehydration reaction, the reaction temperature is reduced, the reaction pressure is improved, and the unit volume production capacity of the reactor can be improved by 3-5 times.
2. The single pass conversion rate of caprolactam reaches 50% -60%, and the selectivity of 6-aminocapronitrile reaches more than 98%.
3. The catalyst can be recycled.
4、［P(C n H 2n+1 )(C m H 2m+1 ) 3 ］-H 2 P 12 W 12 O 40 Has better effect, and after 15 times of application, the conversion rate of caprolactam is 55 percent, and the selectivity of 6-aminocapronitrile is 98 percent.
Detailed Description
The invention will be further illustrated by the following examples, but the invention is not limited to these examples.
Example 1: in [ P (C6H) 13 ) 4 ］ 3 -P 12 W 12 O 40 Preparation of 6-aminocapronitrile for catalyst
Catalyst [ P (C6H) 13 ) 4 ］ 3 -P 12 W 12 O 40、 Caprolactam and 6-aminocapronitrile according to the mass ratio of 0.03:1:3, adding the mixture into a stirring reactor, heating the mixture to a temperature of 280-300 ℃ so that the molar ratio of ammonia to caprolactam is 10:1 total proportion, controlling the uniform adding speed of the gas ammonia, controlling the adding time of the gas ammonia to be 150min, controlling the reaction pressure to be 0.3MPa-0.5 MPa, stirring the reactor at a speed of 1000r/min, and continuing the reaction for 50min after the gas ammonia is added.
Test results: the caprolactam conversion rate is 35%, and the 6-aminocapronitrile selectivity is 80%.
Example 2 in [ P (C) 14 H 29 )(C 6 H 13 ) 3 ］ 3 - P 12 W 12 O 40 Preparation of 6-aminocapronitrile for catalyst
Catalyst [ P (C) 14 H 29 )(C 6 H 13 ) 3 ］ 3 - P 12 W 12 O 40、 Caprolactam and 6-aminocapronitrile according to the mass ratio of 0.03:1:3, adding the mixture into a stirring reactor, heating the mixture to a temperature of 280-300 ℃ so that the molar ratio of ammonia to caprolactam is 10:1 total proportion, controlling the uniform adding speed of the gas ammonia, the adding time of the gas ammonia is 150min, and reactingThe pressure is controlled to be 0.3MPa to 0.5 MPa, the stirring speed of the reactor is 1000r/min, and the reaction is continued for 50min after the gas ammonia is added.
Test results: caprolactam conversion 40%, 6-aminocapronitrile selectivity 83%.
Example 3 in [ P (C) 14 H 29 )(C 6 H 13 ) 3 ］ 2 -H P 12 W 12 O 40 Preparation of 6-aminocapronitrile for catalyst
Catalyst [ P (C) 14 H 29 )(C 6 H 13 ) 3 ］ 2 -H P 12 W 12 O 40、 Caprolactam and 6-aminocapronitrile according to the mass ratio of 0.03:1:3, adding the mixture into a stirring reactor, heating the mixture to a temperature of 280-300 ℃ so that the molar ratio of ammonia to caprolactam is 10:1 total proportion, controlling the uniform adding speed of the gas ammonia, controlling the adding time of the gas ammonia to be 150min, controlling the reaction pressure to be 0.3MPa-0.5 MPa, stirring the reactor at a speed of 1000r/min, and continuing the reaction for 50min after the gas ammonia is added.
Test results: caprolactam conversion was 50% and 6-aminocapronitrile selectivity was 90%.
Example 4 in [ P (C) 14 H 29 )(C 6 H 13 ) 3 ］-H 2 P 12 W 12 O 40 Preparation of 6-aminocapronitrile for catalyst
Catalyst [ P (C) 14 H 29 )(C 6 H 13 ) 3 ］-H 2 P 12 W 12 O 40、 Caprolactam and 6-aminocapronitrile according to the mass ratio of 0.03:1:3, adding the mixture into a stirring reactor, heating the mixture to a temperature of 280-300 ℃ so that the molar ratio of ammonia to caprolactam is 10:1 total proportion, controlling the uniform adding speed of the gas ammonia, controlling the adding time of the gas ammonia to be 150min, controlling the reaction pressure to be 0.3MPa-0.5 MPa, stirring the reactor at a speed of 1000r/min, and continuing the reaction for 50min after the gas ammonia is added.
Test results: caprolactam conversion was 60% and 6-aminocapronitrile selectivity was 95%.
Example 5 in [ P (C) 14 H 29 )(C 6 H 13 ) 3 ］-H 2 P 12 W 12 O 40 Continuous preparation of 6-aminocapronitrile for catalyst
Catalyst [ P (C) 14 H 29 )(C 6 H 13 ) 3 ］-H 2 P 12 W 12 O 40 Caprolactam and 6-aminocapronitrile according to the mass ratio of 0.03:1:3 mixing, heating to 200 ℃ by a preheater, and adding into a stirring reactor at uniform speed in a continuous mode, wherein the molar ratio of ammonia to caprolactam is 10:1 total proportion is controlled to be added into a stirring reactor at uniform speed, and the temperature of the stirring reactor is controlled to be 280-300 ℃. Catalyst [ P (C) 14 H 29 )(C 6 H 13 ) 3 ］-H 2 P 12 W 12 O 40、 Simultaneously adding caprolactam, 6-aminocapronitrile and ammonia, and finishing the addition at the same time, wherein the addition time is controlled to be 100-200 min; the reaction pressure is controlled to be 0.3MPa-0.5 MPa, and the stirring speed of the reactor is 1000r/min.
Test results: caprolactam conversion 58% and 6-aminocapronitrile selectivity 96%.
Example 6 in [ P (C) 14 H 29 )(C 6 H 13 ) 3 ］-H 2 P 12 W 12 O 40 Continuous preparation of 6-aminocapronitrile for catalyst
Catalyst [ P (C) 14 H 29 )(C 6 H 13 ) 3 ］-H 2 P 12 W 12 O 40 Caprolactam and 6-aminocapronitrile according to the mass ratio of 0.03:1:2, mixing, heating to 200 ℃ through a preheater, and adding the mixture into a stirring reactor at uniform speed in a continuous mode, wherein the molar ratio of ammonia to caprolactam is 5:1 total proportion is controlled to be added into a stirring reactor at uniform speed, and the temperature of the stirring reactor is controlled to be 280-300 ℃. Catalyst [ P (C) 14 H 29 )(C 6 H 13 ) 3 ］-H 2 P 12 W 12 O 40、 Simultaneously adding caprolactam, 6-aminocapronitrile and ammonia, and finishing the addition at the same time, wherein the addition time is controlled to be 100-200 min; the reaction pressure is controlled to be 0.3MPa-0.5 MPa, and the stirring speed of the reactor is 1500r/min.
Test results: caprolactam conversion was 60% and 6-aminocapronitrile selectivity was 98%.
The caprolactam conversion is calculated as (moles of caprolactam before single pass reaction-moles of caprolactam after single pass reaction)/moles of caprolactam before single pass reaction;
the selectivity of 6-aminocapronitrile is calculated as moles of 6-aminocapronitrile produced after a single pass/(moles of caprolactam before a single pass-moles of caprolactam after a single pass).
Example 7 [ P (C) 14 H 29 )(C 6 H 13 ) 3 ］-H 2 P 12 W 12 O 40 The catalyst can be recycled
The reaction solution prepared in example 6 was distilled to separate 6-aminocapronitrile, caprolactam and catalyst [ P (C) 14 H 29 )(C 6 H 13 ) 3 ］-H 2 P 12 W 12 O 40 The catalyst isolated was tested for preparation of 6-aminocapronitrile under the conditions of example 6.
Test results: after 15 times of application of the catalyst, the caprolactam conversion rate is 55%, and the selectivity of 6-aminocapronitrile is 98%.
Example 8 [ P (C) 14 H 29 )(C 6 H 13 ) 3 ］ 2 -HP 12 W 12 O 40 The catalyst can be recycled
The reaction solution prepared in example 3 was distilled to separate 6-aminocapronitrile, caprolactam and catalyst [ P (C) 14 H 29 )(C 6 H 13 ) 3 ］ 2 -HP 12 W 12 O 40 The catalyst isolated was tested for preparation of 6-aminocapronitrile under the conditions of example 3.
Test results: after 10 times of application of the catalyst, the conversion rate of caprolactam is 47%, and the selectivity of 6-aminocapronitrile is 88%.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (4)
1. A method for preparing 6-aminocapronitrile by liquid-phase ammoniation and dehydration of caprolactam, which comprises the steps of reacting liquid-phase caprolactam with ammonia in the presence of a quaternary phosphine-phosphotungstic acid ionic liquid catalyst, and carrying out ammoniation and dehydration to obtain 6-aminocapronitrile;
the method is characterized in that:
the quaternary phosphine-phosphotungstic acid ionic liquid is [ P (C) n H 2n+1 )(C m H 2m+1 ) 3 ］H 2 P 12 W 12 O 40 Wherein n=8-14, m=4-6;
the reaction is carried out by adding into thinner, which is 6-aminocapronitrile, the mass ratio of 6-aminocapronitrile to caprolactam is = (2-3) 1;
the ammonification dehydration reaction process conditions are as follows: the reaction temperature is 280-300 ℃ and the reaction pressure is 0.3-0.5 MPa; the stirring speed is 500-1500r/min.
2. The method for preparing 6-aminocapronitrile by liquid-phase ammoniation and dehydration of caprolactam according to claim 1, which is characterized in that the mass ratio of the quaternary phosphine-phosphotungstic acid ionic liquid catalyst to caprolactam is (0.01-0.03): 1.
3. the method for preparing 6-aminocapronitrile by liquid-phase ammonification and dehydration of caprolactam according to claim 1, wherein ammonia is fed into the reactor in a gas-phase continuous mode, caprolactam, diluent and catalyst are mixed and then are added in a continuous mode, and the molar ratio of ammonia to caprolactam is = (2-20): 1, the residence time of the reactants in the reactor is 30min-300min.
4. The method for preparing 6-aminocapronitrile by liquid-phase ammoniation and dehydration of caprolactam according to claim 1, which is characterized in that caprolactam, a diluent and a catalyst are added at one time, ammonia continuously enters a reactor in a gas phase mode, and the adding time of the gas ammonia is controlled to be 20min-200min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CA2259941A1 (en) * | 1996-08-03 | 1998-02-12 | Basf Aktiengesellschaft | Manufacturing process for 6-aminocapronitrile |
| US6121481A (en) * | 1996-08-03 | 2000-09-19 | Basf Aktiengesellschaft | Process for preparing 6-aminocapronitrile |
| CN107739318A (en) * | 2017-10-11 | 2018-02-27 | 中国天辰工程有限公司 | A kind of caprolactam liquid phase method prepares the method and device of 6 amino-capronitriles |
| CN110404582A (en) * | 2019-08-21 | 2019-11-05 | 中触媒新材料股份有限公司 | A kind of preparation method of the catalyst for caprolactam ammonification |
| CN113402418A (en) * | 2021-07-07 | 2021-09-17 | 北京旭阳科技有限公司 | Method for preparing 6-aminocapronitrile |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2259941A1 (en) * | 1996-08-03 | 1998-02-12 | Basf Aktiengesellschaft | Manufacturing process for 6-aminocapronitrile |
| US6121481A (en) * | 1996-08-03 | 2000-09-19 | Basf Aktiengesellschaft | Process for preparing 6-aminocapronitrile |
| CN107739318A (en) * | 2017-10-11 | 2018-02-27 | 中国天辰工程有限公司 | A kind of caprolactam liquid phase method prepares the method and device of 6 amino-capronitriles |
| CN110404582A (en) * | 2019-08-21 | 2019-11-05 | 中触媒新材料股份有限公司 | A kind of preparation method of the catalyst for caprolactam ammonification |
| CN113402418A (en) * | 2021-07-07 | 2021-09-17 | 北京旭阳科技有限公司 | Method for preparing 6-aminocapronitrile |
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